EP0726973B1 - Process for producing a cellulose moulding - Google Patents
Process for producing a cellulose moulding Download PDFInfo
- Publication number
- EP0726973B1 EP0726973B1 EP95922341A EP95922341A EP0726973B1 EP 0726973 B1 EP0726973 B1 EP 0726973B1 EP 95922341 A EP95922341 A EP 95922341A EP 95922341 A EP95922341 A EP 95922341A EP 0726973 B1 EP0726973 B1 EP 0726973B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- suspension
- solution
- containing material
- 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.)
- Expired - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 44
- 239000001913 cellulose Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000465 moulding Methods 0.000 title claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000010893 paper waste Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- 229920000875 Dissolving pulp Polymers 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- 229920000433 Lyocell Polymers 0.000 description 7
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 229920000297 Rayon Polymers 0.000 description 6
- 239000010902 straw Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241001070947 Fagus Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012978 lignocellulosic material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000218631 Coniferophyta Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 cyclic amine Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines cellulosischen Formkörpers.The present invention relates to a method for Production of a cellulosic shaped body.
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, the last Years described a number of procedures in which Cellulose without the formation of a derivative in an organic Solvent, a combination of an organic Solvent with an inorganic salt or in aqueous Saline solutions is dissolved. Cellulose fibers made from such Solutions are produced by BISFA (The International Bureau for the Standardization of man made Fibers) was assigned the generic name Lyocell. As Lyocell will BISFA defines a cellulose fiber that is made possible by a Spinning process obtained from an organic solvent becomes. The "organic solvent" is used by BISFA Mixture of an organic chemical and water Understood. "Solvent spinning" is meant to dissolve and spin mean 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 one method has been used Production of a cellulose fiber of the Lyocell genus up to industrial implementation. With this procedure is used as solvent N-methylmorpholine-N-oxide (NMMO) used. For the purposes of this description representative of the term "tertiary amine oxides" Abbreviation "NMMO" is used, with NMMO additionally for 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 an alternative Known solvents for cellulose. From U.S. Patent 2,179,181 is known, for example, that tertiary amine oxides to dissolve high quality chemical pulp without derivatization assets and that from these solutions by precipitation Cellulosic shaped bodies such as fibers can be obtained. In U.S. Patents 3,447,939, 3,447,956 and 3,508,941 are others Process for the production of cellulosic solutions described cyclic amine oxides being the preferred solvent be used. All of these processes use cellulose physically dissolved at 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 in a twin screw extruder or in a Stirring vessel is prepared, the pulp must Preactivation undergoes the dissolving process to be carried out sufficiently quickly (see "Das Papier", booklet 12, pages 784-788). Education and Regeneration of alkali cellulose or a hydrothermal Pulp treatment suggested.
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, before the solution is prepared, which is also carried out in an extruder, the Preactivated cellulose. The DD-A is based on one NMMO-containing cellulose suspension, initially in one Mixing vessel is homogenized. Then through Centrifuging or pressing the consistency to 12.5 mass% increased, based on a water content of 10 - 15 mass% dried on NMMO) and in an extruder with degassing zone at temperatures between 75 and 120 ° C in a clear solution transferred.
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. EP-A-0 356 419 by the applicant describes a method described, which is carried out in a so-called film truder in which a suspension of the crushed, high quality pulp in an aqueous tertiary amine oxide in the form of a thin layer spread over a heating surface is transported, the surface of this thin layer is exposed to a vacuum. When transporting the suspension Water is evaporated via the heating surface and the cellulose can be brought into solution so that a spinnable cellulose solution is discharged.
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.All of the methods described above use as Starting material high quality chemical pulp, which e.g. out Beech wood or spruce wood is extracted. About use alternative, cellulose-containing materials is in the state of the Little known technology.
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 > 70°C). 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 method is known from WO 86/05526. For the Processing is recommended in relatively aggressive conditions. For example, poplar wood becomes a special one Hydrolysis process and the solid obtained Product at room temperature with NMMO, which has a water content of 13.5%. Trade in the NMMO used it is the solid at room temperature present monohydrate of NMMO (melting point> 70 ° C). The solid mixture is homogenized and heated to 130 ° C and melted, whereby the hydrolyzed wood goes into solution.
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.Also in "Wood Research", 42, pages 21-27 (1988) described that lignocellulosic material in a solution can be dissolved by NMMO in dimethyl sulfoxide. The NMMO used is not an aqueous solution but has a water content of 15%, which is also about the monohydrate corresponds.
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 in the manufacture of Apply less aggressive conditions to cellulose solutions, or to avoid a melting process at all, since from the It is known from the literature that both cellulose and NMMO subject to a degradation process at elevated temperature, and that the degradation products the physical data of the Lyocell fibers, such as strength and elongation.
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 invention has for its object a method for Production of cellulosic moldings, in particular from Lyocell fibers to provide which alternative Pulp materials used, so no cellulose Conifers and hardwoods, the solution preparation if possible should be done gently. A melting of a solid Mix 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,
- a cellulose-containing material is introduced into an aqueous solution of a tertiary amine oxide in order to suspend the cellulose-containing material,
- water is withdrawn from the suspension with intensive mixing and using 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,
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.All annual cellulose plants are grown under annual plants Understand materials other than softwood and hardwood. Annual plants are known to be suitable in the viscose process bad or not at all for making Cellulose fibers. The viscose process uses cellulose from Deciduous and coniferous wood as a starting material. The invention is based on on the realization that the above alternative pulps that are only for the viscose process poorly suited, very good after the Lyocell process can be processed.
Die zur Herstellung der Suspension eingesetzte wässerige Lösung enthält das tertiäre Aminoxid zwischen 60 und 72 Massen%. The aqueous used to prepare the suspension Solution contains the tertiary amine oxide between 60 and 72 Mass%.
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.An advantageous variant of the method according to the invention is that in addition as a cellulosic material high-quality chemical pulp is used, which commonly used to make viscose. It has been shown that by mixing high quality Pulp, e.g. Beech wood pulp, high quality Fibers can be made that are comparable to those are made exclusively from high quality pulp were manufactured.
Das erfindungsgemäße Verfahren wird am besten mit N-Methyl-morpholin-N-oxid durchgeführt.The method according to the invention is best with N-methyl-morpholine-N-oxide performed.
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.
- the suspension of the alternative cellulose material is continuously introduced into an evacuable, heated vessel,
- the suspension introduced is mechanically spread out in layers or films to form two surfaces,
- the spread suspension for supplying heat is brought into contact with a heating surface over a surface,
- the spread suspension is transported over the heating surface with intensive mixing,
- during transportation over the heating surface, the second surface facing away from this heating surface is subjected to a reduced pressure 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 convenient device in which this embodiment of the method according to the invention can be carried out the film truder. It has been shown that a film truder particularly well suited to dissolve alternative pulps. It it is believed that this is due to the high shear forces is due to occur in the film truder.
Mit den nachfolgenden Beispielen wird die Erfindung in einer bevorzugten Ausführungsform näher beschrieben.The following examples illustrate the invention in one preferred embodiment described in more detail.
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 70°C temperiert und in einem Laborkneter auf herkömmliche Weise bei einer Temperatur zwischen 90 und 105°C 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.Waste textiles, which consisted mainly of cotton fibers, were mechanically crushed and without further pretreatment in an aqueous solution of NMMO with a water content of 40 mass% suspended, tempered to 70 ° C and in one Laboratory kneader in the conventional way at one temperature between 90 and 105 ° C and under reduced pressure to a Processed cellulose solution. The content of used textiles was chosen so that a after evaporation of the excess water Cellulose concentration of 10% by mass was obtained.
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 turn into cellulose fibers be spun. The fiber data are in the following Table given, as a comparison the data of fibers are specified that are obtained when higher quality Chemical pulp is processed.
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. Example 1 was repeated, but instead of old textiles deinked waste paper used and the suspension according to the in of the processes described in EP-A-0 356 419 in one Filmtruder was processed into a solution. Some dates of the fibers spun from the moldable cellulose solution are in given in the table.
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 Vorhydrolysesulfatverfahren
aufgeschlossen wurde. Einige Daten der aus der
formbaren Celluloselösung ersponnenen Faser sind in der
Tabelle angegeben.
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. The table shows that the fiber data of the Fibers made from the alternative cellulose waste paper, Waste textiles and straw are made with those dates are comparable that are obtained for fibers that are made from high quality chemical pulp are made.
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.The examples also document that the Lyocell process, which in itself is already far works more environmentally friendly than the viscose process, can be used to process alternative pulps, with their use, another environmental problem can be solved can.
Claims (5)
- Method of producing a cellulosic moulded body, in particular cellulose fibres, whereina cellulose-containing material is introduced into an aqueous solution of a tertiary amine oxide in order to suspend the cellulose-containing material,water is distilled off from the suspension while mixing intensively and while applying elevated temperature and reduced pressure until a solution of cellulose is formed, and in thatthe solution is moulded using a moulding tool, in particular a spinneret, and introduced into a precipitation bath in order to precipitate the dissolved cellulose,
- Method according to Claim 1, characterized in that the aqueous solution used to produce the suspension contains between 60 and 72% by mass of tertiary amine oxide.
- Method according to Claim 1, characterized in that high-grade dissolving pulp is additionally used as cellulosic material.
- Method according to one of Claims 1 to 3, characterized in that N-methylmorpholine N-oxide is used as tertiary amine oxide.
- Method according to one of Claims 1 to 4, characterized in that the solution is formed bycontinuously introducing the suspension into an evacuable, heatable vessel,the suspension introduced is spread out mechanically in sheet-like or film-like fashion to form two surfaces,the suspension spread out is brought into contact with a heating surface for the purpose of supplying heat via one surface,the spread-out suspension is conveyed across the heating surface while mixing intensively,during the conveyance across the heating surface, the second surface remote from said heating surface is exposed to a reduced pressure in order to evaporate water until the cellulose-containing material has dissolved, andthe solution is continuously drawn off from the vessel.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0169894A AT401392B (en) | 1994-09-05 | 1994-09-05 | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
AT1698/94 | 1994-09-05 | ||
PCT/AT1995/000134 WO1996007778A1 (en) | 1994-09-05 | 1995-06-26 | Process for producing a cellulose moulding |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0726973A1 EP0726973A1 (en) | 1996-08-21 |
EP0726973B1 true 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 (30)
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 |
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 |
US6471727B2 (en) | 1996-08-23 | 2002-10-29 | Weyerhaeuser Company | Lyocell fibers, and compositions for making 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 |
US11414789B2 (en) * | 2016-12-06 | 2022-08-16 | Re:Newcell Ab | Cellulose fibers |
CN110249093B (en) | 2017-02-01 | 2022-04-15 | 阿尔托大学注册基金会 | Method for converting mechanical pulp-derived waste 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 |
ES2911218T3 (en) * | 2018-01-15 | 2022-05-18 | Chemiefaser Lenzing Ag | Reuse of Lyocell cellulose fiber for the Lyocell process |
EP3511446A1 (en) * | 2018-01-15 | 2019-07-17 | Lenzing Aktiengesellschaft | Moulded article comprising cellulose incorporated into elastane and method of manufacturing |
EP3511874A1 (en) | 2018-01-15 | 2019-07-17 | Lenzing Aktiengesellschaft | Encoding of a cellulose product |
EP3511448A1 (en) | 2018-01-15 | 2019-07-17 | Lenzing Aktiengesellschaft | Method for the recycling of textile material containing cellulose |
EP3511447A1 (en) | 2018-01-15 | 2019-07-17 | Lenzing Aktiengesellschaft | Functionalization of foreign substances in lyocell method |
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)
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 |
-
1994
- 1994-09-05 AT AT0169894A patent/AT401392B/en not_active IP Right Cessation
-
1995
- 1995-06-06 US US08/483,565 patent/US5601767A/en not_active Expired - Fee Related
- 1995-06-26 EP EP95922341A patent/EP0726973B1/en not_active Expired - Lifetime
- 1995-06-26 WO PCT/AT1995/000134 patent/WO1996007778A1/en active IP Right Grant
- 1995-06-26 BR BR9506352A patent/BR9506352A/en not_active IP Right Cessation
- 1995-06-26 AT AT95922341T patent/ATE171226T1/en not_active IP Right Cessation
- 1995-06-26 AU AU27067/95A patent/AU704880B2/en not_active Ceased
- 1995-06-26 JP JP8509024A patent/JPH09505119A/en not_active Ceased
- 1995-06-26 CA CA002175563A patent/CA2175563A1/en not_active Abandoned
- 1995-06-26 DE DE59503610T patent/DE59503610D1/en not_active Expired - Fee Related
- 1995-06-26 CN CN95190846A patent/CN1040673C/en not_active Expired - Fee Related
- 1995-06-26 DE DE19580976T patent/DE19580976D2/en not_active Expired - Fee Related
- 1995-06-26 GB GB9607855A patent/GB2297056B/en not_active Revoked
- 1995-06-26 MX MX9601671A patent/MX9601671A/en unknown
-
1996
- 1996-05-03 FI FI961902A patent/FI114221B/en not_active IP Right Cessation
- 1996-05-03 NO NO961795A patent/NO308908B1/en not_active IP Right Cessation
-
1998
- 1998-10-13 HK HK98111218A patent/HK1010402A1/en not_active IP Right Cessation
Non-Patent Citations (2)
Title |
---|
H. Temming & H. Grunert: "Temming-Linters", Peter Temming AG, Glückstadt (1965), S.11, 12, 14, 16, 22, 26 * |
Melliand Textilberichte 6/1994, S. 458 * |
Also Published As
Publication number | Publication date |
---|---|
US5601767A (en) | 1997-02-11 |
NO961795L (en) | 1996-05-03 |
MX9601671A (en) | 1997-03-29 |
CN1134732A (en) | 1996-10-30 |
HK1010402A1 (en) | 1999-06-17 |
FI961902A (en) | 1996-05-03 |
GB2297056B (en) | 1998-04-08 |
CA2175563A1 (en) | 1996-03-14 |
WO1996007778A1 (en) | 1996-03-14 |
DE19580976D2 (en) | 1996-09-26 |
JPH09505119A (en) | 1997-05-20 |
NO308908B1 (en) | 2000-11-13 |
GB9607855D0 (en) | 1996-06-19 |
FI961902A0 (en) | 1996-05-03 |
BR9506352A (en) | 1997-09-02 |
DE59503610D1 (en) | 1998-10-22 |
EP0726973A1 (en) | 1996-08-21 |
GB2297056A (en) | 1996-07-24 |
FI114221B (en) | 2004-09-15 |
AU2706795A (en) | 1996-03-27 |
AT401392B (en) | 1996-08-26 |
ATA169894A (en) | 1996-01-15 |
NO961795D0 (en) | 1996-05-03 |
AU704880B2 (en) | 1999-05-06 |
ATE171226T1 (en) | 1998-10-15 |
CN1040673C (en) | 1998-11-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0726973B1 (en) | Process for producing a cellulose moulding | |
AT514123B1 (en) | Polysaccharide film and process for its preparation | |
AT403296B (en) | METHOD FOR PRODUCING A CELLULOSE MOLDED BODY | |
EP2981640B1 (en) | Polysaccharide fibres and method for the production thereof | |
EP0178292B1 (en) | Process for preparing cellulose carbamates | |
DE60302539T2 (en) | Use of low specific gravity wood for the production of lyocell products | |
EP0490870A2 (en) | Process for the production of cellulose articles | |
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 | |
EP3511451A1 (en) | Method for reusing a mixed textile containing cellulose and synthetic plastic | |
EP0683827B1 (en) | Process for producing shaped cellulose bodies | |
EP3511449B1 (en) | Reuse of lyocell cellulose for lyocell method | |
EP0792393B1 (en) | Method of manufacturing a cellulose product | |
EP2116638A1 (en) | Cellulose carbamate spinning solution, cellulose carbamate blown film, method for creating same and applications | |
EP2110468A1 (en) | Cellulose carbamate spinning solution, cellulose carbamate fibre, method for creating same and applications | |
DE4440246C2 (en) | Process for the production of a biodegradable cellulosic fiber composite | |
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 | |
AT413820B (en) | METHOD FOR THE PRODUCTION OF CELLULOSIC FORM BODIES | |
EP3536833A1 (en) | Lyocell fibres without mannan |
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 |