EP0726974B1 - Process for manufacturing cellulose moulded bodies - Google Patents

Process for manufacturing cellulose moulded bodies Download PDF

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Publication number
EP0726974B1
EP0726974B1 EP95928881A EP95928881A EP0726974B1 EP 0726974 B1 EP0726974 B1 EP 0726974B1 EP 95928881 A EP95928881 A EP 95928881A EP 95928881 A EP95928881 A EP 95928881A EP 0726974 B1 EP0726974 B1 EP 0726974B1
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amine oxide
tertiary amine
cellulose
pct
fibers
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German (de)
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EP0726974A1 (en
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Hartmut Rüf
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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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

Definitions

  • compositions come as spinning solutions for the process according to the invention into consideration.
  • the pulp concentration in the dope can be between 5 and 25% vary. However, cellulose contents between 10 and 18% are preferred.

Abstract

PCT No. PCT/AT95/00174 Sec. 371 Date Jun. 21, 1996 Sec. 102(e) Date Jun. 21, 1996 PCT Filed Sep. 4, 1995 PCT Pub. No. WO96/07779 PCT Pub. Date Mar. 14, 1996The disclosure describes a process for the manufacture of cellulosic moulded bodies in which cellulose is dissolved in a mixture of a tertiary amine oxide and a non-solvent for cellulose, e.g. water. The solution is extruded via a moulding tool and the filaments received are led via an air gap to a precipitation bath whilst being drawn. The process is characterised in that the precipitation bath substantially comprises a non-aqueous solvent for the tertiary amine oxide, whereby the molecular weight of the non-aqueous solvent is larger than that of the tertiary amine oxide. In this manner, solvent-spun fibers with a lower fibrillation tendency can be obtained. Polyethylene glycols are preferably used.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von cellulosischen Formkörpern, z.B. Fasern gemäß dem Oberbegriff des Anspruches 1.The invention relates to a process for the production of cellulosic shaped articles, e.g. Fibers according to the preamble of claim 1.

In den letzten Jahrzehnten wurden bedingt durch die Umweltproblematik des bekannten Viskoseverfahrens zur Herstellung cellulosischer Fasern intensive Anstrengungen unternommen, alternative, umweltfreundlichere Verfahren zur Verfügung zu stellen. Als eine besonders interessante Möglichkeit hat sich dabei in den letzten Jahren herauskristallisiert, Cellulose ohne Ausbildung eines Derivates in einem organischen Lösungsmittel aufzulösen und aus dieser Lösung Formkörper zu extrudieren. Solcherart ersponnene Fasern erhielten von der BISFA (The International Bureau for the Standardization of man made fibers) den Gattungsnamen Lyocell zugeteilt, wobei unter einem organischen Lösungsmittel ein Gemisch aus einer organischen Chemikalie und Wasser verstanden wird.In recent decades, the known viscose process has caused environmental problems intensive efforts to produce cellulosic fibers, alternative, to provide more environmentally friendly processes. As a particularly interesting one Possibility has emerged in recent years, cellulose without training dissolve a derivative in an organic solvent and moldings from this solution to extrude. Such spun fibers were obtained from BISFA (The International Bureau for the Standardization of man made fibers) was assigned the generic name Lyocell, whereby under an organic solvent a mixture of an organic chemical and Water is understood.

Es hat sich herausgestellt, daß sich als organisches Lösungsmittel insbesondere ein Gemisch aus einem tertiären Aminoxid und Wasser hervorragend zur Herstellung von Lyocell-Fasern eignet. Als Aminoxid wird dabei vorwiegend N-methyl-morpholin-N-oxid (NMMO) verwendet. Andere geeignete Aminoxide sind in der EP-A 553 070 geoffenbart. Verfahren zur Herstellung cellulosischer Formkörper aus einer Lösung der Cellulose in einem Gemisch aus NMMO und Wasser sind z.B. in der US-PS 4,246,221 geoffenbart. Die solcherart hergestellten Fasern zeichnen sich durch eine hohe Faserfestigkeit im konditionierten sowie im nassen Zustand, einen hohen Naßimodul und eine hohe Schlingenfestigkeit aus.It has been found that in particular a mixture of organic solvents a tertiary amine oxide and water are ideal for the production of Lyocell fibers. N-methyl-morpholine-N-oxide (NMMO) is predominantly used as the amine oxide. Other suitable amine oxides are disclosed in EP-A 553 070. Process for the production of cellulosic Shaped bodies from a solution of cellulose in a mixture of NMMO and water e.g. in U.S. Patent 4,246,221. The fibers produced in this way are characterized by a high fiber strength in the conditioned as well as in the wet state, a high wet modulus and a high loop strength.

Eine spezielle Eigenschaft dieser Fasern ist ihre hohe Neigung zur Fibrillation, insbesondere unter Beanspruchung im nassen Zustand, wie z.B. während eines Waschvorganges. Während diese Eigenschaft für bestimmte Anwendungen der Fasern durchaus erwünscht ist und interessante Effekte ergibt, wird hingegen die Brauchbarkeit für andere Zwecke, wie z.B. Textilien, die Waschbeständigkeit aufweisen sollen, vermindert.A special property of these fibers is their high tendency to fibrillation, especially under Stress when wet, e.g. during a washing process. While this Property for certain applications of the fibers is quite desirable and interesting Effects, on the other hand, the usability for other purposes, such as Textiles that Wash resistance should be reduced.

Es hat daher nicht an Anstrengungen gefehlt, mit bestimmten Maßnahmen das Fibrillationsverhalten zu reduzieren.Efforts have not been lacking, with certain measures, the fibrillation behavior to reduce.

So wird in der PCT-WO 92/07124 vorgeschlagen, eine frisch gesponnene, noch nicht getrocknete Faser mit einer Lösung eines Polymers, welches mehrere kationische Stellen enthält, zu behandeln. For example, PCT-WO 92/07124 proposes a freshly spun, not yet dried Treat fiber with a solution of a polymer that contains several cationic sites.

Gemäß der EP-A- 538 977 werden die Fasern, welche frisch versponnen oder bereits getrocknet sein können, mit einem wäßrigen System behandelt, welches ein chemisches Reagenz mit 2 bis 6 funktionellen Gruppen, welche mit Cellulose reagieren können, enthält.According to EP-A-538 977, the fibers which are freshly spun or have already been dried can be treated with an aqueous system which contains a chemical reagent with 2 to 6 contains functional groups which can react with cellulose.

In der PCT-WO 94/09191 wird vorgeschlagen, daß die funktionellen Gruppen eines chemischen Reagenz, mit welchem die Fasern behandelt werden, elektrophile C=C-Doppelbindungen und andere Reaktivgruppen für Cellulose sind.In PCT-WO 94/09191 it is proposed that the functional groups of a chemical Reagent with which the fibers are treated, electrophilic C = C double bonds and are other reactive groups for cellulose.

Diesen Vorschlägen ist gemeinsam, daß die Verringerung der Fibrillationstendenz der Fasern durch eine chemische Modifizierung der.Faser einerseits durch die Anlagerung von kationischen Verbindungen an die ein negatives Potential aufweisenden Hydroxylgruppen, andererseits durch die Ausbildung kovalenter Bindungen der Cellulose mit den Reaktivgruppen der Verbindungen mit daraus resultierender Vernetzung der Fibrillen, erreicht wird.Common to these proposals is that the reduction in the tendency of the fibers to fibrillate by chemical modification of the fiber on the one hand by the addition of cationic Connections to the hydroxyl groups which have a negative potential, on the other hand by the formation of covalent bonds between the cellulose and the reactive groups of the compounds with the resulting networking of the fibrils.

Andere Arbeiten, wie z.B. die anhängige AT 1348/93 der Anmelderin beschäftigen sich mit der Möglichkeit, durch eine gezielte Variation der Spinnparameter, wie z.B. Ausstoß, Länge des Luftspaltes, Verzug, Luftfeuchte im Luftspalt, ebenfalls eine Reduzierung der Fibrillationsneigung zu erreichen.Other work, such as pending AT 1348/93 of the applicant deal with the Possibility by a specific variation of the spinning parameters, e.g. Output, length of the Air gap, warpage, air humidity in the air gap, also a reduction in the tendency to fibrillation to reach.

Es hat sich nun überraschenderweise gezeigt, daß ein wirkungsvolle Reduzierung der Fibrillationstendenz dadurch erreicht werden kann, daß das Fällbad, in welches die Faser nach der Extrusion unter Verzug über einen Luftspalt geführt wird, im wesentlichen aus einem nichtwäßrigen Lösungsmittel für das tertiäre Aminoxid, insbesondere NMMO, besteht, wobei das Molekulargewicht des nichtwäßrigen Lösungsmittel größer als das des tertiären Aminoxides ist.It has now surprisingly been found that an effective reduction in Fibrillation tendency can be achieved in that the precipitation bath in which the fiber after the Extrusion is performed with delay over an air gap, essentially from a non-aqueous Solvent for the tertiary amine oxide, especially NMMO, there is Molecular weight of the non-aqueous solvent is greater than that of the tertiary amine oxide.

Üblicherweise werden cellulosische Fasern aus einer Lösung in einem tertiären Aminoxid in ein wäßriges Fällbad versponnen.Usually, cellulosic fibers are dissolved in a solution in a tertiary amine oxide spun aqueous precipitation bath.

Die SU- 1 224 362 A beschreibt hingegen ein Verfaheren zur Herstellung von Cellulosefasern mit einem Spinnbad, das sich dadurch auszeichnet, daß es mit dem Ziel der Erhöhung der Bruchdehnung, der Senkung des Schrumpfens bei erhöhten Temperaturen und der Beibehaltung der Dehnung im nassen Zustand unter anderem Isopropanol oder Isobutanol oder Mischungen der beiden mit 5-40% NMMO und 0,8-10% Wasser enthält. Auch die Verwendung von Isoamylalkohol ist in einem Beispiel angegeben.SU-1 224 362 A, on the other hand, describes a process for the production of cellulose fibers a spinning bath, which is characterized in that it has the aim of increasing the elongation at break, reducing shrinkage at elevated temperatures and maintaining Elongation in the wet state including isopropanol or isobutanol or mixtures of the contains both with 5-40% NMMO and 0.8-10% water. Also the use of isoamyl alcohol is given in an example.

Auch die Publikationen Romanov V.V., Lunina O.B., Mil`kova L.P. und Kulichikhin V.G., Khim. Volokna (1989) Nr. 1, S. 29, Romanov V.V., Lunina O.B., Mil'kova L.P., Brusentsova V.G. und Kulichikhin V.G., Khim. Volokna (1989) Nr. 4, S. 33 und Romanov V.V. und Sokira A.N., Khim. Volokna (1988) Nr. 1, S. 27 beschreiben den Einsatz von Isopropanol und Isobutanol im SpinnbadAlso the publications Romanov VV, Lunina OB, Mil`kova LP and Kulichikhin VG, Khim. Volokna (1989) No. 1, p. 29, Romanov VV, Lunina OB, Mil'kova LP, Brusentsova VG and Kulichikhin VG, Khim. Volokna (1989) No. 4, p. 33 and Romanov VV and Sokira AN, Khim. Volokna (1988) No. 1, p. 27 describe the use of isopropanol and isobutanol in the spinning bath

Die Publikationen I. Quenin, "Precipitation de la cellulose à partir de solutions dans les oxydes d'amines tertiaires: application au filage" Dissertation Grenoble 1985 sowie M. Dubé und R.H. Blackwell, "Precipitation and crystallization of cellulose from amine oxide solutions" TAPPI Proceedings, International Dissolving and Specialty Pulps, Boston 1983 untersuchen das Ausmaß der Cellulosekristallisation beim Spinnen in Methanol.The publications I. Quenin, "Precipitation de la cellulose à partir de solutions dans les oxydes d'amines tertiaires: application au filage "Dissertation Grenoble 1985 as well as M. Dubé and R.H. Blackwell, "Precipitation and crystallization of cellulose from amine oxide solutions" TAPPI Proceedings, International Dissolving and Specialty Pulps, Boston 1983 examine the extent the cellulose crystallization when spinning in methanol.

Das Fibrillationsverhalten von aus Aminoxid ersponnenen Fasern wird in P. Weigel, J. Gensrich und H.P. Fink "Challenges in Cellulosic Man-Made Fibres" Viscose Chemistry Seminar, Stockholm 1994 erwähnt: Das Spinnen in Isopropanol soll demnach eine deutliche Verbesserung erbringen.The fibrillation behavior of fibers spun from amine oxide is described in P. Weigel, J. Gensrich and H.P. Fink "Challenges in Cellulosic Man-Made Fibers" Viscose Chemistry Seminar, Stockholm 1994 mentions: Spinning in isopropanol is said to be a significant improvement provide.

Allen diesen Publikationen ist gemeinsam, daß als Fällungsmittel für das Spinnbad niedermolekulare Substanzen mit einem Molekulargewicht eingesetzt werden, das deutlich kleiner als das Molekulargewicht des eingesetzten Aminoxides ist. Die Molmasse von NMMO beträgt 117 g/mol.All of these publications have in common that as a precipitant for the spin bath low molecular weight Substances with a molecular weight that are significantly smaller than that are used Molecular weight of the amine oxide used. The molecular weight of NMMO is 117 g / mol.

Überraschenderweise verbessert sich das Fibrillationsverhalten der ersponnenen Fasern jedoch deutlich, wenn man im Spinnbad Substanzen einsetzt, die ein höheres Molekulargewicht als das verwendete Aminoxid aufweisen.Surprisingly, however, the fibrillation behavior of the spun fibers improves clear if you use substances in the spinning bath that have a higher molecular weight than that have used amine oxide.

Das Spinnbad besteht gemäß dem erfindungsgemäßen Verfahren im wesentlichen aus diesen Substanzen, d.h., daß zusätlich kleine Mengen an Zusatztoffen im Spinnbad enthalten sein können. Es ist auch möglich, kleine Mengen bis zu 10% an tertiärem Aminoxid oder Wasser zum Spinnbad zuzugeben, ohne den erfindungsgemäßen Effekt des Einsatzes von nichtwäßrigen Lösungsmittel für das Aminoxid einzuschränken.According to the method according to the invention, the spinning bath essentially consists of these Substances, i.e. that additional small amounts of additives are contained in the spin bath can. It is also possible to use small amounts of up to 10% of tertiary amine oxide or water Add spin bath without the inventive effect of using non-aqueous Restrict solvents for the amine oxide.

Als eingesetzte Substanzen für das erfindungsgemäße Verfahren eignen sich in hervorragender Weise bestimmte Glykole, Glykolether, Polyglykole und Polyglykolether.The substances used for the process according to the invention are particularly suitable Certain glycols, glycol ethers, polyglycols and polyglycol ethers.

Es hat sich gezeigt, daß insbesondere mit dem Einsatz von Polyethylenglykolen ein sehr gutes Fibrillationsverhalten der Fasern erreicht werden kann.It has been shown that especially with the use of polyethylene glycols a very good one Fibrillation behavior of the fibers can be achieved.

In besonders günstiger Weise kann das erfindungsgemäße Verfahren eingesetzt werden, wenn das verwendete tertiäre Aminoxid N-methyl-morpholin-N-oxid ist. The method according to the invention can be used in a particularly favorable manner if the tertiary amine oxide used is N-methyl-morpholine-N-oxide.

Als Spinnlösungen kommen für das erfindungsgemäße Verfahren alle bekannten Zusammensetzungen in Betracht. Als Ausgangsstoffe kommen die gängigen Zellstoffe, aber auch Zellstoffmischungen in Betracht. Die Zellstoffkonzentration in der Spinnmasse kann zwischen 5 und 25% variieren. Bevorzugt sind jedoch Cellulosegehalte zwischen 10 und 18%.All known compositions come as spinning solutions for the process according to the invention into consideration. The usual pulps, but also cellulose mixtures, come as starting materials into consideration. The pulp concentration in the dope can be between 5 and 25% vary. However, cellulose contents between 10 and 18% are preferred.

Beispiele:Examples: Versuchsapparatur:Experimental equipment:

Es handelt sich um ein in der Plastikverarbeitung gebräuchliches Schmelzindexgerät der Fa. Davenport. Das Gerät besteht aus einem beheizten temperaturregelbaren Zylinder, in den die Spinnmasse eingefüllt wird. Mittels eines Kolbens, dessen Vortrieb über einen Motor gesteuert wird, wird die Spinnmasse durch die an der Unterseite des Zylinders angebrachte Spinndüse extrudiert. Es handelt sich, wie in den der Lyocell-Technologie zugrundeliegenden Patenten beschrieben, um ein Trocken-Näß-Spinnverfahren, d.h.das Filament taucht nach der in den Beispielen angegebenen Luftstrecke in ein Spinnbad (20 cm Badstrecke in Wasser) ein und wird über eine Galette abgezogen.It is a melt index device from Fa. Davenport. The device consists of a heated temperature-controlled cylinder in which the Spinning mass is filled. By means of a piston, the propulsion of which is controlled by a motor the spinning mass is through the spinneret attached to the bottom of the cylinder extruded. It is like in the patents on which Lyocell technology is based described a dry-wet spinning process, i.e. the filament dips into that in the Examples specified air distance in a spinning bath (20 cm bath distance in water) and will subtracted via a godet.

Bedingungen:Conditions:

  • Spinnmasse 12% Zellstoff/ 76% NMMO / 12% WasserSpinning mass 12% pulp / 76% NMMO / 12% water
  • Spinntemperatur 110°CSpinning temperature 110 ° C
  • Düsenlochdurchmesser 100 µmNozzle hole diameter 100 µm
  • Klima im Luftspalt: 22-27°C/12-16% Relative FeuchtigkeitClimate in the air gap: 22-27 ° C / 12-16% relative humidity

    • Diese Parameter wurden für die Versuche konstant gehalten. Es wurde in Spinnbäder aus 13 verschiedenen nichtwäßrigen Lösungsmitteln versponnen und anschließend das Fibrillationsverhalten der Fasern gemessen.These parameters were kept constant for the tests. It was made in 13 different spinning baths spun non-aqueous solvents and then the fibrillation behavior of the fibers measured.

    Messung des Fibrillationsverhaltens:Measurement of fibrillation behavior:

    Die Reibung der Fasern aneinander bei Waschvorgängen bzw. bei Ausrüstvorgängen im nassen Zustand wurde durch folgenden Test simuliert: 8 Fasern wurden mit 4 ml Wasser in ein 20 ml Probenfläschchen gegeben und während 9 Stunden in einem Laborschüttelgerät der Type RO-10 der Fa. Gerhardt, Bonn (BRD) auf Stufe 12 geschüttelt. Das Fibrillationsverhalten der Fasern wurde danach unter dem Mikroskop mittels Auszählen der Anzahl der Fibrillen pro 0,276 mm Faserlänge beurteilt und wird in einer Spleißnote von 0 (keine Fibrillen) bis 6 (starke Fibrillation) angegeben. Beispiel Nr. Substanz im Spinnbad Molekulargewicht (g/mol) Spinnbadtemperatur (°C) Ausstoß g/Loch/min Spleißnote Vergleich Wasser 18 25 0,025 5,0 / 5,0 1a Isopropanol 60 25 0,025 4,0 / 4,5 1b 0,005 5,0 / 5,0 1c 0,1 4,75 / 5 2a Glycerin 92 25 0,025 4,0 / 4,0 2b 0,05 4,0 / 4,0 2c 0,1 4,0 / 4,0 2d 50 0,025 3,0 / 4,0 2e 0,05 4,0 / 3,5 2f 0,1 4,0 / 4,0 3a Diethylenglykol 106 25 0,025 3,5 / 3,75 3b 0,05 3,0 / 2,5 3c 0,1 4,5 / 4,75 3d 50 0,025 3,75 4a Triethanolamin 149 25 0,025 3,5 / 3,0 4b 0,05 3,0 / 2,5 4c 0,1 4,0 / 4,0 5a Butylpolyglykol 161-337 25 0,025 1,0 / 1,5 6a Tetraethylenglykol-dimethylether 222 25 0,025 3,0 / 2,5 6b 50 0,025 2,0 / 2,0 7a Polyethylenglykol 200 200 25 0,025 2,5 / 2,5 7b 0,05 3,0 / 2,5 7c 50 0,025 3,5 / 3,0 8a Polyethylenglykol 300 300 25 0,025 2,0 / 2,0 8b 0,05 3,5 / 3,0 8c 50 0,025 3,5 / 3,0 8d 0,05 2,5 / 2,5 9a Polyethylenglykol 400 400 25 0,025 2,5 / 3 9b 0,05 2,5 / 2,0 9c 0,1 2,5 / 2,5 9d 50 0,025 1,5 / 1,5 9e 0,05 1,5 / 1,0 9f 0,1 1,5 / 1,0 10a Polyethylenglykol 500 500 25 0,05 0,5 / 0,5 10b 0,1 0,5 / 0 10c 50 0,025 0,5 / 1,0 10d 0,05 0,5 / 0,5 10e 0,1 0 / 0,5 11a Polyethylenglykol 600 600 25 0,025 0-1,5 / 0-1,5 11b 0,05 0-1,5 / 0-1,5 11c 0,1 0 / 1 11d 50 0,025 0-2 / 0,5 11e 0,05 0,5 / 0,5 11f 0,1 0,5 / 0,5 12a Polyethylenglykol 1000 1000 40 0,025 1,0 / 1,0 13a Polyethylenglykol 3000 3000 60 0,025 0 / 0,5 13b 0,05 0,5 / 0,5 Legende: Nicht ausgefüllte Spalten bedeuten "Wert der letzten Eintragung". Die zweifachen Werte bei der Spleißnote bedeuten jeweils die Durchschnittswerte zweier unabhängiger Meßreihen an 8 Einzelfasern. The friction of the fibers against one another during washing processes or during finishing processes when wet was simulated by the following test: 8 fibers were placed in a 20 ml sample vial with 4 ml of water and in a laboratory shaker type RO-10 from Gerhardt for 9 hours, Bonn (FRG) shaken at level 12. The fibrillation behavior of the fibers was then assessed under the microscope by counting the number of fibrils per 0.276 mm fiber length and is given in a splice grade from 0 (no fibrils) to 6 (strong fibrillation). Example No. Substance in the spinning bath Molecular weight (g / mol) Spinning bath temperature (° C) Output g / hole / min Splice note comparison water 18th 25th 0.025 5.0 / 5.0 1a Isopropanol 60 25th 0.025 4.0 / 4.5 1b 0.005 5.0 / 5.0 1c 0.1 4.75 / 5 2a Glycerin 92 25th 0.025 4.0 / 4.0 2 B 0.05 4.0 / 4.0 2c 0.1 4.0 / 4.0 2d 50 0.025 3.0 / 4.0 2e 0.05 4.0 / 3.5 2f 0.1 4.0 / 4.0 3a Diethylene glycol 106 25th 0.025 3.5 / 3.75 3b 0.05 3.0 / 2.5 3c 0.1 4.5 / 4.75 3d 50 0.025 3.75 4a Triethanolamine 149 25th 0.025 3.5 / 3.0 4b 0.05 3.0 / 2.5 4c 0.1 4.0 / 4.0 5a Butyl polyglycol 161-337 25th 0.025 1.0 / 1.5 6a Tetraethylene glycol dimethyl ether 222 25th 0.025 3.0 / 2.5 6b 50 0.025 2.0 / 2.0 7a Polyethylene glycol 200 200 25th 0.025 2.5 / 2.5 7b 0.05 3.0 / 2.5 7c 50 0.025 3.5 / 3.0 8a Polyethylene glycol 300 300 25th 0.025 2.0 / 2.0 8b 0.05 3.5 / 3.0 8c 50 0.025 3.5 / 3.0 8d 0.05 2.5 / 2.5 9a Polyethylene glycol 400 400 25th 0.025 2.5 / 3 9b 0.05 2.5 / 2.0 9c 0.1 2.5 / 2.5 9d 50 0.025 1.5 / 1.5 9e 0.05 1.5 / 1.0 9f 0.1 1.5 / 1.0 10a Polyethylene glycol 500 500 25th 0.05 0.5 / 0.5 10b 0.1 0.5 / 0 10c 50 0.025 0.5 / 1.0 10d 0.05 0.5 / 0.5 10e 0.1 0 / 0.5 11a Polyethylene glycol 600 600 25th 0.025 0-1.5 / 0-1.5 11b 0.05 0-1.5 / 0-1.5 11c 0.1 0/1 11d 50 0.025 0-2 / 0.5 11e 0.05 0.5 / 0.5 11f 0.1 0.5 / 0.5 12a Polyethylene glycol 1000 1000 40 0.025 1.0 / 1.0 13a Polyethylene glycol 3000 3000 60 0.025 0 / 0.5 13b 0.05 0.5 / 0.5 Legend: Columns not filled in mean "value of last entry". The double values for the splice grade mean the average values of two independent measurement series on 8 individual fibers.

    Aus der Tabelle geht hervor, daß bei vergleichbaren Versuchsbedingungen organische Lösemittel mit einem Molekulargewicht, das deutlich unter dem von NMMO liegt, keinerlei wesentliche Verbesserung der Fibrillationstendenz der ersponnenen Fasern bewirken. Insbesondere ist im Gegensatz zur Literatur eine solche Verbesserung auch bei Isopropanol nicht zu beobachten.The table shows that, under comparable test conditions, organic solvents with a molecular weight that is significantly lower than that of NMMO, no essential Improve the tendency to fibrillation of the spun fibers. In particular, In contrast to the literature, such an improvement cannot be observed even with isopropanol.

    Ab einem Molekulargewicht, das dem von NMMO entspricht oder höher ist, ist eine deutliche Verbesserung der Fibrillationstendenz festzustellen. Diese Verbesserung ist besonders ab einem Molekulargewicht von 200 g/mol ausgeprägt. Mit Polyethylenglykolen höheren Molekulargewichts lassen sich sogar Fasern mit Spleißnoten von 0 oder 0,5 herstellen, das bedeutet, daß keine oder praktisch keine Fibrillenabspaltung mehr stattfindet. Der Einsatz von Polyethylenglykolen mit sehr hohem Molekulargewicht (ab etwa 3000) ist lediglich dadurch begrenzt, daß diese Stoffe für eine Verwendung im Spinnbad auf höhere Temperaturen z.B. ca. 50°C gebracht werden müssen.From a molecular weight that is equal to or higher than that of NMMO, a clear one is evident Improvement in the tendency to fibrillation. This improvement is especially from one Pronounced molecular weight of 200 g / mol. With higher molecular weight polyethylene glycols even fibers with splice scores of 0 or 0.5 can be produced, which means that there is no or practically no fibril splitting. The use of polyethylene glycols with a very high molecular weight (from about 3000) is only limited by the fact that these fabrics for use in the spin bath at higher temperatures e.g. brought about 50 ° C Need to become.

    Wie aus der Tabelle ersichtlich ist, hat der Ausstoß keinerlei wesentlichen Einfluß auf das Fibrillationsverhalten der Fasern. Insbesondere ist keine merkliche Verschlechterung der Fibrillationstendenz beim Übergang zu höheren Ausstoßraten festzustellen. Es wird dadurch im Unterschied zu bisher bekannten Verfahren möglich, auch mit höheren Ausstoßraten (z.B. 0,1 g/Loch/min) fibrillationsarme Fasern herzustellen, wodurch eine wirtschaftlichere Verfahrensweise ermöglicht wird.As can be seen from the table, the output has no significant influence on the fibrillation behavior of the fibers. In particular, there is no noticeable deterioration in the fibrillation tendency in the transition to higher output rates. It makes it different from previously known methods possible, even with higher output rates (e.g. 0.1 g / hole / min) To produce low-fibrillation fibers, which enables a more economical procedure becomes.

    Claims (4)

    1. Process for the manufacture of cellulosic moulded bodies in which cellulose is dissolved in a mixture of a tertiary amine oxide and a non-solvent for cellulose, e.g. water, the solution being extruded via a moulding tool and the filaments obtained being led into a precipitation bath via an air gap whilst being drawn, characterised in that the precipitation bath substantially comprises a non-aqueous solvent for the tertiary amine oxide whereby the molecular weight of the non-aqueous solvent is larger than that of the tertiary amine oxide.
    2. Process according to claim 1 characterised in that the non-aqueous solvent comes from the group consisting of glycols, glycol ethers, polyglycols and polyglycol ethers.
    3. Process according to claim 1 or 2 characterised in that the non-aqueous solvent is polyethylene glycol.
    4. Process according to at least one of the preceding claims characterised in that the tertiary amine oxide is N-methyl-morpholine-N-oxide.
    EP95928881A 1994-09-05 1995-09-04 Process for manufacturing cellulose moulded bodies Expired - Lifetime EP0726974B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    AT0169594A AT401063B (en) 1994-09-05 1994-09-05 METHOD FOR PRODUCING CELLULOSIC SHAPED BODIES
    AT1695/94 1994-09-05
    PCT/AT1995/000174 WO1996007779A1 (en) 1994-09-05 1995-09-04 Process for manufacturing cellulose moulded bodies

    Publications (2)

    Publication Number Publication Date
    EP0726974A1 EP0726974A1 (en) 1996-08-21
    EP0726974B1 true EP0726974B1 (en) 1998-06-17

    Family

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    Application Number Title Priority Date Filing Date
    EP95928881A Expired - Lifetime EP0726974B1 (en) 1994-09-05 1995-09-04 Process for manufacturing cellulose moulded bodies

    Country Status (12)

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    US (1) US5827463A (en)
    EP (1) EP0726974B1 (en)
    JP (1) JPH09505120A (en)
    CN (1) CN1135242A (en)
    AT (2) AT401063B (en)
    AU (1) AU693589B2 (en)
    BR (1) BR9506355A (en)
    CA (1) CA2175462A1 (en)
    DE (1) DE59502591D1 (en)
    FI (1) FI961903A (en)
    NO (1) NO961782D0 (en)
    WO (1) WO1996007779A1 (en)

    Families Citing this family (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE4446491C2 (en) * 1994-12-23 2000-06-15 Fraunhofer Ges Forschung Process for the production of cellulose fibers and cellulose fibers with reduced tendency to fibrillate
    AT404032B (en) * 1996-03-04 1998-07-27 Chemiefaser Lenzing Ag METHOD FOR PRODUCING CELLULOSIC FIBERS
    SE509894C2 (en) 1996-08-27 1999-03-15 Akzo Nobel Surface Chem Use of a Linear Synthetic Polymer to Improve the Properties of a Cellulose Form Body Made by a Tertiary Amine Oxide Process
    EP0853146A3 (en) * 1997-01-09 1999-03-24 Akzo Nobel N.V. Method of producing cellulosic fibres and cellulosic fibres
    DE10019660B4 (en) * 2000-04-20 2004-04-29 Zimmer Ag Process for spinning a spinning solution and spinning head
    AT410319B (en) * 2001-07-25 2003-03-25 Chemiefaser Lenzing Ag CELLULOSE SPONGE AND METHOD FOR THE PRODUCTION THEREOF
    DE10137171A1 (en) * 2001-07-31 2003-02-13 Stockhausen Chem Fab Gmbh Preparation of celluosic shaped bodies having superabsorber properties useful for production of disposable diapers, tampons, bandages, incontinence articles, moisture absorbers, clothing, filters, and packaging materials
    AT502743B1 (en) * 2005-08-26 2008-06-15 Chemiefaser Lenzing Ag CELLULOSIC FORM BODY, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF
    DE102006022009B3 (en) * 2006-05-10 2007-12-06 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Process for producing cellulosic multicomponent fibers
    TWI667378B (en) 2014-01-03 2019-08-01 奧地利商蘭精股份有限公司 Cellulosic fibre

    Family Cites Families (10)

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    Publication number Priority date Publication date Assignee Title
    AT134893B (en) * 1931-11-07 1933-10-10 Warszawska Spolka Akcyjna Budo Crankless motor compressor with two counter-rotating free-flight pistons.
    US4246221A (en) * 1979-03-02 1981-01-20 Akzona Incorporated Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent
    IT1194603B (en) * 1979-12-21 1988-09-22 Snia Viscosa PROCEDURE FOR THE PREPARATION OF BODIES FORMED OF CELLULOSE REGENERATED FROM SOLUTIONS OF CELLULOSE DERIVATIVES IN ORGANIC SOLVENTS
    DD218121A1 (en) * 1983-10-17 1985-01-30 Chemiefaser Komb Schwarza Wilh PROCESS FOR PREPARING FORM BODIES FROM CELLULOSE SOLUTIONS
    SU1224362A1 (en) * 1984-06-29 1986-04-15 Предприятие П/Я А-3844 Method of producing cellulose fibres
    GB9022175D0 (en) * 1990-10-12 1990-11-28 Courtaulds Plc Treatment of fibres
    GB9122318D0 (en) * 1991-10-21 1991-12-04 Courtaulds Plc Treatment of elongate members
    AT396930B (en) * 1992-01-23 1993-12-27 Chemiefaser Lenzing Ag AMINOXIDE
    GB9222059D0 (en) * 1992-10-21 1992-12-02 Courtaulds Plc Fibre treatment
    GB9304887D0 (en) * 1993-03-10 1993-04-28 Courtaulds Plc Fibre treatment

    Also Published As

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    EP0726974A1 (en) 1996-08-21
    CN1135242A (en) 1996-11-06
    AU693589B2 (en) 1998-07-02
    DE59502591D1 (en) 1998-07-23
    NO961782L (en) 1996-05-02
    US5827463A (en) 1998-10-27
    AU3246295A (en) 1996-03-27
    FI961903A0 (en) 1996-05-03
    WO1996007779A1 (en) 1996-03-14
    ATE167533T1 (en) 1998-07-15
    NO961782D0 (en) 1996-05-02
    CA2175462A1 (en) 1996-03-14
    JPH09505120A (en) 1997-05-20
    ATA169594A (en) 1995-10-15
    FI961903A (en) 1996-05-03
    AT401063B (en) 1996-06-25
    BR9506355A (en) 1997-09-16

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