WO1997004148A1 - Fibres de cellulose - Google Patents

Fibres de cellulose Download PDF

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Publication number
WO1997004148A1
WO1997004148A1 PCT/AT1996/000131 AT9600131W WO9704148A1 WO 1997004148 A1 WO1997004148 A1 WO 1997004148A1 AT 9600131 W AT9600131 W AT 9600131W WO 9704148 A1 WO9704148 A1 WO 9704148A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
solution
carbamate
fiber
cellulose carbamate
Prior art date
Application number
PCT/AT1996/000131
Other languages
German (de)
English (en)
Inventor
Jörg Schlangen
Original Assignee
Lenzing Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lenzing Aktiengesellschaft filed Critical Lenzing Aktiengesellschaft
Priority to AU63480/96A priority Critical patent/AU6348096A/en
Publication of WO1997004148A1 publication Critical patent/WO1997004148A1/fr

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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/22—Cellulose xanthate
    • 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
    • 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

Definitions

  • the invention relates to a process for the production of modified viscose fibers by mixing a solution of cellulose carbamate with a solution of cellulose xanthate, spinning the resulting mixed solution and precipitating the solution in one or more precipitation baths and modified viscose fibers with increased crimp and increased water retention capacity, which can be obtained by the process are.
  • cellulosic fibers from cellulose carbamate, a cellulose derivative produced by reacting the cellulose with urea is a known technology and has been used e.g. in US-A 2, 134,825.
  • the solvent used to prepare the cellulose carbamate solution is usually a dilute alkali hydroxide solution.
  • the cellulose carbamate solution is spun at low temperatures and in acidic precipitation baths, e.g. contain dilute sulfuric acid, precipitated into fibers.
  • modified viscose fibers by adding solutions of cellulose carbamate to a solution of cellulose xanthate (viscose) and spinning the resulting mixed solution.
  • a method and modified viscose fibers thus produced are e.g. in the Polish patent application PL-AI 293243.
  • the weight ratio of the cellulose regenerated from the cellulose xanthate and the cellulose carbamate should be 99: 1 to 1:99 and preferably 60:40 to 10:90.
  • the cellulose carbamate solution used should not contain more than 15% by weight of cellulose carbamate, preferably 6 to 10% by weight of cellulose carbamate.
  • the nitrogen content of the cellulose carbamate used which is a measure of the degree of substitution of the cellulose with the carbamate group, should be between 0.5% by weight and 4.5% by weight.
  • the mixed solution of viscose and cellulose carbamate solution produced according to this publication is spun according to known methods of viscose fiber technology. Fibers produced in this way have an increased water retention capacity and an increased strength with an increasing proportion of cellulose carbamate.
  • the object of the present invention is to provide conditions for the production of modified viscose fibers with excellent properties in the known process for the production of modified viscose fibers from a mixed solution of viscose and a solution of cellulose carbamate.
  • the weight ratio of cellulose carbamate to cellulose xanthate in the mixed solution is from 2: 100 to 9: 100, preferably from 5: 100 to 8: 100.
  • Modified viscose fibers like standard viscose fibers, have essentially arcuate deviations from the longitudinal direction. When relaxing a completely stretched fiber, this in turn forms these deviations from the longitudinal state, which is noticeable in a change in length. If one measures the change in length when relaxing a completely stretched but not yet stretched fiber and divides this value by the length of the completely stretched fiber, the value obtained is called the crimp of the fiber.
  • the value obtained is called the crimping of the fiber.
  • the measured uncrimping of a fiber is usually higher than the measured crimping, since an already stretched fiber can no longer form the full crimp of the originally completely relaxed state when it is relaxed.
  • High crimp values of the fiber particularly facilitate the processability at subsequent stages of fiber processing, for example carding and other steps.
  • the further increase in the water retention capacity of the modified viscose fibers produced by the process according to the invention is particularly surprising since it is known from the prior art that the best values in relation to the water retention capacity of modified viscose fibers are achieved with the highest possible cellulose carbamate contents.
  • the water retention of the modified fibers also increases with increasing carbamate concentration, but excellent water retention and crimp values are achieved at a very low weight ratio of cellulose carbamate to cellulose xanthate and within a relatively narrow range of this weight ratio.
  • the water retention capacity indicates the amount of moisture fibers can absorb in a short time when they are soaked with water. The determined
  • the amount of water is essentially between the individual fibers. This property is naturally essential for the applicability of the fiber in woven or non-woven textiles, e.g. be used in hygiene articles or other areas of application for absorbing large quantities of liquid certain products.
  • the water retention capacity also called swelling value
  • WV water retention capacity
  • cellulose carbamate in a weight ratio of 5: 100 to 8: 100 to the cellulose xanthate present in the mixed solution has proven to be particularly advantageous.
  • the method according to the invention is advantageously designed such that a cellulose carbamate solution with a cellulose carbamate concentration of 4% by weight to 5% by weight is used. It has been shown that when cellulose carbamate solutions with the cellulose carbamate content provided according to the invention are used, the spinning security when spinning the resulting mixed solution increases by leaps and bounds compared to cellulose carbamate solutions which were produced according to the prior art with higher concentrations of cellulose carbamate. Increased spinning safety is expressed in a consistently low pressure in front of the spinneret and in the absence of thread breaks in the precipitation bath.
  • the cellulose carbamate used can have a nitrogen content of 0.5% by weight to 5% by weight.
  • the temperature of the solution of cellulose xanthate can advantageously be up to 15 ° C. before mixing with the cellulose carbamate solution.
  • the solution when using a cellulose carbamate solution with a cellulose carbamate concentration of 4% by weight to 5% by weight, the solution can also be processed at temperatures higher than 5 ° C. It is even possible to use viscose with a temperature of up to 15 ° C for mixing with the cellulose carbamate solution. Since the viscose in the mixed solution is always present in a large excess in the process according to the invention, the economics of the process can be increased considerably since the viscose, which is already kept to lower temperatures of around 20 ° C. for so-called maturation, is not significantly further must be cooled.
  • the ripeness of the viscose used is preferably less than 12 ° Ho (Hottenroth), preferably 8 ° Ho to 10 ° Ho.
  • Hottenroth number describes the colloidal chemical maturity of viscose, i.e. the coagulability of the viscose through electrolyte solutions.
  • the viscose is subjected to post-ripening before spinning, in which a decrease in the degree of substitution by the xanthate groups and changes in viscosity occur.
  • Different degrees of ripeness can be set in the viscose by controlling the duration and the conditions of the maturation.
  • a further advantageous embodiment of the present invention is characterized in that the cellulose carbamate is completely decomposed to cellulose during the aftertreatment of the fiber.
  • a further advantageous embodiment of the invention is characterized in that at least one non-ionic surfactant is added to the mixed solution in a concentration of 0.2% by weight to 1% by weight.
  • the addition of surfactants to the spinning solution is known from the standard viscose process to reduce the mutual sticking of spun fibers and thus to increase the spinning safety.
  • the addition of surfactants surprisingly brings about a further increase in the ripple values and the water holding capacity, advantageous effects being observed in particular in the case of surfactants with a nonionic character.
  • the present invention furthermore relates to a modified viscose fiber which can be obtained by the process according to the invention.
  • Modified viscose fibers according to the invention have, inter alia, a crimp of at least 5.5% and a crimp of at least 10%.
  • the modified viscose fibers according to the invention also have a water holding capacity of up to 30 g H2 ⁇ / g fiber.
  • the fibers can be produced by known measures such as changes in the spinneret hole diameter or the draw-off in different titer ranges, the weight ratio of cellulose carbamate provided by the invention increasing
  • Cellulose xanthate in the mixed solution caused increases in water retention and crimp in both fine-titer fibers with a titer of e.g. 1.7 dtex and fibers with a larger titer can be observed.
  • the modified viscose fibers according to the present invention further unexpectedly have an increased fibrillation tendency compared to standard viscose fibers.
  • Fibrillation of cellulosic fibers is understood to mean the splitting off of fibrils transversely to the longitudinal direction of the fiber when the fiber is mechanically stressed in the moist state. While practically no tendency to fibrillation can be observed with conventional viscose fibers, the modified viscose fibers according to the invention show a slightly increased tendency to fibrillation, which is advantageous for numerous fields of application, for example in non-woven textile fabrics.
  • the cellulose carbamate solutions used for the experiments were prepared in a known manner by dissolving the cellulose carbamate in dilute aqueous sodium hydroxide. An alkali content of about 9% by weight was set in the solutions. A cellulose carbamate with a nitrogen content of 2.9% by weight was used. The amount of cellulose carbamate required to achieve the desired concentration in the solution was first mixed with the corresponding amount of water at a temperature of 5 ° C. and placed in the refrigerator for swelling for 30 minutes. The corresponding amount of 18% NaOH was then placed in a double-walled autoclave at 0 ° C. and the swollen carbamate was added in portions with stirring. The temperature must not rise above 10 ° C during this process. After a short time, a clear, almost colorless, viscous liquid is formed. This solution was stirred at a temperature of 3-5 ° C for 2 hours.
  • the mixed solution is made much easier if the cellulose carbamate solution is added to the viscose immediately before the fiber is spun out.
  • the cellulose carbamate solution was filtered through a cooled filter bowl (mesh size 3 ⁇ m) and mixed with the viscose in a homogenizer.
  • the mixed solution was spun using conventional viscose methods into a spinning bath corresponding to the conventional viscose method with approx. 95-110 g / 1 H2SO4, 335-345 g / 1 Na2SO4 and 16-18 g / 1 ZnSÜ4.
  • the after-treatment of the fibers spun in this way was carried out using the conventional methods of the viscose process.
  • the table shows that when setting a concentration of the
  • This example shows the influence of the weight ratio of cellulose carbamate to cellulose xanthate on the properties of the spun modified viscose fibers.
  • Modified viscose fibers were spun under the following spinning parameters while observing the above process steps and using a cellulose carbamate solution with a cellulose carbamate content of 4% by weight:
  • Approximately 0.5 g of the fiber is placed in a centrifugal vessel and the vessel is filled with an aqueous solution containing 1.5% by weight of a surfactant (Nekal BX, manufacturer BASF).
  • a surfactant Nakal BX, manufacturer BASF.
  • the filled vessel was left to stand for 2 hours and then centrifuged for 10 minutes at 3500 revolutions per minute.
  • the fibers were then weighed (gives measured value Ml), then dried at 105 ° C. for 16-18 hours and weighed again (gave measured value M2).
  • the source value is according to the formula
  • Fiber strength and fiber elongation in a conditioned state were tested in accordance with the BISFA regulation "Internationally agreed methods for testing viscose, modal, cupro, lyocell, acetate and triacetate stable fibers and tows", edition 1993. Determination of crimp and uncrimp:
  • the crimping of the fiber is understood to mean the difference in length between the fiber in the stretched (but not stretched) and relaxed state, based on the length in the stretched state:
  • the crimping is determined according to the measuring method described in AT-B 359.321 by gradually reducing the tension of a fiber clamped in a measuring apparatus and the lengths for the completely drawn fiber from the measured values obtained for the tension of the fiber and the length of the fiber and the completely relaxed fiber is extrapolated.
  • the uncrimping is determined by applying a voltage to the relaxed fiber until it is fully stretched (but not yet stretched), again the measured value being the difference between the lengths of the fully stretched or relaxed fiber, based on the length of the completely stretched fiber.
  • the measurement of the crimping of the fiber is also carried out, however in reverse order, according to the measuring method described in AT-B 359.321.
  • modified viscose fibers produced according to the invention were subjected to an otherwise constant alkaline treatment, with the aftertreatment remaining the same, whereby part or, in one example, virtually all carbamate groups were removed from the fiber.
  • the weight ratio of cellulose carbamate to cellulose xanthate was 8: 100 in these experiments.
  • the following table summarizes properties of the modified viscose fibers obtained in this way:
  • a modified viscose fiber produced according to the invention (weight ratio cellulose carbamate to cellulose xanthate in the mixed solution 5: 100) was analyzed in accordance with the method described in PCT-WO 94/24343 for assessing the tendency to fibrillation.
  • the modified viscose fiber had an average of 38 fibrils over a fiber length of 0.276 mm. With standard viscose fibers, practically no fibrils are observed after performing the same test.

Abstract

L'invention concerne un procédé de fabrication de fibres de viscose modifiée, selon lequel on mélange une solution de carbamate de cellulose avec une solution de xanthogénate de cellulose, on effectue le filage de la solution mélangée résultante et on précipite la solution dans un ou plusieurs bains de précipitation. Ce procédé est caractérisé en ce que, dans la solution mélangée, le rapport en poids entre le carbamate de cellulose et le xanthagénate de cellulose est de 2:100 à 9:100, de préférence de 5:100 à 8:100. La concentration en carbamate de cellulose dans la solution de carbamate de cellulose est comprise de préférence entre environ 4 % en poids et 5 % en poids. Les fibres de viscose modifiées fabriquées conformément à l'invention présentent une crispation en arrière de 5,5 % à 7 % et un défrisage de 10 % à 12 %. Le pouvoir de rétention d'eau des fibres de viscose modifiée conformes à l'invention peut atteindre 30 g/g.
PCT/AT1996/000131 1995-07-20 1996-07-18 Fibres de cellulose WO1997004148A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63480/96A AU6348096A (en) 1995-07-20 1996-07-18 Cellulose fibre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA1237/95 1995-07-20
AT123795A ATA123795A (de) 1995-07-20 1995-07-20 Verfahren zur herstellung von modifizierten viskosefasern und modifizierte viskosefaser

Publications (1)

Publication Number Publication Date
WO1997004148A1 true WO1997004148A1 (fr) 1997-02-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1996/000131 WO1997004148A1 (fr) 1995-07-20 1996-07-18 Fibres de cellulose

Country Status (3)

Country Link
AT (1) ATA123795A (fr)
AU (1) AU6348096A (fr)
WO (1) WO1997004148A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT513536A1 (de) * 2012-11-15 2014-05-15 Glanzstoff Bohemia S R O Verfahren zur Herstellung von zellulosischen Formkörpern
WO2014201484A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide à fort pouvoir absorbant et leur utilisation
WO2014201483A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide et leur procédé de production
US10030323B2 (en) 2013-04-05 2018-07-24 Lenzing Aktiengesellschaft Method for the production of polysaccharide fibers with an increased fibrillation tendency
WO2018137757A1 (fr) * 2017-01-24 2018-08-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé
US10196758B2 (en) 2013-06-18 2019-02-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for producing same
US10221502B2 (en) 2013-04-05 2019-03-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for the production thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
PL168080B1 (pl) * 1992-01-20 1995-12-30 Inst Wlokien Chem Modyfikowane włókna wiskozowe o podwyższonej sorpcji wilgoci i sposób wytwarzania modyfikowanych włókien wiskozowych o podwyższonej sorpcji wilgoci
CZ280948B6 (cs) * 1991-12-19 1996-05-15 Výskumný Ústav Chemických Vlákien, A.S. Spôsob prípravy tvarovaných článkov z derivátov celulózy

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CZ280948B6 (cs) * 1991-12-19 1996-05-15 Výskumný Ústav Chemických Vlákien, A.S. Spôsob prípravy tvarovaných článkov z derivátov celulózy
PL168080B1 (pl) * 1992-01-20 1995-12-30 Inst Wlokien Chem Modyfikowane włókna wiskozowe o podwyższonej sorpcji wilgoci i sposób wytwarzania modyfikowanych włókien wiskozowych o podwyższonej sorpcji wilgoci

Non-Patent Citations (3)

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Title
DATABASE WPI Week 9340, Derwent World Patents Index; AN 93-312231 *
STRUSZCYK H: "Cellulose fibers: state of the art and development forecast", CHEMICAL FIBERS INTERNATIONAL, vol. 46, no. 4, September 1996 (1996-09-01), FRANKFURT AM MAIN, D, pages 265 - 267, XP002020509 *
URBANOWSKI A: "Cellulose carbamate: a new raw material for the manufacture of cellulosic fibers", CHEMICAL FIBERS INTERNATIONAL, vol. 46, no. 4, September 1996 (1996-09-01), FRANKFURT AM MAIN, D, pages 260 - 262, XP002020508 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT513536A1 (de) * 2012-11-15 2014-05-15 Glanzstoff Bohemia S R O Verfahren zur Herstellung von zellulosischen Formkörpern
US10030323B2 (en) 2013-04-05 2018-07-24 Lenzing Aktiengesellschaft Method for the production of polysaccharide fibers with an increased fibrillation tendency
US10221502B2 (en) 2013-04-05 2019-03-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for the production thereof
WO2014201484A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide à fort pouvoir absorbant et leur utilisation
WO2014201483A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide et leur procédé de production
CN105705690A (zh) * 2013-06-17 2016-06-22 连津格股份公司 高吸收性多糖纤维及其用途
CN105745370A (zh) * 2013-06-17 2016-07-06 连津格股份公司 多糖纤维及其制备方法
CN105705690B (zh) * 2013-06-17 2018-12-14 连津格股份公司 高吸收性多糖纤维及其用途
US10220111B2 (en) 2013-06-17 2019-03-05 Lenzing Aktiengesellschaft Highly absorbent polysaccharide fiber and use thereof
CN105745370B (zh) * 2013-06-17 2020-12-08 杜邦工业生物科学美国有限责任公司 多糖纤维及其制备方法
US10196758B2 (en) 2013-06-18 2019-02-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for producing same
WO2018137757A1 (fr) * 2017-01-24 2018-08-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Solution de filage contenant du carbamate de cellulose et du xanthogénate de cellulose, procédé de fabrication de corps façonnés et corps façonnés fabriqués selon ce procédé

Also Published As

Publication number Publication date
AU6348096A (en) 1997-02-18
ATA123795A (de) 1997-02-15

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