EP0901533B1 - Method for producing a reinforced fiber composite - Google Patents

Method for producing a reinforced fiber composite Download PDF

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Publication number
EP0901533B1
EP0901533B1 EP98903942A EP98903942A EP0901533B1 EP 0901533 B1 EP0901533 B1 EP 0901533B1 EP 98903942 A EP98903942 A EP 98903942A EP 98903942 A EP98903942 A EP 98903942A EP 0901533 B1 EP0901533 B1 EP 0901533B1
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EP
European Patent Office
Prior art keywords
nmmo
fiber composite
solution
aqueous
cellulose
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EP98903942A
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German (de)
French (fr)
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EP0901533A1 (en
Inventor
Hartmut Rüf
Heinrich Firgo
Siegfried Ambrosch
Christian Schlossnikl
Raimund Jurkovic
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D04H1/645—Impregnation followed by a solidification process
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/388—Amine oxides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the present invention relates to a method for Production of a consolidated fiber composite, which contains cellulosic fibers. If the cellulose in the Crystal structure cellulose II is present by contacting the Fiber composite with an aqueous solution of N-methylmorpholine-N-oxide (NMMO) at elevated temperature and subsequent washing of the fiber composite solidifies the Verbund achieved if defined conditions are met.
  • NMMO N-methylmorpholine-N-oxide
  • fiber composite denote any type of fabric, fleece or scrim.
  • NMMO N-methylmorpholine-N-oxide
  • 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.
  • EP-A-0 356 419 by the applicant describes a method described, preferably in a thin film treatment apparatus is carried out in which a suspension of crushed pulp in an aqueous tertiary amine oxide, spread out in the form of a thin layer, over a Heating surface is transported, the surface of this thin layer is exposed to a vacuum. While transporting water is evaporated from the suspension over the heating surface and the cellulose can be brought into solution so that from the Thin film treatment apparatus a spinnable Cellulose solution is discharged.
  • a method and an apparatus for spinning Cellulose solutions are e.g. from WO 93/19230 by the applicant known.
  • the spinning solution becomes warm spun and the filaments obtained are in a precipitation bath introduced to precipitate the cellulose contained, the Filaments are cooled down before being placed in the precipitation bath. Cooling is done immediately after molding and consists preferably in a horizontal blowing of the cellulosic molded body with air.
  • German patent specification No. 902 427 describes this Solidifying a fleece made of cellulose fibers using a Lye bath containing 5 to 15% NaOH. With the lye bath the cellulose fibers are swollen, causing a Consolidation takes place.
  • WO 95/07386 by the applicant describes a method for Manufacture of paper known in which an aqueous Suspension of crushed cellulosic material treated mechanically and then one Sheet formation is subjected to the suspension contains tertiary amine oxide. This procedure allows the Manufacture of high strength paper.
  • One method is to solidify a fibrous material known from US-A-3,447,956.
  • the consolidation will made by the fibrous material with an amine oxide soaked and heated to a temperature at which the Amine oxide can solidify the fibrous material.
  • a fibrous Materials become fabrics and nonwovens, which are natural cellulosic fibers, e.g. Pulp, cotton, linen, but also synthetic fibers, e.g. Rayon (viscose fibers) involve, proposed.
  • NMMO will be there apparently as a monohydrate in molten or liquid form or in solution with a volatile, evaporable Solvent used.
  • fiber composites which with a cellulosic coating, impregnation or wrapping are provided. These fiber composites are manufactured by the fiber composite with a solution of cellulose in one aqueous NMMO is coated on one side, after which the layer is coagulated in a water bath.
  • the invention has for its object a method of to provide the type mentioned at the beginning, in which a Fiber composite without complex evaporation of a volatile Solvent or without the need to Use NMMO monohydrate or by evaporation produce, can be solidified.
  • the process according to the invention for producing a consolidated fiber composite which contains cellulosic fibers, the cellulose being present in the cellulose II crystal structure, by contacting the fiber composite with an aqueous solution of N-methylmorpholine-N-oxide (NMMO) at elevated temperature and then washing the Fiber composite, is characterized in that the contacting is carried out so that the relationship -947 + 0.30xlog (10) t + 0.046xT - 3.53xC + 645xlog (10) C in which t is the time in minutes that the fiber composite is contacted with the aqueous NMMO solution, T is the temperature of the aqueous NMMO solution in ° C, and C is the concentration of the NMMO in mass%, based on the aqueous NMMO Solution means a number in the range from 0.30 and 1.70, preferably in the range from 0.5 to 1.5, and particularly preferably in the range from 0.8 to 1.2, with the proviso that the temperature T is less than 130 ° C and the concentration C
  • the invention is based on the knowledge that for solidification a network, e.g. a fleece, made of cellulose fibers apparently the three parameters mentioned, i.e. the concentration the NMMO solution, its temperature and the impregnation time, are essential and sufficient and that they also go beyond must be chosen so that the above relationship is satisfied becomes. However, if these parameters are chosen so that the Relationship is less than 0.30, none can Solidification of the bond can be achieved. Will the On the other hand, parameters are chosen so that the relationship is one If the value is higher than 1.70, the fiber composite will dissolve observed in the NMMO solution.
  • the temperature T is preferred in the process according to the invention less than 100 ° C.
  • a special embodiment of the invention is characterized in that the fiber composite is pressed before washing.
  • the pressing can on simple way e.g. be made so that the fleece is guided between two rollers that put pressure on the Exercise fiber composite.
  • the parameters to be set according to the invention namely the concentration of the respective NMMO solution (in% by mass NMMO, based on the total mass of the solution), its temperature (in ° C.) and the impregnation time (in Minutes) were chosen as indicated in Table 1 below. All of the examples meet the relationship given above. The value resulting from the parameters is also given in the table. E.g.
  • Examples 1 to 15 are in accordance with the invention, since they deal with the NMMO concentration, the temperature and the impregnation time resulting values from the above relationship in range specified according to the invention. All fleeces proved after the treatment according to the invention as solidified.

Landscapes

  • Textile Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Nonwoven Fabrics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Paper (AREA)

Abstract

The invention relates to a method for producing a reinforced fiber composite which contains cellulosic fibers, the cellulose being present in the crystalline structure cellulose II, by bringing said fiber composite into contact with an aqueous solution of N-methylmorpholin-N-oxide (NMMO) at an elevated temperature and subsequently washing said fiber composite. Said method is characterized in that the fiber composite is brought into contact with the aqueous solution in such a way that the reationship -947 + 0.30xlog(10)t + 0.046xT - 3.53xC + 645xlog(10)C where t is the time in minutes during which the fiber composite is kept in contact with the aqueous NMMO solution, T is the temperature of the aqueous NMMO solution in DEG C and C is the concentration of the NMMO in % mass in relation to the aqueous NMMO solution, gives a figure in the region of 0.30 and 1.70 on the condition that the temperature T is less than 130 DEG C and the concentration C lies in the region of 70 to 84 % mass.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines verfestigten Faserverbundes, welcher cellulosische Fasern enthält. Wenn die Cellulose in der Kristallstruktur Cellulose II vorliegt, wird durch Kontaktieren des Faserverbundes mit einer wässerigen Lösung von N-Methylmorpholin-N-oxid (NMMO) bei erhöhter Temperatur und anschließendem Waschen des Faserverbundes eine verfestigung des Verbundes erzielt, wenn definierte Bedingungen eingehalten werden.The present invention relates to a method for Production of a consolidated fiber composite, which contains cellulosic fibers. If the cellulose in the Crystal structure cellulose II is present by contacting the Fiber composite with an aqueous solution of N-methylmorpholine-N-oxide (NMMO) at elevated temperature and subsequent washing of the fiber composite solidifies the Verbund achieved if defined conditions are met.

Für die Zwecke der vorliegenden Beschreibung und der vorliegenden Patentansprüche soll der Ausdruck "Faserverbund" jegliche Art von Gewebe, Vlies oder Gelege bezeichnen.For the purposes of this description and the the present patent claims, the term "fiber composite" denote any type of fabric, fleece or scrim.

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.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 Roger that.

Bis heute hat sich jedoch nur ein einziges Verfahren zur Herstellung einer cellulosefaser der Gattung Lyocell bis zur industriellen Realisierung durchgesetzt, und zwar das Aminoxidverfahren. Bei diesem Verfahren wird als Lösungsmittel bevorzugt 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, namely Amine oxide process. This process uses as a solvent preferably N-methylmorpholine-N-oxide (NMMO) used. For the Purpose of the present description is for the term "Tertiary amine oxides" represent the abbreviation "NMMO" used, with NMMO additionally for today preferably used N-methylmorpholine-N-oxide.

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.

In der EP-A - 0 356 419 der Anmelderin wird ein Verfahren beschrieben, das vorzugsweise in einem Dünnschichtbehandlungsapparat durchgeführt wird, in welchem eine Suspension des zerkleinerten 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 Dünnschichtbehandlungsapparat eine verspinnbare Celluloselösung ausgetragen wird.EP-A-0 356 419 by the applicant describes a method described, preferably in a thin film treatment apparatus is carried out in which a suspension of crushed pulp in an aqueous tertiary amine oxide, spread out in the form of a thin layer, over a Heating surface is transported, the surface of this thin layer is exposed to a vacuum. While transporting water is evaporated from the suspension over the heating surface and the cellulose can be brought into solution so that from the Thin film treatment apparatus a spinnable Cellulose solution is discharged.

Ein Verfahren und eine Vorrichtung zum Verspinnen von Celluloselösungen sind z.B. aus der WO 93/19230 der Anmelderin bekannt. Dabei wird die Spinnlösung in warmem Zustand versponnen und werden die erhaltenen Filamente in ein Fällbad eingebracht, um die enthaltene Cellulose zu fällen, wobei die Filamente vor dem Einbringen in das Fällbad abgekühlt werden. Die Kühlung wird unmittelbar nach dem Formen vorgenommen und besteht vorzugsweise in einem horizontalen Anblasen des cellulosischen Formkörpers mit Luft. A method and an apparatus for spinning Cellulose solutions are e.g. from WO 93/19230 by the applicant known. The spinning solution becomes warm spun and the filaments obtained are in a precipitation bath introduced to precipitate the cellulose contained, the Filaments are cooled down before being placed in the precipitation bath. Cooling is done immediately after molding and consists preferably in a horizontal blowing of the cellulosic molded body with air.

Die deutsche Patentschrift Nr. 902 427 beschreibt das Verfestigen eines Vlieses aus Cellulosefasern mittels eines Laugebades, welches 5 bis 15% NaOH enthält. Mit dem Laugebad werden die Cellulosefasern angequollen, wodurch eine Verfestigung stattfindet.German patent specification No. 902 427 describes this Solidifying a fleece made of cellulose fibers using a Lye bath containing 5 to 15% NaOH. With the lye bath the cellulose fibers are swollen, causing a Consolidation takes place.

Aus der WO 95/07386 der Anmelderin ist ein Verfahren zur Herstellung von Papier bekannt, bei welchem eine wässerige Suspension von zerkleinertem cellulosischem Material mechanisch behandelt und anschließend einem Blattbildungsvorgang unterzogen wird, wobei die Suspension ein tertiäres Aminoxid enthält. Dieses Verfahren gestattet die Herstellung von Papier hoher Festigkeit.WO 95/07386 by the applicant describes a method for Manufacture of paper known in which an aqueous Suspension of crushed cellulosic material treated mechanically and then one Sheet formation is subjected to the suspension contains tertiary amine oxide. This procedure allows the Manufacture of high strength paper.

Ein Verfahren zum Verfestigen eines faserigen Materials ist aus der US-A - 3,447,956 bekannt. Die Verfestigung wird vorgenommen, indem das faserige Material mit einem Aminoxid getränkt und auf eine Temperatur erhitzt wird, bei welcher das Aminoxid das faserige Material verfestigen kann. Als faseriges Material werden Gewebe und Nonwovens, welche natürliche cellulosische Fasern, wie z.B. Zellstoff, Baumwolle, Leinen, aber auch synthetische Fasern, wie z.B. Rayon (Viskosefasern) beinhalten, vorgeschlagen. Insbesondere bervorzugt ist die Behandlung von Papier mit dem Aminoxid. NMMO wird dabei offenbar als Monohydrat in geschmolzener bzw. flüssiger Form oder in Lösung mit einem flüchtigen, eindampfbaren Lösungsmittel eingesetzt.One method is to solidify a fibrous material known from US-A-3,447,956. The consolidation will made by the fibrous material with an amine oxide soaked and heated to a temperature at which the Amine oxide can solidify the fibrous material. As a fibrous Materials become fabrics and nonwovens, which are natural cellulosic fibers, e.g. Pulp, cotton, linen, but also synthetic fibers, e.g. Rayon (viscose fibers) involve, proposed. The is particularly preferred Treatment of paper with the amine oxide. NMMO will be there apparently as a monohydrate in molten or liquid form or in solution with a volatile, evaporable Solvent used.

Aus der WO 96/37653 sind Faserverbunde bekannt, die mit einer cellulosischen Beschichtung, Imprägnierung oder Umhüllung versehen sind. Diese Faserverbunde werden hergestellt, indem der Faserverbund mit einer Lösung von Cellulose in einem wäßrigen NMMO einseitig beschichtet wird, wonach die Schicht in einem Wasserbad koaguliert wird.From WO 96/37653 fiber composites are known, which with a cellulosic coating, impregnation or wrapping are provided. These fiber composites are manufactured by the fiber composite with a solution of cellulose in one aqueous NMMO is coated on one side, after which the layer is coagulated in a water bath.

Die US-A - 4,196,282 beschreibt das Dreikomponentensystem NMMO/H2O/Cellulose und das sogenannte "Lösefenster", also jene Bedingungen, unter denen sich die Cellulose im wäßrigen NMMO auflöst.US Pat. No. 4,196,282 describes the three-component system NMMO / H 2 O / cellulose and the so-called "dissolving window", that is to say those conditions under which the cellulose dissolves in the aqueous NMMO.

Ferner ist bekannt, daß Cellulosefasern mit NMMO gequollen werden können (Chancy et al., "Swelling and Dissolution of Cellulose in Amine Oxide/Water Systems"; J.App.Pol.Sci: Appl.Pol.Symp. 37, 239-259 (1983)).It is also known that cellulose fibers swelled with NMMO (Chancy et al., "Swelling and Dissolution of Cellulose in Amine Oxide / Water Systems "; J.App.Pol.Sci: Appl.Pol.Symp. 37: 239-259 (1983)).

Die Erfindung stellt sich die Aufgabe, ein Verfahren der eingangs erwähnten Art bereitzustellen, bei welchem ein Faserverbund ohne aufwendiges Eindampfen eines flüchtigen Lösungsmittels bzw. ohne die Notwendigkeit, ein NMMO-Monohydrat einzusetzen bzw. durch Eindampfen herzustellen, verfestigt werden kann.The invention has for its object a method of to provide the type mentioned at the beginning, in which a Fiber composite without complex evaporation of a volatile Solvent or without the need to Use NMMO monohydrate or by evaporation produce, can be solidified.

Das erfindungsgemäße Verfahren zur Herstellung eines verfestigten Faserverbundes, welcher cellulosische Fasern enthält, wobei die Cellulose in der Kristallstruktur Cellulose II vorliegt, durch Kontaktieren des Faserverbundes mit einer wässerigen Lösung von N-Methylmorpholin-N-oxid (NMMO) bei erhöhter Temperatur und anschließendem Waschen des Faserverbundes, ist dadurch gekennzeichnet, daß das Kontaktieren so ausgeführt wird, daß die Beziehung -947 + 0,30xlog(10)t + 0,046xT - 3,53xC + 645xlog(10)C in welcher t die Zeit in Minuten bedeutet, die der Faserverbund mit der wässerigen NMMO-Lösung kontaktiert wird, T die Temperatur der wässerigen NMMO-Lösung in °C bedeutet, und C die Konzentration des NMMO in Masse-%, bezogen auf die wässerige NMMO-Lösung, bedeutet, eine Zahl im Bereich von 0,30 und 1,70, bevorzugt im Bereich von 0,5 bis 1,5, und besonders bevorzugt im Bereich von 0,8 bis 1,2, ergibt,
mit der Maßgabe, daß die Temperatur T kleiner als 130°C ist und die Konzentration C im Bereich von 70 bis 84 Masse-% liegt. The process according to the invention for producing a consolidated fiber composite which contains cellulosic fibers, the cellulose being present in the cellulose II crystal structure, by contacting the fiber composite with an aqueous solution of N-methylmorpholine-N-oxide (NMMO) at elevated temperature and then washing the Fiber composite, is characterized in that the contacting is carried out so that the relationship -947 + 0.30xlog (10) t + 0.046xT - 3.53xC + 645xlog (10) C in which t is the time in minutes that the fiber composite is contacted with the aqueous NMMO solution, T is the temperature of the aqueous NMMO solution in ° C, and C is the concentration of the NMMO in mass%, based on the aqueous NMMO Solution means a number in the range from 0.30 and 1.70, preferably in the range from 0.5 to 1.5, and particularly preferably in the range from 0.8 to 1.2,
with the proviso that the temperature T is less than 130 ° C and the concentration C is in the range of 70 to 84% by mass.

Die Erfindung beruht auf der Erkenntnis, daß zur Verfestigung eines Verbundes, z.B. eines Vlieses, aus Cellulosefasern offenbar die drei genannten Parameter, also die Konzentration der NMMO-Lösung, ihre Temperatur und die Imprägnierzeit, wesentlich und ausreichend sind und daß sie darüberhinaus noch so gewählt werden müssen, daß die obige Beziehung erfüllt wird. Werden diese Parameter hingegen so gewählt, daß die Beziehung einen kleineren Wert als 0,30 ergibt, so kann keine Verfestigung des Verbundes erzielt werden. Werden die Parameter andererseits so gewählt, daß die Beziehung einen Wert über 1,70 ergibt, so wird ein Auflösen des Faserverbundes in der NMMO-Lösung beobachtet.The invention is based on the knowledge that for solidification a network, e.g. a fleece, made of cellulose fibers apparently the three parameters mentioned, i.e. the concentration the NMMO solution, its temperature and the impregnation time, are essential and sufficient and that they also go beyond must be chosen so that the above relationship is satisfied becomes. However, if these parameters are chosen so that the Relationship is less than 0.30, none can Solidification of the bond can be achieved. Will the On the other hand, parameters are chosen so that the relationship is one If the value is higher than 1.70, the fiber composite will dissolve observed in the NMMO solution.

Im erfindungsgemäßen Verfahren ist die Temperatur T bevorzugt kleiner als 100°C.The temperature T is preferred in the process according to the invention less than 100 ° C.

Eine besondere Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß der Faserverbund vor dem Waschen verpreßt wird. Das Verpressen kann auf einfache Weise z.B. so vorgenommen werden, daß das Vlies zwischen zwei Walzen geführt wird, die einen Druck auf den Faserverbund ausüben.A special embodiment of the invention The method is characterized in that the fiber composite is pressed before washing. The pressing can on simple way e.g. be made so that the fleece is guided between two rollers that put pressure on the Exercise fiber composite.

Im erfindungsgemäßen Verfahren hat sich der Einsatz eines Faserverbundes besonders bewährt, dessen Fasern zumindest teilweise nach dem Aminoxidverfahren oder dem Viskoseverfahren hergestellt wurden.In the method according to the invention, the use of a Fiber composite particularly proven, the fibers at least partly by the amine oxide process or the viscose process were manufactured.

Mit den nachfolgenden Beispielen wird die Erfindung noch näher beschrieben.The invention is illustrated in more detail with the following examples described.

Allgemeine ArbeitsvorschriftGeneral working instructions

Schwach genadelte Viskosefaservliese mit einer Größe von jeweils 12 x 16 cm und einem Flächengewicht von etwa 70 g/cm2 wurden zwischen zwei Sieben in eine wäßrige NMMO-Lösung getaucht und Imprägnieren gelassen, wonach die imprägnierten Vliese mittels einer Laborpresse verpreßt wurden (Preßdruck: 3 bar; entsprechend einem Liniendruck von 12,6 N/mm bei einer Vliesbreite von 12 cm). Anschließend wurden die verpreßten Vliese 15 Minuten mit Leitungswasser gewaschen.Weakly needled viscose nonwovens with a size of 12 x 16 cm and a weight per unit area of about 70 g / cm 2 were immersed in an aqueous NMMO solution between two sieves and left to impregnate, after which the impregnated nonwovens were pressed using a laboratory press (pressing pressure: 3 bar; corresponding to a line pressure of 12.6 N / mm with a fleece width of 12 cm). The pressed nonwovens were then washed with tap water for 15 minutes.

BeispieleExamples

Gemäß obiger allgemeiner Arbeitsvorschrift wurden mehrere Versuche durchgeführt, wobei die erfindungsgemäß einzustellenden Parameter, nämlich die Konzentration der jeweiligen NMMO-Lösung (in Masse-% NMMO, bezogen auf die Gesamtmasse der Lösung), ihre Temperatur (in °C) und die Imprägnierzeit (in Minuten) so gewählt wurden, wie sie in der folgenden Tabelle 1 angegeben sind. Sämtliche Beispiele erfüllen die oben angegebene Beziehung. Der sich mit den Parametern ergebende Wert ist ebenfalls in der Tabelle angegeben. Bsp. NMMO-Konzentration Temperatur Zeit Wert 1 84,0 80 0,08 0,95 2 82,0 80 0,08 1,30 3 82,0 70 0,17 0,94 4 80,6 70 0,50 1,20 5 80,6 80 0,08 1,42 6 80,6 80 0,50 1,66 7 78,2 70 1,00 1,29 8 76,2 70 0,50 1,00 9 76,2 80 0,17 1,32 10 73,9 70 4,00 0,81 11 74,2 80 0,50 1,07 12 74,2 90 0,17 1,39 13 71,9 90 2,00 1,02 14 71,9 100 0,17 1,16 15 70,0 100 0,50 0,49 According to the above general working procedure, several tests were carried out, the parameters to be set according to the invention, namely the concentration of the respective NMMO solution (in% by mass NMMO, based on the total mass of the solution), its temperature (in ° C.) and the impregnation time (in Minutes) were chosen as indicated in Table 1 below. All of the examples meet the relationship given above. The value resulting from the parameters is also given in the table. E.g. NMMO concentration temperature time value 1 84.0 80 0.08 0.95 2nd 82.0 80 0.08 1.30 3rd 82.0 70 0.17 0.94 4th 80.6 70 0.50 1.20 5 80.6 80 0.08 1.42 6 80.6 80 0.50 1.66 7 78.2 70 1.00 1.29 8th 76.2 70 0.50 1.00 9 76.2 80 0.17 1.32 10th 73.9 70 4.00 0.81 11 74.2 80 0.50 1.07 12th 74.2 90 0.17 1.39 13 71.9 90 2.00 1.02 14 71.9 100 0.17 1.16 15 70.0 100 0.50 0.49

Die Beispiele 1 bis 15 sind erfindungsgemäß, da die sich mit der NMMO-Konzentration, der Temperatur und der Imprägnierzeit ergebenden Werte aus der oben genannten Beziehung im erfindungsgemäß angegebenen Bereich liegen. Sämtliche Vliese erwiesen sich nach der erfindungsgemäßen Behandlung als verfestigt.Examples 1 to 15 are in accordance with the invention, since they deal with the NMMO concentration, the temperature and the impregnation time resulting values from the above relationship in range specified according to the invention. All fleeces proved after the treatment according to the invention as solidified.

Ähnlich gute Ergebnisse konnten mit einem Faservlies erhalten werden, welches aus Fasern bestand, die nach dem Aminoxidverfahren hergestellt worden waren.Similarly good results could be obtained with a nonwoven be, which consisted of fibers, which after the Amine oxide processes had been prepared.

VergleichsbeispieleComparative examples

Zum Vergleich wurden gemäß der allgemeinen Arbeitsvorschrift weitere Versuche durchgeführt, wobei jedoch die Parameter so gewählt wurden, daß die Beziehung nicht erfüllt wurde. Diese Beispiele sind in der Tabelle 2 angegeben. Bsp. NMMO-Konzentration Temperatur Zeit Wert 16 82,0 90 0,17 1,86 17 80,6 80 1,00 1,75 18 80,6 90 0,08 1,88 19 78,2 80 2,00 1,84 20 78,2 90 0,08 1,88 21 76,2 90 0,50 1,92 22 76,2 100 0,08 2,14 23 74,2 100 0,08 1,75 24 72,2 70 4,00 0,29 25 72,2 120 4,00 2,59 26 70,0 80 12,0 -0,10 27 70,0 90 2,00 0,21 28 70,0 100 0,08 0,25 For comparison, further tests were carried out in accordance with the general working procedure, but the parameters were chosen such that the relationship was not fulfilled. These examples are given in Table 2. E.g. NMMO concentration temperature time value 16 82.0 90 0.17 1.86 17th 80.6 80 1.00 1.75 18th 80.6 90 0.08 1.88 19th 78.2 80 2.00 1.84 20th 78.2 90 0.08 1.88 21 76.2 90 0.50 1.92 22 76.2 100 0.08 2.14 23 74.2 100 0.08 1.75 24th 72.2 70 4.00 0.29 25th 72.2 120 4.00 2.59 26 70.0 80 12.0 -0.10 27 70.0 90 2.00 0.21 28 70.0 100 0.08 0.25

Im Fall der Beispiele 16 bis 23 und 25, deren Parameter einen Wert von größer als 1,70 ergeben, löste sich das Vlies in der NMMO-Lösung auf. In the case of Examples 16 to 23 and 25, whose parameters are one If the value is greater than 1.70, the fleece detached in the NMMO solution.

Im Fall der Beispiele 24 und 26 bis 28, deren Parameter einen Wert von kleiner als 0,30 ergeben, konnte keine Vliesverfestigung erzielt werden.In the case of Examples 24 and 26 to 28, whose parameters are one None could result in a value of less than 0.30 Fleece bonding can be achieved.

Claims (7)

  1. A process for producing a strengthened fiber assembly containing cellulosic fibers, wherein the cellulose is present in the crystalline structure of cellulose II, by contacting the fiber assembly with an aqueous solution of N-methylmorpholine-N-oxide (NMMO) at elevated temperature and subsequently washing the fiber assembly, and wherein contacting is effected in a manner that from the relation -947 + 0.30xlog(10)t + 0.046xT - 3.53xC + 645xlog(10)C wherein t indicates the time in minutes during which the fiber assembly is contacted with the aqueous NMMO solution, T indicates the temperature of the aqueous NMMO solution in °C and C is the concentration of NMMO in % by mass, based on the aqueous NMMO solution, a number in the range of 0.30 to 1.70 results with the proviso that the temperature T is smaller than 130°C and the concentration C ranges between 70 and 84 % by mass.
  2. A process according to claim 1, characterized in that the parameters t, T and C are chosen such that a number in the range of 0.5 to 1.5 results from the relation.
  3. A process according to claim 2, characterized in that the parameters t, T and C are chosen such that a number in the range of 0.8 to 1.2 results from the relation.
  4. A process according to any one of claims 1 to 3, characterized in that the temperature T is smaller than 100°C.
  5. A process according to any one of claims 1 to 4, characterized in that the fiber assembly is pressed prior to washing.
  6. A process according to any one of claims 1 to 5, characterized in that a fiber assembly whose fibers have at least partially been produced according to the amine oxide process is used for strengthening.
  7. A process according to any one of claims 1 to 5, characterized in that a fiber assembly whose fibers have at least partially been produced according to the viscose process is used for strengthening.
EP98903942A 1997-02-25 1998-02-25 Method for producing a reinforced fiber composite Expired - Lifetime EP0901533B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AT0031997A AT404368B (en) 1997-02-25 1997-02-25 METHOD FOR PRODUCING A FASTENED FIBER COMPOSITE
AT31997 1997-02-25
AT319/97 1997-02-25
PCT/AT1998/000040 WO1998038373A1 (en) 1997-02-25 1998-02-25 Method for producing a reinforced fiber composite

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EP0901533B1 true EP0901533B1 (en) 2000-09-13

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DE202015102564U1 (en) 2015-05-19 2015-08-13 W. Pelz Gmbh & Co. Kg Oral tobacco pack

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DE102009028306B4 (en) * 2009-08-06 2011-04-21 Tpr Fiberdur Gmbh & Co. Kg double tube
EP2363108B1 (en) 2010-03-02 2017-08-30 Neubourg Skin Care GmbH & Co. KG Foam formulation containing at least one triterpenoid
CN105728565A (en) * 2016-04-22 2016-07-06 安徽联盟模具工业股份有限公司 Rotating flip type no-indention mold

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DE902427C (en) * 1948-10-12 1955-04-04 Dr Otto Eisenhut Process for the production of strong, washable, fabric-like, felted fabrics from cellulose fibers without spinning and weaving
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
AT401072B (en) * 1993-09-06 1996-06-25 Chemiefaser Lenzing Ag METHOD FOR PRODUCING PAPER
JP3488302B2 (en) * 1995-01-31 2004-01-19 ユニチカ株式会社 Hand processing method of cellulose fiber cloth
JP3445865B2 (en) * 1995-04-06 2003-09-08 花王株式会社 Cellulosic fiber modification method
EP0827557A1 (en) * 1995-05-22 1998-03-11 Akzo Nobel N.V. Shaped bodies coated, impregnated or covered with a cellulosic composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202015102564U1 (en) 2015-05-19 2015-08-13 W. Pelz Gmbh & Co. Kg Oral tobacco pack

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EP0901533A1 (en) 1999-03-17
ES2152745T3 (en) 2001-02-01
ATE196329T1 (en) 2000-09-15
CN1224474A (en) 1999-07-28
JP2000509771A (en) 2000-08-02
AU6200198A (en) 1998-09-18
BR9805914A (en) 1999-08-24
NO984883D0 (en) 1998-10-20
ID20258A (en) 1998-11-12
WO1998038373A1 (en) 1998-09-03
CN1105798C (en) 2003-04-16
CA2251728A1 (en) 1998-09-03
AT404368B (en) 1998-11-25
DE59800265D1 (en) 2000-10-19
ATA31997A (en) 1998-03-15
AU727252B2 (en) 2000-12-07
NO310205B1 (en) 2001-06-05

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