EP0726973A1 - Process for producing a cellulose moulding - Google Patents

Process for producing a cellulose moulding

Info

Publication number
EP0726973A1
EP0726973A1 EP95922341A EP95922341A EP0726973A1 EP 0726973 A1 EP0726973 A1 EP 0726973A1 EP 95922341 A EP95922341 A EP 95922341A EP 95922341 A EP95922341 A EP 95922341A EP 0726973 A1 EP0726973 A1 EP 0726973A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
suspension
solution
shredded
heating surface
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
EP95922341A
Other languages
German (de)
French (fr)
Other versions
EP0726973B1 (en
Inventor
Heinrich Firgo
Dieter Eichinger
Markus Eibl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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 AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Publication of EP0726973A1 publication Critical patent/EP0726973A1/en
Application granted granted Critical
Publication of EP0726973B1 publication Critical patent/EP0726973B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Definitions

  • the present invention relates to a method for producing a cellulosic molding.
  • N-methylmorpholine-N-oxide is used as the solvent.
  • NMMO N-methylmorpholine-N-oxide
  • the abbreviation "NMMO” is used for the term “tertiary amine oxides”, NMMO additionally representing the N-methylmorpholine-N-oxide which is preferably used today.
  • Tertiary amine oxides have long been known as alternative solvents for cellulose. From US Pat. No. 2,179,181 it is known, for example, that tertiary amine oxides are able to dissolve high-quality chemical pulp without derivatization and that from these solutions by precipitation Cellulosic shaped bodies such as fibers can be obtained. US Pat. Nos. 3,447,939, 3,447,956 and 3,508,941 describe further processes for the preparation of cellulosic solutions, cyclic amine oxides preferably being used as solvents. In all of these processes, cellulose is physically dissolved at an elevated temperature.
  • the pulp must be subjected to a preactivation in order to carry out the dissolving process sufficiently quickly (see "The Paper", volume 12, pages 784-788).
  • preactivation the formation and regeneration of alkali cellulose or a hydrothermal cellulose treatment are proposed.
  • the cellulose is preactivated before the solution preparation, which is also carried out in an extruder.
  • the DD-A mentioned is based on an NMMO-containing cellulose suspension which is first homogenized in a stirred vessel. The consistency is then increased to 12.5% by mass by centrifugation or pressing, dried to a water content of 10 to 15% by mass (based on NMMO) and converted into a clear solution in an extruder with a degassing zone at temperatures between 75 and 120 ° C. .
  • EP-A-0 356 419 by the applicant describes a process which is carried out in a so-called film truder in which a suspension of the comminuted, high-quality pulp in an aqueous tertiary amine oxide is transported in the form of a thin layer and is transported over a heating surface, the surface of this thin layer being subjected to a vacuum.
  • a suspension of the comminuted, high-quality pulp in an aqueous tertiary amine oxide is transported in the form of a thin layer and is transported over a heating surface, the surface of this thin layer being subjected to a vacuum.
  • water is evaporated off and the cellulose can be brought into solution, so that a spinnable cellulose solution is discharged from the film spinner.
  • All of the processes described above use high-quality chemical pulp as a starting material, which is obtained, for example, from beech wood or spruce wood. Little is known in the prior art about the use of alternative cellulose-containing materials.
  • NMMO Processing lignocellulosic materials in the NMMO process is known from WO 86/05526. Relatively aggressive conditions are recommended for processing. For example, poplar wood is first subjected to a special hydrolysis process and the solid product obtained is mixed at room temperature with NMMO, which has a water content of 13.5%.
  • the NMMO used is the monohydrate of the NMMO present at room temperature in the solid state (melting point> 70 ⁇ C). The solid mixture is homogenized and heated to 130 ° C. and melted, the hydrolyzed wood dissolving.
  • lignocellulosic material can be dissolved in a solution of NMMO in dimethyl sulfoxide.
  • the NMMO used is not an aqueous solution but has a water content of 15%, which also corresponds approximately to the monohydrate.
  • the object of the invention is to provide a process for the production of cellulosic moldings, in particular lyocell fibers, which uses alternative cellulose materials, ie no cellulose Softwoods and hardwoods, the solution preparation should be as gentle as possible. Melting of a solid mixture product should be avoided.
  • the process according to the invention for producing a cellulosic shaped body, in particular cellulose fibers is characterized by the combination of the measures that a cellulose-containing material is introduced into an aqueous solution of a tertiary amine oxide in order to suspend the cellulose-containing material, from the suspension with intensive mixing and using water is withdrawn from the elevated temperature and reduced pressure until a solution of cellulose is formed, and that the solution is shaped using a molding tool, in particular a spinneret, and introduced into a precipitation bath in order to precipitate the dissolved cellulose with which Provided that essentially shredded waste paper, shredded cellulosic fiber structures and / or shredded, mechanically and / or chemically digested annual plants are used as the cellulose-containing material.
  • Annual plants are understood to mean all cellulose-containing materials apart from coniferous and deciduous trees. Annual plants are known to be poorly or not at all suitable for the production of cellulose fibers in the viscose process.
  • the viscose process uses cellulose from deciduous and coniferous wood as the starting material.
  • the invention is based i.a. recognizing that the above-mentioned alternative pulps, which are only poorly suited for the viscose process, can be processed very well by the Lyocell process.
  • the aqueous solution used to prepare the suspension contains the tertiary amine oxide between 60 and 72% by mass.
  • An advantageous variant of the method according to the invention is that high-quality chemical pulp, which is usually used for the production of viscose, is additionally used as the cellulosic material. It has been shown that by adding high-quality pulp, for example beech wood pulp, high-quality fibers can be produced which are comparable to those which were produced exclusively from high-quality pulp.
  • the process according to the invention is best carried out using N-methylmorpholine-N-oxide.
  • a preferred embodiment of the method according to the invention consists in that the solution is formed by continuously introducing the suspension of the alternative pulp material into an evacuable, heatable vessel, mechanically spreading the introduced suspension to form two surfaces in a layer-like or film-like manner, which spreads out Suspension for the supply of heat is brought into contact with a heating surface over a surface, the spread suspension is transported over the heating surface with vigorous mixing, while the second surface facing away from this heating surface is subjected to a reduced pressure during transport over the heating surface in order to evaporate water, until the cellulose-containing material has dissolved and the solution is continuously withdrawn from the vessel.
  • a useful device in which this embodiment of the method according to the invention can be carried out is the film truder. It has been shown that a film truder is particularly well suited to dissolving alternative pulps. It it is believed that this is due to the high shear forces that occur in the film truder.
  • Used textiles which largely consisted of cotton fibers were mechanically crushed and suspended without further pretreatment in an aqueous solution of NMMO having a water content of 40 mass%, heated to 70 ⁇ C and in a laboratory kneader in a conventional manner at a temperature from 90 to 105 ⁇ C and processed under reduced pressure to a cellulose solution.
  • the content of waste textiles was chosen so that a cellulose concentration of 10% by mass was obtained after the excess water had been evaporated.
  • the cellulose solution was formable and could be spun into cellulose fibers.
  • the fiber data are given in the table below, comparing the data of fibers obtained when high quality chemical pulp is processed.
  • Example 1 was repeated, but instead of waste textiles, deinked waste paper was used and the suspension was processed into a solution in a film truder in accordance with the process described in EP-A-0 356 419. Some data of the fiber spun from the moldable cellulose solution are given in the table.
  • Example 3 (straw pulp)
  • Example 2 was repeated, but instead of old textiles, shredded straw pulp with only 75% ⁇ -cellulose was used.
  • the straw pulp was obtained by digesting straw in a conventional manner using the pre-hydrolysis sulfate process. Some data of the fiber spun from the moldable cellulose solution are given in the table.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Artificial Filaments (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

A process for producing a cellulose moulding, especially cellulose fibres, by the combination of steps in which a cellulose-containing material is introduced into an aqueous solution of a tertiary amine oxide in order to put it in suspension, water is extracted from the suspension with intensive mixing and the application of high temperature and reduced pressure until a cellulose solution is formed, and the solution is moulded using a moulding tool, especially a spinneret, in order to precipitate the dissolved cellulose, with the condition that the dissolved cellulose consists essentially of shredded waste paper, shredded waste cellulose-containing fabrics and/or shredded, mechanically and/or chemically digested annual plants.

Description

Verfahren zur Herstellung eines cellulosischen FormkörpersProcess for producing a cellulosic shaped body
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines cellulosischen Formkörpers.The present invention relates to a method for producing a cellulosic molding.
Als Alternative zum Viskoseverfahren wurden in den letzten Jahren eine Reihe von Verfahren beschrieben, bei denen Cellulose ohne Bildung eines Derivats in einem organischen Lösungsmittel, einer Kombination eines organischen Lösungsmittels mit einem anorganischen Salz oder in wässerigen Salzlösungen gelöst wird. Cellulosefasern, die aus solchen Lösungen hergestellt werden, erhielten von der BISFA (The International Bureau for the Standardisation of man made Fibres) den Gattungsnamen Lyocell zugeteilt. Als Lyocell wird von der BISFA eine Cellulosefaser definiert, die durch ein Spinnverfahren aus einem organischen Lösungsmittel erhalten wird. Unter "organisches Lösungsmittel" wird von der BISFA ein Gemisch aus einer organischen Chemikalie und Wasser verstanden. "Lösungsmittelspinnen" soll Auflösen und Spinnen ohne Derivatisierung bedeuten.As an alternative to the viscose process, a number of processes have been described in recent years in which cellulose is dissolved in an organic solvent, a combination of an organic solvent with an inorganic salt or in aqueous salt solutions without the formation of a derivative. Cellulose fibers made from such solutions were given the generic name Lyocell by BISFA (The International Bureau for the Standardization of man made Fibers). BISFA defines a cellulose fiber as Lyocell, which is obtained from an organic solvent by a spinning process. BISFA understands "organic solvent" as a mixture of an organic chemical and water. "Solvent spinning" is intended to mean dissolving and spinning without derivatization.
Bis heute hat sich jedoch nur ein einziges Verfahren zur Herstellung einer Cellulosefaser der Gattung Lyocell bis zur industriellen Realisierung durchgesetzt. Bei diesem Verfahren wird als Lösungsmittel N-Methylmorpholin-N-oxid (NMMO) verwendet. Für die Zwecke der vorliegenden Beschreibung wird für den Begriff "tertiäre Aminoxide" stellvertretend die Abkürzung "NMMO" verwendet, wobei NMMO noch zusätzlich für das heute vorzugsweise verwendete N-Methylmorpholin-N-oxid steht.To date, however, only a single process for the production of a cellulose fiber of the Lyocell type has prevailed until industrial implementation. In this process, N-methylmorpholine-N-oxide (NMMO) is used as the solvent. For the purposes of the present description, the abbreviation "NMMO" is used for the term "tertiary amine oxides", NMMO additionally representing the N-methylmorpholine-N-oxide which is preferably used today.
Tertiäre Aminoxide sind schon seit langem als alternative Lösungsmittel für Cellulose bekannt. Aus der US-PS 2,179,181 ist beispielsweise bekannt, daß tertiäre Aminoxide hochwertigen Chemiezellstoff ohne Derivatisierung zu lösen vermögen und daß aus diesen Lösungen durch Fällung cellulosische Formkörper wie Fasern gewonnen werden können. In den US-PSen 3,447,939, 3,447,956 und 3,508,941 werden weitere Verfahren zur Herstellung cellulosischer Lösungen beschrieben, wobei als Lösungsmittel bevorzugt cyclische Aminoxide eingesetzt werden. Bei allen diesen Verfahren wird Cellulose bei erhöhter Temperatur physikalisch gelöst.Tertiary amine oxides have long been known as alternative solvents for cellulose. From US Pat. No. 2,179,181 it is known, for example, that tertiary amine oxides are able to dissolve high-quality chemical pulp without derivatization and that from these solutions by precipitation Cellulosic shaped bodies such as fibers can be obtained. US Pat. Nos. 3,447,939, 3,447,956 and 3,508,941 describe further processes for the preparation of cellulosic solutions, cyclic amine oxides preferably being used as solvents. In all of these processes, cellulose is physically dissolved at an elevated temperature.
Wenn die Lösung in einem Doppelschneckenextruder oder in einem Rührgefäß bereitet wird, muß der Zellstoff einer Voraktivierung unterzogen werden, um den Löseprozeß ausreichend schnell zu vollziehen (siehe "Das Papier", Heft 12, Seiten 784-788). Als Voraktivierung werden die Bildung und Regenerierung von Alkalicellulose oder eine hydrothermische Zellstoffbehandlung vorgeschlagen.If the solution is prepared in a twin-screw extruder or in a stirred vessel, the pulp must be subjected to a preactivation in order to carry out the dissolving process sufficiently quickly (see "The Paper", volume 12, pages 784-788). As preactivation, the formation and regeneration of alkali cellulose or a hydrothermal cellulose treatment are proposed.
Auch gemäß der DD-A - 226 573 wird vor der Lösungsbereitung, die ebenfalls in einem Extruder durchgeführt wird, die Cellulose voraktiviert. Die genannte DD-A geht von einer NMMO-hältigen Cellulose-Suspension aus, die zunächst in einem Rührgefäß homogenisiert wird. Anschließend wird durch Zentrifugieren oder Abpressen die Stoffdichte auf 12,5 Massen% erhöht, auf einen Wassergehalt von 10 - 15 Massen% (bezogen auf NMMO) getrocknet und in einem Extruder mit Entgasungszone bei Temperaturen zwischen 75 und 120"C in eine klare Lösung übergeführt.According to DD-A - 226 573, the cellulose is preactivated before the solution preparation, which is also carried out in an extruder. The DD-A mentioned is based on an NMMO-containing cellulose suspension which is first homogenized in a stirred vessel. The consistency is then increased to 12.5% by mass by centrifugation or pressing, dried to a water content of 10 to 15% by mass (based on NMMO) and converted into a clear solution in an extruder with a degassing zone at temperatures between 75 and 120 ° C. .
In der EP-A - 0 356 419 der Anmelderin wird ein Verfahren beschrieben, das in einem sogenannten Filmtruder durchgeführt wird, in welchem eine Suspension des zerkleinerten, hochwertigen Zellstoffs in einem wäßrigen tertiären Aminoxid in Form einer dünnen Schicht ausgebreitet über eine Heizfläche transportiert wird, wobei die Oberfläche dieser dünnen Schicht einem Vakuum ausgesetzt wird. Beim Transport der Suspension über die Heizfläche wird Wasser abgedampft und die Cellulose kann in Lösung gebracht werden, sodaß aus dem Filmtruder eine verspinnbare Celluloselösung ausgetragen wird. Sämtliche der oben beschriebenen Verfahren verwenden als Ausgangsmaterial hochwertigen Chemiezellstoff, der z.B. aus Buchenholz oder Fichtenholz gewonnen wird. Über die Verwendung alternativer, cellulosehaltiger Materialien ist im Stand der Technik wenig bekannt.EP-A-0 356 419 by the applicant describes a process which is carried out in a so-called film truder in which a suspension of the comminuted, high-quality pulp in an aqueous tertiary amine oxide is transported in the form of a thin layer and is transported over a heating surface, the surface of this thin layer being subjected to a vacuum. When the suspension is transported over the heating surface, water is evaporated off and the cellulose can be brought into solution, so that a spinnable cellulose solution is discharged from the film spinner. All of the processes described above use high-quality chemical pulp as a starting material, which is obtained, for example, from beech wood or spruce wood. Little is known in the prior art about the use of alternative cellulose-containing materials.
Eine Verarbeitung lignocellulosischer Materialien im NMMO-Verfahren ist aus der WO 86/05526 bekannt. Für die Verarbeitung werden relativ aggressive Bedingungen empfohlen. So wird beispielsweise Pappelholz zunächst einem speziellen Hydrolyseverfahren unterzogen und das dabei erhaltene feste Produkt bei Raumtemperatur mit NMMO, das einen Wassergehalt von 13,5% aufweist, vermischt. Beim verwendeten NMMO handelt es sich um das bei Raumtemperatur in festem Zustand vorliegende Monohydrat des NMMO (Schmelzpunkt > 70βC). Die feste Mischung wird homogenisiert und auf 130°C erhitzt und aufgeschmolzen, wobei das hydrolysierte Holz in Lösung geht.Processing lignocellulosic materials in the NMMO process is known from WO 86/05526. Relatively aggressive conditions are recommended for processing. For example, poplar wood is first subjected to a special hydrolysis process and the solid product obtained is mixed at room temperature with NMMO, which has a water content of 13.5%. The NMMO used is the monohydrate of the NMMO present at room temperature in the solid state (melting point> 70 β C). The solid mixture is homogenized and heated to 130 ° C. and melted, the hydrolyzed wood dissolving.
Auch in "Holzforschung", 42 , Seiten 21-27 (1988) ist beschrieben, daß lignocellulosisches Material in einer Lösung von NMMO in Dimethylsulfoxid gelöst werden kann. Das eingesetzte NMMO ist keine wäßrige Lösung sondern besitzt einen Wassergehalt von 15%, was ebenfalls etwa dem Monohydrat entspricht."Holzforschung", 42, pages 21-27 (1988) also describes that lignocellulosic material can be dissolved in a solution of NMMO in dimethyl sulfoxide. The NMMO used is not an aqueous solution but has a water content of 15%, which also corresponds approximately to the monohydrate.
Es ist wünschenswert, bei der Herstellung von Celluloselösungen weniger aggressive Bedingungen anzuwenden, bzw. einen Aufschmelzprozeß überhaupt zu vermeiden, da aus der Literatur bekannt ist, daß sowohl die Cellulose als auch NMMO bei erhöhter Temperatur einem Abbauprozeß unterliegen, und daß die Abbauprodukte die physikalischen Daten der Lyocell-Fasern, wie Festigkeit und Dehnung, verschlechtern.It is desirable to use less aggressive conditions in the production of cellulose solutions, or to avoid a melting process at all, since it is known from the literature that both the cellulose and NMMO are subject to a degradation process at elevated temperature and that the degradation products contain the physical data of Lyocell fibers, such as strength and elongation, deteriorate.
Die Erfindung stellt sich die Aufgabe, ein Verfahren zur Herstellung cellulosischer Formkörper, insbesondere von Lyocell-Fasern, zur Verfügung zu stellen, welches alternative Zellstoffmaterialien verwendet, also keine Cellulose aus Nadel- und Laubhölzern, wobei die Lösungsbereitung möglichst schonend erfolgen soll. Ein Aufschmelzen eines festen Mischungsproduktes soll vermieden werden.The object of the invention is to provide a process for the production of cellulosic moldings, in particular lyocell fibers, which uses alternative cellulose materials, ie no cellulose Softwoods and hardwoods, the solution preparation should be as gentle as possible. Melting of a solid mixture product should be avoided.
Das erfindungsgemäße Verfahren zur Herstellung eines cellulosischen Formkörpers, insbesondere Cellulosefasern, ist gekennzeichnet durch die Kombination der Maßnahmen, daß ein cellulosehaltiges Material in eine wässerige Lösung eines tertiären Aminoxids eingebracht wird, um das cellulosehaltige Material zu suspendieren, aus der Suspension unter intensivem Mischen und unter Anwendung von erhöhter Temperatur und verringertem Druck so lange Wasser abgezogen wird, bis eine Lösung von Cellulose gebildet wird, und daß die Lösung unter Verwendung eines Formwerkzeuges, insbesondere einer Spinndüse, geformt und in ein Fällbad eingebracht wird, um die gelöste Cellulose zu fällen, mit der Maßgabe, daß als cellulosehaltiges Material im wesentlichen zerkleinertes Altpapier, zerkleinerte cellulosehaltige Fasergebilde und/oder zerkleinerte, mechanisch und/oder chemisch aufgeschlossene Einjahrespflanzen eingesetzt werden.The process according to the invention for producing a cellulosic shaped body, in particular cellulose fibers, is characterized by the combination of the measures that a cellulose-containing material is introduced into an aqueous solution of a tertiary amine oxide in order to suspend the cellulose-containing material, from the suspension with intensive mixing and using water is withdrawn from the elevated temperature and reduced pressure until a solution of cellulose is formed, and that the solution is shaped using a molding tool, in particular a spinneret, and introduced into a precipitation bath in order to precipitate the dissolved cellulose with which Provided that essentially shredded waste paper, shredded cellulosic fiber structures and / or shredded, mechanically and / or chemically digested annual plants are used as the cellulose-containing material.
Unter Einjahrespflanzen werden sämtliche cellulosehaltigen Materialien außer den Nadel- und Laubhölzern verstanden. Einjahrespflanzen eignen sich bekanntlich im Viskoseverfahren schlecht oder überhaupt nicht zur Herstellung von Cellulosefasern. Das Viskoseverfahren verwendet Cellulose von Laub- und Nadelhölzer als Ausgangsmaterial. Die Erfindung beruht u.a. auf der Erkenntnis, daß die oben genannten alternativen Zellstoffe, die sich für das Viskoseverfahren nur schlecht eignen, nach dem Lyocell-Verfahren sehr gut verarbeitet werden können.Annual plants are understood to mean all cellulose-containing materials apart from coniferous and deciduous trees. Annual plants are known to be poorly or not at all suitable for the production of cellulose fibers in the viscose process. The viscose process uses cellulose from deciduous and coniferous wood as the starting material. The invention is based i.a. recognizing that the above-mentioned alternative pulps, which are only poorly suited for the viscose process, can be processed very well by the Lyocell process.
Die zur Herstellung der Suspension eingesetzte wässerige Lösung enthält das tertiäre Aminoxid zwischen 60 und 72 Massen%. Eine vorteilhafte Variante des erfindungsgemäßen Verfahrens besteht darin, daß als cellulosisches Material zusätzlich hochwertiger Chemiezellstoff eingesetzt wird, welcher üblicherweise zur Herstellung von Viskose verwendet wird. Es hat sich gezeigt, daß durch Zumischen von hochwertigem Zellstoff, z.B. Buchenholzzellstoff, qualitativ hochstehende Fasern hergestellt werden können, die mit jenen vergleichbar sind, welche ausschließlich aus hochwertigem Zellstoff hergestellt wurden.The aqueous solution used to prepare the suspension contains the tertiary amine oxide between 60 and 72% by mass. An advantageous variant of the method according to the invention is that high-quality chemical pulp, which is usually used for the production of viscose, is additionally used as the cellulosic material. It has been shown that by adding high-quality pulp, for example beech wood pulp, high-quality fibers can be produced which are comparable to those which were produced exclusively from high-quality pulp.
Das erfindungsgemäße Verfahren wird am besten mit N-Methyl-morpholin-N-oxid durchgeführt.The process according to the invention is best carried out using N-methylmorpholine-N-oxide.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß die Lösung gebildet wird, indem die Suspension des alternativen Zellstoffmaterials kontinuierlich in ein evakuierbares, beheizbares Gefäß eingebracht wird, die eingebrachte Suspension zur Bildung von zwei Oberflächen schicht- bzw. filmartig mechanisch ausgebreitet wird, die ausgebreitete Suspension zur Wärmezufuhr über eine Oberfläche mit einer Heizfläche in Kontakt gebracht wird, die ausgebreitete Suspension unter intensivem Mischen über die Heizfläche transportiert wird, während des Transportes über die Heizfläche die dieser Heizfläche abgewandte, zweite Oberfläche einem verminderten Druck ausgesetzt wird, um Wasser zu verdampfen, bis das cellulosehaltige Material in Lösung gegangen ist, und die Lösung aus dem Gefäß kontinuierlich abgezogen wird.A preferred embodiment of the method according to the invention consists in that the solution is formed by continuously introducing the suspension of the alternative pulp material into an evacuable, heatable vessel, mechanically spreading the introduced suspension to form two surfaces in a layer-like or film-like manner, which spreads out Suspension for the supply of heat is brought into contact with a heating surface over a surface, the spread suspension is transported over the heating surface with vigorous mixing, while the second surface facing away from this heating surface is subjected to a reduced pressure during transport over the heating surface in order to evaporate water, until the cellulose-containing material has dissolved and the solution is continuously withdrawn from the vessel.
Eine zweckmäßige Einrichtung, in welcher diese Ausführungsform des erfindungsgemäßen Verfahren durchgeführt werden kann, ist der Filmtruder. Es hat sich gezeigt, daß sich ein Filmtruder ganz besonders gut eignet, alternative Zellstoffe zu lösen. Es wird angenommen, daß dies auf die hohen Scherkräfte zurückzuführen ist, die im Filmtruder auftreten.A useful device in which this embodiment of the method according to the invention can be carried out is the film truder. It has been shown that a film truder is particularly well suited to dissolving alternative pulps. It it is believed that this is due to the high shear forces that occur in the film truder.
Mit den nachfolgenden Beispielen wird die Erfindung in einer bevorzugten Ausführungsform näher beschrieben.The invention is described in more detail in a preferred embodiment with the following examples.
Beipiel 1 (Alttextilien)Example 1 (used textiles)
Alttextilien, die überwiegend aus Baumwollfasern bestanden, wurden mechanisch zerkleinert und ohne weitere Vorbehandlung in einer wäßrigen Lösung von NMMO mit einem Wassergehalt von 40 Massen% suspendiert, auf 70βC temperiert und in einem Laborkneter auf herkömmliche Weise bei einer Temperatur zwischen 90 und 105βC und unter vermindertem Druck zu einer Celluloselösung verarbeitet. Der Gehalt an Alttextilien wurde so gewählt, daß nach Abdampfen des überschüssigen Wassers eine Cellulosekonzentration von 10 Masse% erhalten wurde.Used textiles, which largely consisted of cotton fibers were mechanically crushed and suspended without further pretreatment in an aqueous solution of NMMO having a water content of 40 mass%, heated to 70 β C and in a laboratory kneader in a conventional manner at a temperature from 90 to 105 β C and processed under reduced pressure to a cellulose solution. The content of waste textiles was chosen so that a cellulose concentration of 10% by mass was obtained after the excess water had been evaporated.
Die Celluloselösung war formbar und konnte zu Cellulosefasern versponnen werden. Die Faserdaten sind in der nachfolgenden Tabelle angegeben, wobei als Vergleich die Daten von Fasern angegeben sind, die erhalten werden, wenn hochwertiger Chemiezellstoff verarbeitet wird.The cellulose solution was formable and could be spun into cellulose fibers. The fiber data are given in the table below, comparing the data of fibers obtained when high quality chemical pulp is processed.
Beispiel 2 (Altpapier)Example 2 (waste paper)
Beispiel 1 wurde wiederholt, wobei jedoch statt Alttextilien deinktes Altpapier eingesetzt und die Suspension gemäß dem in der EP-A - 0 356 419 beschriebenen Verfahren in einem Filmtruder zu einer Lösung verarbeitet wurde. Einige Daten der aus der formbaren Celluloselösung ersponnenen Faser sind in der Tabelle angegeben. Beispiel 3 (Strohzellstoff)Example 1 was repeated, but instead of waste textiles, deinked waste paper was used and the suspension was processed into a solution in a film truder in accordance with the process described in EP-A-0 356 419. Some data of the fiber spun from the moldable cellulose solution are given in the table. Example 3 (straw pulp)
Beispiel 2 wurde wiederholt, wobei jedoch statt Alttextilien zerkleinerter Strohzellstoff mit lediglich 75% α-Cellulose eingesetzt wurde. Der Strohzellstoff wurde gewonnen, indem Stroh auf herkömmliche Weise nach dem Vorhydrolysesulfat- verfahren aufgeschlossen wurde. Einige Daten der aus der formbaren Celluloselösung ersponnenen Faser sind in der Tabelle angegeben.Example 2 was repeated, but instead of old textiles, shredded straw pulp with only 75% α-cellulose was used. The straw pulp was obtained by digesting straw in a conventional manner using the pre-hydrolysis sulfate process. Some data of the fiber spun from the moldable cellulose solution are given in the table.
Tabelletable
Einsatzmaterial Chemie- Stroh- Altpapier Alttextilien Zellstoff ZellstoffFeed material chemical straw old paper waste textiles cellulose cellulose
Faserfestigkeit 36 31 20 37 kond. (cN/tex)Fiber strength 36 31 20 37 cond. (cN / tex)
Faserdehnung kond. (%) 11 10 10 10Fiber elongation cond. (%) 11 10 10 10
Faserfestigkeit naß (cN/tex) 30 23 n.b. 32Fiber strength wet (cN / tex) 30 23 n.b. 32
Faserdehnung naß (%) 13 13 n.b. 14Fiber elongation wet (%) 13 13 n.a. 14
n.b. = nicht bestimmtn.b. = not determined
Der Tabelle kann entnommen werden, daß die Faserdaten der Fasern, die aus den alternativen Zellstoffen Altpapier, Alttextil und Stroh hergestellt werden, mit jenen Daten vergleichbar sind, die für Fasern erhalten werden, die aus hochwertigem Chemiezellstoff hergestellt sind. Mit den Beispielen wird weiters dokumentiert, daß das Lyocell-Verfahren, welches an sich bereits weit umweltverträglicher arbeitet als das Viskoseverfahren, eingesetzt werden kann, alternative Zellstoffe zu verarbeiten, mit deren Einsatz ein weiteres Umweltproblem gelöst werden kann. From the table it can be seen that the fiber data of the fibers which are produced from the alternative cellulose waste paper, waste textile and straw are comparable with the data which are obtained for fibers which are made from high quality chemical pulp. The examples further document that the lyocell process, which in itself works far more environmentally friendly than the viscose process, can be used to process alternative pulps, the use of which can solve a further environmental problem.

Claims

Patentansprüche: Claims:
1. Verfahren zur Herstellung eines cellulosischen Formkörpers, insbesondere Cellulosefasern, gekennzeichnet durch die Kombination der Maßnahmen, daß ein cellulosehaltiges Material in eine wässerige Lösung eines tertiären Aminoxids eingebracht wird, um das cellulosehaltige Material zu suspendieren, aus der Suspension unter intensivem Mischen und unter Anwendung von erhöhter Temperatur und verringertem Druck so lange Wasser abgezogen wird, bis eine Lösung von Cellulose gebildet wird, und daß die Lösung unter Verwendung eines Formwerkzeuges, insbesondere einer Spinndüse, geformt und in ein Fällbad eingebracht wird, um die gelöste Cellulose zu fällen, mit der Maßgabe, daß als cellulosehaltiges Material im wesentlichen zerkleinertes Altpapier, zerkleinerte ce1lulosehaltige Fasergebilde und/oder zerkleinerte, ir hanisch und/oder chemisch aufgeschlossene Einjahrespflanzen eingesetzt werden.1. A process for the production of a cellulosic molding, in particular cellulose fibers, characterized by the combination of the measures that a cellulose-containing material is introduced into an aqueous solution of a tertiary amine oxide in order to suspend the cellulose-containing material, from the suspension with intensive mixing and using elevated temperature and reduced pressure until water is withdrawn until a solution of cellulose is formed and that the solution is shaped using a molding tool, particularly a spinneret, and placed in a coagulation bath to precipitate the dissolved cellulose, with the proviso that essentially shredded waste paper, shredded ce 1- containing cellulose-containing fiber structures and / or shredded iranian and / or chemically digested annual plants are used as cellulosic material.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die zur Herstellung der Suspension eingesetzte wässerige Lösung das tertiäre Aminoxid zwischen 60 und 72 Massen% enthält.2. The method according to claim 1, characterized in that the aqueous solution used to prepare the suspension contains the tertiary amine oxide between 60 and 72 mass%.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als cellulosisches Material zusätzlich hochwertiger Chemiezellstoff eingesetzt wird.3. The method according to claim 1, characterized in that high-quality chemical pulp is additionally used as cellulosic material.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als tertiäres Aminoxid N-Methyl-morpholin- -N-oxid eingesetzt wird.4. The method according to any one of claims 1 to 3, characterized in that N-methyl-morpholine -N-oxide is used as the tertiary amine oxide.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Lösung gebildet wird, indem die Suspension kontinuierlich in ein evakuierbares, beheizbares Gefäß eingebracht wird, die eingebrachte Suspension zur Bildung von zwei Oberflächen Schicht- bzw. filmartig mechanisch ausgebreitet wird, die ausgebreitete Suspension zur Wärmezufuhr über eine Oberfläche mit einer Heizfläche in Kontakt gebracht wird, die ausgebreitete Suspension unter intensivem Mischen über die Heizfläche transportiert wird, während des Transportes über die Heizfläche die dieser Heizfläche abgewandte, zweite Oberfläche einem verminderten Druck ausgesetzt wird, um Wasser zu verdampfen, bis das cellulosehaltige Material in Lösung gegangen ist, und die Lösung aus dem Gefäß kontinuierlich abgezogen wird. 5. The method according to any one of claims 1 to 4, characterized in that the solution is formed by the suspension is continuously introduced into an evacuable, heatable vessel, the introduced suspension is mechanically spread out to form two surfaces in a layer or film-like manner, the spread suspension is brought into contact with a heating surface via a surface for supplying heat, and the spreading suspension is intensively exposed Mixing is transported over the heating surface, while the second surface facing away from this heating surface is subjected to a reduced pressure during the transport over the heating surface in order to evaporate water until the cellulose-containing material has dissolved and the solution is continuously drawn off from the vessel.
EP95922341A 1994-09-05 1995-06-26 Process for producing a cellulose moulding Expired - Lifetime EP0726973B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT1698/94 1994-09-05
AT0169894A AT401392B (en) 1994-09-05 1994-09-05 METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY
PCT/AT1995/000134 WO1996007778A1 (en) 1994-09-05 1995-06-26 Process for producing a cellulose moulding

Publications (2)

Publication Number Publication Date
EP0726973A1 true EP0726973A1 (en) 1996-08-21
EP0726973B1 EP0726973B1 (en) 1998-09-16

Family

ID=3519060

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95922341A Expired - Lifetime EP0726973B1 (en) 1994-09-05 1995-06-26 Process for producing a cellulose moulding

Country Status (15)

Country Link
US (1) US5601767A (en)
EP (1) EP0726973B1 (en)
JP (1) JPH09505119A (en)
CN (1) CN1040673C (en)
AT (2) AT401392B (en)
AU (1) AU704880B2 (en)
BR (1) BR9506352A (en)
CA (1) CA2175563A1 (en)
DE (2) DE59503610D1 (en)
FI (1) FI114221B (en)
GB (1) GB2297056B (en)
HK (1) HK1010402A1 (en)
MX (1) MX9601671A (en)
NO (1) NO308908B1 (en)
WO (1) WO1996007778A1 (en)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5603884A (en) * 1994-11-18 1997-02-18 Viskase Corporation Reinforced cellulosic film
AT408547B (en) * 1995-09-26 2001-12-27 Chemiefaser Lenzing Ag METHOD FOR TRANSPORTING A SOLUTION OF CELLULOSE IN AN AQUEOUS TERTIARY AMINOXIDE
AT402741B (en) * 1995-10-13 1997-08-25 Chemiefaser Lenzing Ag METHOD FOR PRODUCING CELLULOSIC FIBERS
US6210801B1 (en) 1996-08-23 2001-04-03 Weyerhaeuser Company Lyocell fibers, and compositions for making same
US6306334B1 (en) 1996-08-23 2001-10-23 The Weyerhaeuser Company Process for melt blowing continuous lyocell fibers
US6471727B2 (en) 1996-08-23 2002-10-29 Weyerhaeuser Company Lyocell fibers, and compositions for making the same
US6331354B1 (en) 1996-08-23 2001-12-18 Weyerhaeuser Company Alkaline pulp having low average degree of polymerization values and method of producing the same
CN1061106C (en) * 1997-12-09 2001-01-24 宜宾丝丽雅集团有限公司 Method for producing cellulose fiber by dissolvant method
WO2001086042A1 (en) * 2000-05-10 2001-11-15 Toyo Boseki Kabushiki Kaisya Method for producing formed product of cellulose
AT410319B (en) * 2001-07-25 2003-03-25 Chemiefaser Lenzing Ag CELLULOSE SPONGE AND METHOD FOR THE PRODUCTION THEREOF
US8597518B2 (en) * 2009-08-19 2013-12-03 The University Of Connecticut Pervaporation composite membrane for aqueous solution separation and methods for using the same
AT512601B1 (en) * 2012-03-05 2014-06-15 Chemiefaser Lenzing Ag Process for the preparation of a cellulosic suspension
JP5308554B2 (en) * 2012-04-23 2013-10-09 オーミケンシ株式会社 Non-wood regenerated cellulose fiber and fiber product containing the fiber
US11034817B2 (en) 2013-04-17 2021-06-15 Evrnu, Spc Methods and systems for processing mixed textile feedstock, isolating constituent molecules, and regenerating cellulosic and polyester fibers
AT515174B1 (en) 2013-10-15 2019-05-15 Chemiefaser Lenzing Ag Cellulose suspension, process for its preparation and use
AT515180B1 (en) 2013-10-15 2016-06-15 Chemiefaser Lenzing Ag Three-dimensional cellulosic molding, process for its preparation and its use
AT515152B1 (en) 2013-11-26 2015-12-15 Chemiefaser Lenzing Ag A process for pretreating recovered cotton fibers for use in the manufacture of regenerated cellulose moldings
AT517020B1 (en) 2015-02-06 2020-02-15 Chemiefaser Lenzing Ag Recycling of cellulosic synthetic fibers
EP4219808A1 (en) * 2016-12-06 2023-08-02 Re:NewCell AB Cellulose fibers
WO2018142025A1 (en) 2017-02-01 2018-08-09 Aalto University Foundation Sr A method to convert mechanical pulp derived waste material into value added cellulose products
CN107326530A (en) * 2017-06-15 2017-11-07 东华大学 A kind of preparation method of increasing material manufacturing cotton fiber fabric
EP3511874A1 (en) 2018-01-15 2019-07-17 Lenzing Aktiengesellschaft Encoding of a cellulose product
EP3511451A1 (en) 2018-01-15 2019-07-17 Lenzing Aktiengesellschaft Method for reusing a mixed textile containing cellulose and synthetic plastic
EP4400540A2 (en) * 2018-01-15 2024-07-17 Lenzing Aktiengesellschaft Functionalization of foreign materials in lyocell methods
PL3511449T3 (en) * 2018-01-15 2022-07-18 Lenzing Aktiengesellschaft Reuse of lyocell cellulose for lyocell method
EP3868929A1 (en) * 2018-01-15 2021-08-25 Lenzing Aktiengesellschaft Moulded article comprising cellulose incorporated into elastane and method of manufacturing
EP3511448A1 (en) 2018-01-15 2019-07-17 Lenzing Aktiengesellschaft Method for the recycling of textile material containing cellulose
FR3095819B1 (en) * 2019-05-10 2021-06-18 Inst De Rech Tech Jules Verne PROCESS FOR MANUFACTURING A CARBON FIBER FROM A PAPER PRODUCT
EP3748072A1 (en) * 2019-06-04 2020-12-09 Lenzing Aktiengesellschaft Method for continuously producing a cellulose-comprising prepared material
WO2023180181A1 (en) 2022-03-21 2023-09-28 Phoenxt Pty. Ltd Regenerating cellulose from waste textile
CN115637602A (en) * 2022-10-28 2023-01-24 武汉纺织大学 Method for extracting cellulose in rice straw by adopting organic solvent

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE226573C (en) *
US2179181A (en) * 1936-04-21 1939-11-07 Soc Of Chemical Ind Cellulose solutions and process of making same
US3447939A (en) * 1966-09-02 1969-06-03 Eastman Kodak Co Compounds dissolved in cyclic amine oxides
US3447956A (en) * 1966-09-02 1969-06-03 Eastman Kodak Co Process for strengthening swellable fibrous material with an amine oxide and the resulting material
US4416698A (en) * 1977-07-26 1983-11-22 Akzona Incorporated Shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent and a process for making the article
FR2578865B1 (en) * 1985-03-14 1987-04-10 Centre Nat Rech Scient PROCESS FOR THE PREPARATION OF SOLUTIONS OF A LIGNO-CELLULOSIC MATERIAL AND SOLUTIONS OBTAINED.
AT392972B (en) * 1988-08-16 1991-07-25 Chemiefaser Lenzing Ag METHOD FOR PRODUCING SOLUTIONS OF CELLULOSE AND DEVICE FOR IMPLEMENTING THE METHOD
US5094690A (en) * 1988-08-16 1992-03-10 Lenzing Aktiengesellschaft Process and arrangement for preparing a solution of cellulose

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9607778A1 *

Also Published As

Publication number Publication date
GB2297056A (en) 1996-07-24
GB2297056B (en) 1998-04-08
CA2175563A1 (en) 1996-03-14
JPH09505119A (en) 1997-05-20
NO308908B1 (en) 2000-11-13
MX9601671A (en) 1997-03-29
CN1134732A (en) 1996-10-30
NO961795L (en) 1996-05-03
US5601767A (en) 1997-02-11
DE59503610D1 (en) 1998-10-22
AU704880B2 (en) 1999-05-06
AU2706795A (en) 1996-03-27
NO961795D0 (en) 1996-05-03
GB9607855D0 (en) 1996-06-19
ATE171226T1 (en) 1998-10-15
BR9506352A (en) 1997-09-02
FI961902A0 (en) 1996-05-03
FI114221B (en) 2004-09-15
EP0726973B1 (en) 1998-09-16
HK1010402A1 (en) 1999-06-17
DE19580976D2 (en) 1996-09-26
WO1996007778A1 (en) 1996-03-14
CN1040673C (en) 1998-11-11
ATA169894A (en) 1996-01-15
AT401392B (en) 1996-08-26
FI961902A (en) 1996-05-03

Similar Documents

Publication Publication Date Title
AT401392B (en) METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY
AT403296B (en) METHOD FOR PRODUCING A CELLULOSE MOLDED BODY
DE60122169T2 (en) ALKALINE PULP WITH A LOW AVERAGE POLYMERIZATION LEVEL AND METHOD FOR THE PRODUCTION THEREOF
EP0178292B1 (en) Process for preparing cellulose carbamates
AT514123B1 (en) Polysaccharide film and process for its preparation
DE60302539T2 (en) Use of low specific gravity wood for the production of lyocell products
DE2830685A1 (en) METHOD FOR PRODUCING A SOLUTION OF CELLULOSE IN AN AMINOXYD
EP2524980A1 (en) Method for producing precursor fibres and carbon fibres containing lignine
EP0490870A2 (en) Process for the production of cellulose articles
DE3027033A1 (en) METHOD FOR DISSOLVING CELLULOSE
DE60303900T2 (en) Use of low specific gravity wood for the production of lyocell products
DE60302540T2 (en) Use of low specific gravity wood for the production of lyocell products
DE60123377T2 (en) METHOD FOR PRODUCING FIBERS, FILMS AND OTHER PRODUCTS FROM MODIFIED SOLUBLE CELLULOSE
DE60318810T2 (en) Use of low specific gravity wood for lyocell products
EP0683827B1 (en) Process for producing shaped cellulose bodies
EP2116638B1 (en) Method for creating a cellulose carbamate blown film
AT402739B (en) METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY
EP2110468B1 (en) Cellulose carbamate spinning solution, cellulose carbamate fibre, method for creating same and applications
DE4439149C2 (en) Process for the preparation of a homogeneous cellulose solution
EP0796358B1 (en) Cellulose fibres
DE4440246C2 (en) Process for the production of a biodegradable cellulosic fiber composite
AT413820B (en) METHOD FOR THE PRODUCTION OF CELLULOSIC FORM BODIES
DE4446491C2 (en) Process for the production of cellulose fibers and cellulose fibers with reduced tendency to fibrillate
EP0901533B1 (en) Method for producing a reinforced fiber composite
WO2022170373A1 (en) Method for the chemically assisted mechanical pulping of wood chips or wood shavings

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960424

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: LT PAYMENT 960424;LV PAYMENT 960424;SI PAYMENT 960424

RAX Requested extension states of the european patent have changed

Free format text: LT PAYMENT 960424;LV PAYMENT 960424;SI PAYMENT 960424

17Q First examination report despatched

Effective date: 19970225

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: LT PAYMENT 960424;LV PAYMENT 960424;SI PAYMENT 960424

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980916

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980916

REF Corresponds to:

Ref document number: 171226

Country of ref document: AT

Date of ref document: 19981015

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19980917

REF Corresponds to:

Ref document number: 59503610

Country of ref document: DE

Date of ref document: 19981022

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981216

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 19981106

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19990430

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991231

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000626

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20040520

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20040528

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20040530

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20040603

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20040604

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20040609

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20040709

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050626

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060103

EUG Se: european patent has lapsed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060228

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20050626

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20060101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060228

BERE Be: lapsed

Owner name: *LENZING A.G.

Effective date: 20050630