EP1299583A1 - Method for producing cellulose fibres - Google Patents

Method for producing cellulose fibres

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Publication number
EP1299583A1
EP1299583A1 EP01944725A EP01944725A EP1299583A1 EP 1299583 A1 EP1299583 A1 EP 1299583A1 EP 01944725 A EP01944725 A EP 01944725A EP 01944725 A EP01944725 A EP 01944725A EP 1299583 A1 EP1299583 A1 EP 1299583A1
Authority
EP
European Patent Office
Prior art keywords
fibers
filaments
air
cellulose
temperature
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP01944725A
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German (de)
French (fr)
Other versions
EP1299583B1 (en
Inventor
Hartmut Rüf
Christoph Schrempf
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Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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Publication date
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to AT01944725T priority Critical patent/ATE269434T1/en
Publication of EP1299583A1 publication Critical patent/EP1299583A1/en
Application granted granted Critical
Publication of EP1299583B1 publication Critical patent/EP1299583B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • 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

Definitions

  • the invention relates to a method according to the preamble of patent claim 1.
  • “Lyocell” is the generic name given by BISFA (The International Bureau for the Standardization of man made fibers) for cellulose fibers which are produced by dissolving cellulose in an organic solvent without the formation of a derivative and extruding fibers from this solution.
  • An organic solvent is understood to mean a mixture of an organic chemical and water.
  • Such fibers are also known under the term “solvent-spun fibers”.
  • As an organic solvent N-methyl-morpholine-N-oxide is used today on a commercial scale.
  • PCT-WO 94/28218 describes a method similar to PCT-WO 93/19230. According to this document, the temperature of the cooling air should be kept below 50 ° C.
  • PCT-WO 95/02082 A method is known from PCT-WO 95/02082, according to which the spinning hole diameter, the spinning mass output per hole, the titer of the individual filament, the width of the air gap and the humidity of the air in the air gap are kept in certain ranges by means of a mathematical expression should be.
  • the temperature of the cooling air In the examples of PCT-WO 95/02082 there is no information about the temperature of the cooling air. In the Descriptions are generally temperatures between 10 ° C and 60 ° C, preferably between 20 ° C and 40 ° C.
  • PCT-WO 96/17118 deals with the moisture content of the cooling air.
  • the highest temperature of the cooling air specified in this document is 40 ° C.
  • the temperature of the cooling air can be 0 ° C to 40 ° C.
  • the temperature of the cooling air is given as -10 ° C to 50 ° C.
  • PCT-WO 98/58103 describes that with a large number of extruded filaments, i.e. when using spinnerets with a large number of spinning holes, a very humid climate is established in the air gap. In order to ensure the stability of the spinning process even under these conditions, it is proposed in PCT-WO 98/58103 that the spinning solution should contain a certain proportion of cellulose and / or another polymer with a higher molecular weight immediately before spinning.
  • a problem with spinning cellulose solutions in NMMO is that in solutions with a high viscosity the spinning solution has to be spun at elevated temperatures.
  • High viscosities of the spinning solution result, for example, when the cellulose concentration in the solution is high, which is of course desirable from an economic point of view.
  • the temperature of the spinning solution must also be kept high if fibers with a low titer, e.g. want to spin less than 1 dtex. In the case of such fibers, the filaments in the air gap must be stretched particularly strongly. Without increasing the temperature of the spinning solution, the viscosity of the spinning solution would also be too high for this stretching.
  • the temperature of the spinning solution should be 80 ° C to 120 ° C, especially 100 ° C to 120 ° C during spinning. Since solutions of cellulose in NMMO are thermally unstable and tend to exothermic decomposition reactions, it is not desirable to increase the temperature of the cellulose solution.
  • the present invention has for its object to provide a method according to the generic term with which cellulose solutions of high viscosity can be better spun and fibers with small titers can be better produced.
  • This object is achieved in that the temperature (T) of the cooling air before contact with the filaments is 60 ° C ⁇ T ⁇ 90 ° C.
  • fibers which are produced using cooling air at higher temperatures have higher strength values than fibers which are produced at the same temperature of the spinning solution using cooling air at a lower temperature.
  • the cooling air preferably has a moisture content of 4 g H 2 O / kg air to 15 g H 2 O / kg air.
  • the method according to the invention is particularly suitable for producing fibers with a titer of less than 1 dtex.
  • a spinning solution with 15% by weight cellulose (cellulose: Cellunier F, manufacturer Rayonnier), 10% by weight water and 75% by weight NMMO was spun into fibers using cooling air at different temperatures.
  • the minimum achievable titer of the fibers was measured in each case: For this purpose, the maximum withdrawal speed (m / min) of the fibers is determined by the Take-off speed is increased until the thread breaks. This speed is noted and used to calculate the titer according to the calculation method described in PCT-WO 98/58103.
  • the strength of the spun fibers was determined in a conditioned state.
  • the table shows that the minimum achievable titer drops significantly at temperatures of the cooling air of over 60 ° C. Furthermore, the strength of the fibers increases significantly.
  • a spinning solution with 14.6% by weight cellulose (cellulose Borregaard LVU); 9.5% by weight of water and 75.9% by weight of> NMMO was spun into fibers with a titer of 1.3 dtex in a continuous test installation. At various temperatures of the cooling air used, the spinning mass temperature was measured in order to be able to produce fibers with this titer without problems.
  • the table shows that when using cooling air at a temperature of 65 ° C it is possible to produce the fibers at a significantly lower temperature of the spinning solution.
  • a spinning solution with 15% by weight cellulose (pulp Alicell VLV; manufacturer Western Pulp) 10% by weight) water and 75% by weight o NMMO was spun into fibers using cooling air at different temperatures.
  • the minimum achievable titer of the fibers and the strength of the spun fibers in a conditioned state were determined as described in Example 1:
  • the table shows that when cooling air with higher temperatures is used, it is possible to produce fibers with a titer of less than 1 dtex.

Abstract

The invention relates to a method for producing cellulose fibres. According to said method, a solution of cellulose in a tertiary amino oxide is extruded through the spinning holes of a spinneret and the extruded filaments are fed into a precipitation bath whilst being drawn via an air gap. The filaments are exposed to a gaseous stream in the air gap. The invention is characterised in that the temperature (T) of the gas prior to the contact with the filaments is represented by the formula: 60 °C < T < 90 °C.

Description

Verfahren zur Herstellung cellulosischer FasernProcess for the production of cellulosic fibers
Die Erfindung betrifft ein Verfahren gemäß dem Oberbegriff des Patentanspruches 1.The invention relates to a method according to the preamble of patent claim 1.
Solche Verfahren zur Herstellung cellulosischer Fasern sind unter dem Namen „Aminoxidverfahren" oder „Lyocellverfahren" bekannt.Such processes for producing cellulosic fibers are known under the name “amine oxide process” or “lyocell process”.
„Lyocell" ist der von der BISFA (The International Bureau for the Standardization of man made fibers) vergebene Gattungsnamen für Cellulosefasern, welche dadurch hergestellt werden, daß Cellulose ohne Ausbildung eines Derivates in einem organischen Lösungsmittel aufgelöst wird und aus dieser Lösung Fasern extrudiert werden. Unter einem organischen Lösungsmittel wird dabei ein Gemisch aus einer organischen Chemikalie und Wasser verstanden. Solche Fasern sind auch unter dem Begriff „lösungsmittelgesponnene Fasern" bekannt. Als organisches Lösungsmittel wird heute in kommerziellem Maßstab N-Methyl- Morpholin-N-Oxid eingesetzt."Lyocell" is the generic name given by BISFA (The International Bureau for the Standardization of man made fibers) for cellulose fibers which are produced by dissolving cellulose in an organic solvent without the formation of a derivative and extruding fibers from this solution. An organic solvent is understood to mean a mixture of an organic chemical and water. Such fibers are also known under the term “solvent-spun fibers”. As an organic solvent, N-methyl-morpholine-N-oxide is used today on a commercial scale.
Es ist bekannt, daß die Eigenschaften von Lyocellfasern sowie die Stabilität des Spinnverfahrens maßgeblich von den Bedingungen beeinflußt werden, welche im sogenannten Luftspalt zwischen der Spinndüse und der Fällbadoberfläche herrschen.It is known that the properties of lyocell fibers and the stability of the spinning process are significantly influenced by the conditions which exist in the so-called air gap between the spinneret and the surface of the precipitation bath.
So ist aus der PCT- WO 93/19230 bekannt, die extrudierten Filamente unmittelbar nach dem Formen mittels eines Gasstromes zu kühlen. Im folgenden wird dieser Gasstrom als „Kühlluft" bezeichnet. Die Temperatur der Kühlluft beträgt in den Beispielen der PCT-WO 93/19230 -6°C bis 24°C.It is known from PCT-WO 93/19230 to cool the extruded filaments immediately after shaping by means of a gas stream. In the following, this gas flow is referred to as "cooling air". The temperature of the cooling air in the examples of PCT-WO 93/19230 is -6 ° C. to 24 ° C.
Die PCT-WO 94/28218 beschreibt ein ähnliches Verfahren wie die PCT-WO 93/19230. Gemäß diesem Dokument soll die Temperatur der Kühlluft unter 50°C gehalten werden.PCT-WO 94/28218 describes a method similar to PCT-WO 93/19230. According to this document, the temperature of the cooling air should be kept below 50 ° C.
Aus der PCT-WO 95/02082 ist ein Verfahren bekannt, gemäß dem der Spinnloch- durchmesser, der Spinnmasseausstoß pro Loch, der Titer des einzelnen Filamentes, die Breite des Luftspaltes und die Feuchte der Luft im Luftspalt mittels eines mathematischen Ausdruckes in gewissen Bereichen gehalten werden sollen. In den Beispielen der PCT-WO 95/02082 sind keine Angaben über die Temperatur der Kühlluft vorhanden. In der Beschreibung werden allgemein Temperaturen zwischen 10°C und 60°C, bevorzugt zwischen 20°C und 40°C angegeben.A method is known from PCT-WO 95/02082, according to which the spinning hole diameter, the spinning mass output per hole, the titer of the individual filament, the width of the air gap and the humidity of the air in the air gap are kept in certain ranges by means of a mathematical expression should be. In the examples of PCT-WO 95/02082 there is no information about the temperature of the cooling air. In the Descriptions are generally temperatures between 10 ° C and 60 ° C, preferably between 20 ° C and 40 ° C.
Die PCT-WO 96/17118 befaßt sich mit dem Feuchtegehalt der Kühlluft. Die höchste in diesem Dokument angegebene Temperatur der Kühlluft liegt bei 40°C.PCT-WO 96/17118 deals with the moisture content of the cooling air. The highest temperature of the cooling air specified in this document is 40 ° C.
Gemäß der PCT-WO 96/21758 kann die Temperatur der Kühlluft 0°C bis 40°C betragen. In der PCT-WO 97/38153 wird die Temperatur der Kühlluft mit -10°C bis 50°C angegeben.According to PCT-WO 96/21758, the temperature of the cooling air can be 0 ° C to 40 ° C. In PCT-WO 97/38153 the temperature of the cooling air is given as -10 ° C to 50 ° C.
In der PCT-WO 98/58103 wird beschrieben, daß sich bei einer großen Anzahl von extrudierten Filamenten, d.h. bei Verwendung von Spinndüsen mit sehr vielen Spinnlöchern, im Luftspalt ein sehr feuchtes Klima einstellt. Um die Stabilität des Spinnverfahrens auch unter diesen Bedingungen zu gewährleisten, wird in der PCT-WO 98/58103 vorgeschlagen, daß die Spinnlösung unmittelbar vor dem Verspinnen einen gewissen Anteil an Cellulose und/oder einem anderen Polymer mit einem höheren Molekulargewicht enthalten soll.PCT-WO 98/58103 describes that with a large number of extruded filaments, i.e. when using spinnerets with a large number of spinning holes, a very humid climate is established in the air gap. In order to ensure the stability of the spinning process even under these conditions, it is proposed in PCT-WO 98/58103 that the spinning solution should contain a certain proportion of cellulose and / or another polymer with a higher molecular weight immediately before spinning.
Ein Problem beim Verspinnen von Celluloselösungen in NMMO besteht darin, daß man bei Lösungen mit einer hohen Viskosität die Spinnlösung bei erhöhten Temperaturen verspinnen muß. Hohe Viskositäten der Spinnlösung ergeben sich beispielsweise dann, wenn die Cellulosekonzentration in der Lösung hoch ist, was natürlich aus ökonomischer Sicht erwünscht ist. Weiters ergeben sich hohe Viskositäten bei der Verwendung von Zellstoffen mit hohen Anteilen von hochmolekularer Cellulose.A problem with spinning cellulose solutions in NMMO is that in solutions with a high viscosity the spinning solution has to be spun at elevated temperatures. High viscosities of the spinning solution result, for example, when the cellulose concentration in the solution is high, which is of course desirable from an economic point of view. Furthermore, there are high viscosities when using cellulose with high proportions of high molecular cellulose.
Die Temperatur der Spinnlösung muß aber auch dann hoch gehalten werden, wenn man Fasern mit einem geringen Titer, z.B. kleiner als 1 dtex erspinnen möchte. Bei solchen Fasern müssen die Filamente im Luftspalt besonders stark verstreckt werden. Ohne Erhöhung der Temperatur der Spinnlösung wäre auch hier die Viskosität der Spinnlösung für diese Verstreckung zu hoch.However, the temperature of the spinning solution must also be kept high if fibers with a low titer, e.g. want to spin less than 1 dtex. In the case of such fibers, the filaments in the air gap must be stretched particularly strongly. Without increasing the temperature of the spinning solution, the viscosity of the spinning solution would also be too high for this stretching.
Üblicherweise sollte die Temperatur der Spinnlösung beim Verspinnen 80°C bis 120°C, insbesondere 100°C bis 120°C betragen. Da Lösungen von Cellulose in NMMO thermisch instabil sind und zu exothermen Zersetzungsreaktionen neigen, ist es aber nicht erwünscht, die Temperatur der Celluloselösung zu erhöhen. Die vorliegende Erfindung stellt sich zur Aufgabe, ein Verfahren gemäß dem Gattungsbegriff zur Verfügung zu stellen, mit welchem Celluloselösungen von hoher Viskosität besser versponnen und Fasern mit kleinen Titern besser hergestellt werden können.Usually the temperature of the spinning solution should be 80 ° C to 120 ° C, especially 100 ° C to 120 ° C during spinning. Since solutions of cellulose in NMMO are thermally unstable and tend to exothermic decomposition reactions, it is not desirable to increase the temperature of the cellulose solution. The present invention has for its object to provide a method according to the generic term with which cellulose solutions of high viscosity can be better spun and fibers with small titers can be better produced.
Diese Aufgabe wird dadurch gelöst, daß für die Temperatur (T) der Kühlluft vor dem Kontakt mit den Filamenten gilt 60°C < T < 90°C.This object is achieved in that the temperature (T) of the cooling air before contact with the filaments is 60 ° C <T <90 ° C.
Es hat sich überraschenderweise gezeigt, daß bei Verwendung von Kühlluft mit höheren Temperaturen im Bereich gemäß Patentanspruch 1 auch höherviskose Celluloselösungen gut versponnen werden können, ohne daß die Temperatur der Spinnlösung angehoben werden muß. Auch Fasern mit niedrigen Titern, z.B. 0,9 dtex, können ohne Anheben der Temperatur der Spinnlösung gut versponnen werden.It has surprisingly been found that when using cooling air with higher temperatures in the range of claim 1, even higher-viscosity cellulose solutions can be spun well without the temperature of the spinning solution having to be raised. Also fibers with low titers, e.g. 0.9 dtex, can be spun well without raising the temperature of the spinning solution.
Weiters weisen Fasern, die unter Verwendung von Kühlluft mit höheren Temperaturen hergestellt werden, im Vergleich zu Fasern, die bei gleicher Temperatur der Spinnlösung unter Verwendung von Kühlluft mit geringerer Temperatur hergestellt werden, höhere Festigkeitswerte auf.Furthermore, fibers which are produced using cooling air at higher temperatures have higher strength values than fibers which are produced at the same temperature of the spinning solution using cooling air at a lower temperature.
Bevorzugt weist die Kühlluft einen Feuchtegehalt von 4 g H2O / kg Luft bis 15 g H2O / kg Luft auf.The cooling air preferably has a moisture content of 4 g H 2 O / kg air to 15 g H 2 O / kg air.
Insbesondere eignet sich das erfindungsgemäße Verfahren zur Herstellung von Fasern mit einem Titer von weniger als 1 dtex.The method according to the invention is particularly suitable for producing fibers with a titer of less than 1 dtex.
Beispiel 1 :Example 1 :
Eine Spinnlösung mit 15 Gew.% Cellulose (Zellstoff: Cellunier F, Hersteller Fa. Rayonnier), 10 Gew.% Wasser und 75 Gew.% NMMO wurde unter Verwendung von Kühlluft mit verschiedenen Temperaturen zu Fasern versponnen.A spinning solution with 15% by weight cellulose (cellulose: Cellunier F, manufacturer Rayonnier), 10% by weight water and 75% by weight NMMO was spun into fibers using cooling air at different temperatures.
Es wurde jeweils der minimal erreichbare Titer der Fasern gemessen: Dazu wird die maximale Abzugsgeschwindigkeit (m/min) der Fasern ermittelt, indem die Abzugsgeschwindigkeit solange gesteigert wird, bis der Faden reißt. Diese Geschwindigkeit wird notiert und zur Berechnung des Titers nach der in der PCT-WO 98/58103 beschriebenen Berechnungsmethode herangezogen.The minimum achievable titer of the fibers was measured in each case: For this purpose, the maximum withdrawal speed (m / min) of the fibers is determined by the Take-off speed is increased until the thread breaks. This speed is noted and used to calculate the titer according to the calculation method described in PCT-WO 98/58103.
Weiters wurde jeweils die Festigkeit der versponnenen Fasern in konditioniertem Zustand ermittelt.Furthermore, the strength of the spun fibers was determined in a conditioned state.
Aus der Tabelle geht hervor, daß bei Temperaturen der Kühlluft von über 60°C der minimal erreichbare Titer deutlich sinkt. Weiters steigt die Festigkeit der Fasern deutlich an.The table shows that the minimum achievable titer drops significantly at temperatures of the cooling air of over 60 ° C. Furthermore, the strength of the fibers increases significantly.
Beispiel 2:Example 2:
Eine Spinnlösung mit 14,6 Gew.% Cellulose (Zellstoff Borregaard LVU); 9,5 Gew.% Wasser und 75,9 Gew.%> NMMO wurde an einer kontinuierlichen Versuchsanlage zu Fasern mit einem Titer von 1,3 dtex versponnen. Es wurde bei verschiedenen Temperaturen der eingesetzten Kühlluft gemessen, welche Spinnmassetemperatur erforderlich war, um Fasern mit diesem Titer störungsfrei herstellen zu können.A spinning solution with 14.6% by weight cellulose (cellulose Borregaard LVU); 9.5% by weight of water and 75.9% by weight of> NMMO was spun into fibers with a titer of 1.3 dtex in a continuous test installation. At various temperatures of the cooling air used, the spinning mass temperature was measured in order to be able to produce fibers with this titer without problems.
Aus der Tabelle geht hervor, daß es bei Verwendung von Kühlluft mit einer Temperatur von 65 °C möglich ist, die Fasern bei einer deutlich geringeren Temperatur der Spinnlösung herzustellen. The table shows that when using cooling air at a temperature of 65 ° C it is possible to produce the fibers at a significantly lower temperature of the spinning solution.
Beispiel 3 :Example 3:
Eine Spinnlösung mit 15 Gew.% Cellulose (Zellstoff Alicell VLV; Hersteller Western Pulp) 10 Gew.%) Wasser und 75 Gew.%o NMMO wurde unter Verwendung von Kühlluft mit verschiedenen Temperaturen zu Fasern versponnen. Es wurden wie im Beispiel 1 beschrieben der minimal erreichbare Titer der Fasern sowie die Festigkeit der versponnenen Fasern in konditioniertem Zustand ermittelt:A spinning solution with 15% by weight cellulose (pulp Alicell VLV; manufacturer Western Pulp) 10% by weight) water and 75% by weight o NMMO was spun into fibers using cooling air at different temperatures. The minimum achievable titer of the fibers and the strength of the spun fibers in a conditioned state were determined as described in Example 1:
Aus der Tabelle geht hervor, daß es bei Verwendung von Kühlluft mit höheren Temperaturen gut möglich ist, Fasern mit einem Titer von weniger als 1 dtex herzustellen. The table shows that when cooling air with higher temperatures is used, it is possible to produce fibers with a titer of less than 1 dtex.

Claims

Patentansprüche : Claims:
1. Verfahren zur Herstellung cellulosischer Fasern, indem eine Lösung von Cellulose in einem tertiären Aminoxid durch Spinnlöcher einer Spinndüse extrudiert und die extrudierten Filamente über einen Luftspalt unter Verzug in ein Fällbad geführt werden, wobei die Filamente im Luftspalt der Strömung eines Gases ausgesetzt werden, dadurch gekennzeichnet, daß für die Temperatur (T) des Gases vor dem Kontakt mit den Filamenten gilt 60°C < T < 90°C.1. A process for producing cellulosic fibers by extruding a solution of cellulose in a tertiary amine oxide through spinning holes in a spinneret and passing the extruded filaments over an air gap with delay into a precipitation bath, the filaments in the air gap being exposed to the flow of a gas, thereby characterized in that the temperature (T) of the gas before contact with the filaments applies 60 ° C <T <90 ° C.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Gas Luft ist.2. The method according to claim 1, characterized in that the gas is air.
3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß die strömende Luft einen Feuchtegehalt von 4 g H O / kg Luft bis 15 g H2O / kg Luft aufweist.3. The method according to claim 2, characterized in that the flowing air has a moisture content of 4 g HO / kg air to 15 g H 2 O / kg air.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß Filamente mit einem Titer von weniger als 1 dtex hergestellt werden. 4. The method according to any one of claims 1 to 3, characterized in that filaments are produced with a titer of less than 1 dtex.
EP01944725A 2000-06-29 2001-06-28 Method for producing cellulose fibres Expired - Lifetime EP1299583B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT01944725T ATE269434T1 (en) 2000-06-29 2001-06-28 METHOD FOR PRODUCING CELLULOSIC FIBERS

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT11212000 2000-06-29
AT0112100A AT408355B (en) 2000-06-29 2000-06-29 Process for producing cellulosic fibres
PCT/AT2001/000212 WO2002000975A1 (en) 2000-06-29 2001-06-28 Method for producing cellulose fibres

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EP1299583A1 true EP1299583A1 (en) 2003-04-09
EP1299583B1 EP1299583B1 (en) 2004-06-16

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EP (1) EP1299583B1 (en)
JP (1) JP2004501296A (en)
CN (1) CN1180142C (en)
AT (1) AT408355B (en)
AU (2) AU6712701A (en)
BR (1) BR0112036A (en)
CA (1) CA2413706A1 (en)
DE (1) DE50102613D1 (en)
NO (1) NO20026186L (en)
TR (1) TR200401926T4 (en)
TW (1) TW534932B (en)
WO (1) WO2002000975A1 (en)

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AT506268B1 (en) 2008-01-11 2014-08-15 Chemiefaser Lenzing Ag MICROFIBRE
WO2018156352A1 (en) 2017-02-21 2018-08-30 Apdn (B.V.I) Inc. Nucleic acid coated submicron particles for authentication

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ATA53792A (en) * 1992-03-17 1995-02-15 Chemiefaser Lenzing Ag METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE
ES2120243T5 (en) * 1994-12-02 2006-11-16 NEWCELL GMBH &amp; CO. KG PROCEDURE FOR THE PRODUCTION OF CELLULOSED MOLDED BODIES AND A SPIN OF CELLULOSIC FILAMENTS.
US6210801B1 (en) * 1996-08-23 2001-04-03 Weyerhaeuser Company Lyocell fibers, and compositions for making same
US6221487B1 (en) * 1996-08-23 2001-04-24 The Weyerhauser Company Lyocell fibers having enhanced CV properties
AT405531B (en) * 1997-06-17 1999-09-27 Chemiefaser Lenzing Ag METHOD FOR PRODUCING CELLULOSIC FIBERS
AT408656B (en) * 1998-06-04 2002-02-25 Chemiefaser Lenzing Ag METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES

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WO2002000975A1 (en) 2002-01-03
US20030173700A1 (en) 2003-09-18
ATA11212000A (en) 2001-03-15
AU2001267127B2 (en) 2005-03-24
CA2413706A1 (en) 2002-12-24
AU6712701A (en) 2002-01-08
NO20026186D0 (en) 2002-12-23
NO20026186L (en) 2002-12-23
TW534932B (en) 2003-06-01
EP1299583B1 (en) 2004-06-16
CN1439065A (en) 2003-08-27
BR0112036A (en) 2003-05-13
AT408355B (en) 2001-11-26
DE50102613D1 (en) 2004-07-22
JP2004501296A (en) 2004-01-15
CN1180142C (en) 2004-12-15

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