EP0901533A1 - Method for producing a reinforced fiber composite - Google Patents

Method for producing a reinforced fiber composite

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Publication number
EP0901533A1
EP0901533A1 EP98903942A EP98903942A EP0901533A1 EP 0901533 A1 EP0901533 A1 EP 0901533A1 EP 98903942 A EP98903942 A EP 98903942A EP 98903942 A EP98903942 A EP 98903942A EP 0901533 A1 EP0901533 A1 EP 0901533A1
Authority
EP
European Patent Office
Prior art keywords
fiber composite
nmmo
cellulose
aqueous
solution
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
EP98903942A
Other languages
German (de)
French (fr)
Other versions
EP0901533B1 (en
Inventor
Hartmut Rüf
Heinrich Firgo
Siegfried Ambrosch
Christian Schlossnikl
Raimund Jurkovic
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Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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Publication of EP0901533A1 publication Critical patent/EP0901533A1/en
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Publication of EP0901533B1 publication Critical patent/EP0901533B1/en
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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 producing a solidified 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.
  • NMMO N-methylmorpholine-N-oxide
  • fiber composite is intended to denote any type of fabric, fleece or scrim.
  • N-methylmorpholine-N-oxide is preferably used as the solvent.
  • NMMO N-methylmorpholine-N-oxide
  • the abbreviation "NMMO” is used for the term “tertiary amine oxides” used, NMMO additionally stands for 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 can dissolve high-quality chemical pulp without derivatization and that cellulosic shaped bodies such as fibers can be obtained from these solutions by precipitation. 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.
  • EP-A-0 356 419 by the applicant describes a process which is preferably carried out in a thin-film treatment apparatus in which a suspension of the comminuted pulp in an aqueous tertiary amine oxide, spread out in the form of a thin layer, is transported over a heating surface , the surface of this thin layer being subjected to a vacuum.
  • a suspension of the comminuted pulp in an aqueous tertiary amine oxide, spread out in the form of a thin layer 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 thin-film treatment apparatus.
  • a method and an apparatus for spinning cellulose solutions are known, for example, from WO 93/19230 by the applicant.
  • the spinning solution is spun in a warm state and the filaments obtained are introduced into a precipitation bath to precipitate the cellulose contained, the filaments being cooled before being introduced into the precipitation bath.
  • the cooling is carried out immediately after molding and preferably consists of blowing the cellulosic molding horizontally with air.
  • German Patent No. 902 427 describes the consolidation of a nonwoven made of cellulose fibers by means of a lye bath which contains 5 to 15% NaOH. The cellulose fibers are swollen with the lye bath, causing a consolidation.
  • Sheet formation process is subjected, wherein the suspension contains a tertiary amine oxide. This process allows the production of high strength paper.
  • a method for solidifying a fibrous material is known from US-A-3,447,956.
  • the solidification is carried out by impregnating the fibrous material with an amine oxide and heating it to a temperature at which the amine oxide can solidify the fibrous material.
  • Woven and nonwovens which are natural cellulosic fibers, such as e.g. Pulp, cotton, linen, but also synthetic fibers, e.g. Include rayon (viscose fibers), suggested.
  • the treatment of paper with the amine oxide is particularly preferred.
  • NMMO is apparently used as a monohydrate in molten or liquid form or in solution with a volatile, evaporable solvent.
  • fiber composites which are provided with a cellulosic coating, impregnation or covering. These fiber composites are produced by coating the fiber composite on one side with a solution of cellulose in an aqueous NMMO, after which the layer is coagulated in a water bath.
  • the US-A-4,196,282 describes the three-component system MMO / H 2 0 / cellulose and the so-called "release window", that is Conditions under which the cellulose dissolves in the aqueous NMMO.
  • the object of the invention is to provide a method of the type mentioned at the outset in which a fiber composite can be solidified without complex evaporation of a volatile solvent or without the need to use an NMMO monohydrate or to produce it by evaporation.
  • 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
  • T means the temperature of the aqueous NMMO solution in ° C
  • C 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 that the temperature T is less than 130 ° C and the concentration C is in the range of 70 to 84 mass%.
  • the invention is based on the knowledge that the three parameters mentioned, that is to say the concentration of the NMMO solution, its temperature and the impregnation time, are apparently essential and sufficient for the strengthening of a composite, for example a nonwoven, of cellulose fibers, and that they are also chosen in this way the above relationship must be satisfied. If, on the other hand, these parameters are chosen so that the relationship is less than 0.30, the bond cannot be strengthened. On the other hand, if the parameters are chosen so that the relationship gives a value above 1.70, then a dissolution of the fiber composite in the NMMO solution is observed.
  • the temperature T is preferably less than 100 ° C.
  • a special embodiment of the method according to the invention is characterized in that the fiber composite is pressed before washing.
  • the pressing can be carried out in a simple manner e.g. be made so that the fleece is guided between two rollers that exert pressure on the fiber composite.
  • the use of a fiber composite has proven particularly useful, the fibers of which have been produced at least in part by the amine oxide process or the viscose process.
  • the parameters to be set according to the invention namely the concentration of the respective NMMO solution (in mass% NMMO, based on the total mass of the solution), its temperature (in ° C.) and the impregnation time (in Minutes) were selected 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.
  • Examples 1 to 15 are according to the invention, since the values resulting from the above-mentioned relationship with the NMMO concentration, the temperature and the impregnation time are in the range specified according to the invention. All of the nonwovens proved to be consolidated after the treatment according to the invention.

Landscapes

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

Verfahren zur Herstellung eines verfestigten FaserverbundesProcess for producing a consolidated fiber composite
Die vorliegende Erfindung betrifft ein 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 .The present invention relates to a method for producing a solidified 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.
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 the present description and the present claims, the term "fiber composite" is intended to 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, 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.
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 a single process for the production of a cellulose fiber of the Lyocell type has prevailed until industrial implementation, namely the amine oxide process. In this process, N-methylmorpholine-N-oxide (NMMO) is preferably used as the solvent. For the purposes of the present description, the abbreviation "NMMO" is used for the term "tertiary amine oxides" used, NMMO additionally stands 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 known as alternative solvents for cellulose. From US Pat. No. 2,179,181 it is known, for example, that tertiary amine oxides can dissolve high-quality chemical pulp without derivatization and that cellulosic shaped bodies such as fibers can be obtained from these solutions by precipitation. 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.
In der EP-A - 0 356 419 der Anmelderin wird ein Verfahren beschrieben, das vorzugsweise in einem Dünnschichtbehandlungs- apparat 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 process which is preferably carried out in a thin-film treatment apparatus in which a suspension of the comminuted pulp in an aqueous tertiary amine oxide, spread out in the form of a thin layer, 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 thin-film treatment apparatus.
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. 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.A method and an apparatus for spinning cellulose solutions are known, for example, from WO 93/19230 by the applicant. The spinning solution is spun in a warm state and the filaments obtained are introduced into a precipitation bath to precipitate the cellulose contained, the filaments being cooled before being introduced into the precipitation bath. The cooling is carried out immediately after molding and preferably consists of blowing the cellulosic molding horizontally with air. German Patent No. 902 427 describes the consolidation of a nonwoven made of cellulose fibers by means of a lye bath which contains 5 to 15% NaOH. The cellulose fibers are swollen with the lye bath, causing a consolidation.
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 einemFrom WO 95/07386 by the applicant a process for the production of paper is known, in which an aqueous suspension of shredded cellulosic material is treated mechanically and then one
Blattbildungsvorgang unterzogen wird, wobei die Suspension ein tertiäres Aminoxid enthält. Dieses Verfahren gestattet die Herstellung von Papier hoher Festigkeit.Sheet formation process is subjected, wherein the suspension contains a tertiary amine oxide. This process allows the production 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 .A method for solidifying a fibrous material is known from US-A-3,447,956. The solidification is carried out by impregnating the fibrous material with an amine oxide and heating it to a temperature at which the amine oxide can solidify the fibrous material. Woven and nonwovens, which are natural cellulosic fibers, such as e.g. Pulp, cotton, linen, but also synthetic fibers, e.g. Include rayon (viscose fibers), suggested. The treatment of paper with the amine oxide is particularly preferred. NMMO is apparently used as a monohydrate in molten or liquid form or in solution with a volatile, evaporable solvent.
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 are provided with a cellulosic coating, impregnation or covering. These fiber composites are produced by coating the fiber composite on one side with a solution of cellulose in an aqueous NMMO, after which the layer is coagulated in a water bath.
Die US-A - 4,196,282 beschreibt das Dreikomponentensystem MMO/H20/Cellulose und das sogenannte "Lösefenster", also jene Bedingungen, unter denen sich die Cellulose im wäßrigen NMMO auflöst.The US-A-4,196,282 describes the three-component system MMO / H 2 0 / cellulose and the so-called "release window", that is 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 .Sei: Appl.Pol.Symp. 37, 239-259 (1983)).It is also known that cellulose fibers can be swollen with NMMO (Chancy et al., "Swelling and Dissolution of Cellulose in Amine Oxide / Water Systems"; J.App. Pol. Sei: 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 object of the invention is to provide a method of the type mentioned at the outset in which a fiber composite can be solidified without complex evaporation of a volatile solvent or without the need to use an NMMO monohydrate or to produce it by evaporation.
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 BeziehungThe 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/1(.,t + 0,046xT - 3,53xC + 645xlog,1(..C-947 + 0.30xlog / 1 ( ., T + 0.046xT - 3.53xC + 645xlog, 1 ( ..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. 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.in which t means the time in minutes that the fiber composite is contacted with the aqueous NMMO solution, T means the temperature of the aqueous NMMO solution in ° C, and C 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 that the temperature T is less than 130 ° C and the concentration C is in the range of 70 to 84 mass%. The invention is based on the knowledge that the three parameters mentioned, that is to say the concentration of the NMMO solution, its temperature and the impregnation time, are apparently essential and sufficient for the strengthening of a composite, for example a nonwoven, of cellulose fibers, and that they are also chosen in this way the above relationship must be satisfied. If, on the other hand, these parameters are chosen so that the relationship is less than 0.30, the bond cannot be strengthened. On the other hand, if the parameters are chosen so that the relationship gives a value above 1.70, then a dissolution of the fiber composite in the NMMO solution is observed.
Im erfindungsgemäßen Verfahren ist die Temperatur T bevorzugt kleiner als 100°C.In the process according to the invention, the temperature T is preferably 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 method according to the invention is characterized in that the fiber composite is pressed before washing. The pressing can be carried out in a simple manner e.g. be made so that the fleece is guided between two rollers that exert pressure on the 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 process according to the invention, the use of a fiber composite has proven particularly useful, the fibers of which have been produced at least in part by the amine oxide process or the viscose process.
Mit den nachfolgenden Beispielen wird die Erfindung noch näher beschrieben.The invention is described in more detail with the following examples.
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: Ξ 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, each measuring 12 x 16 cm and with a basis weight of approximately 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: Ξ 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 .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 mass% NMMO, based on the total mass of the solution), its temperature (in ° C.) and the impregnation time (in Minutes) were selected 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.
Tabelle 1Table 1
Bsp. NMMO-Konzentration Temperatur Zeit WertEg NMMO concentration temperature time value
1 84,0 80 0,08 0,951 84.0 80 0.08 0.95
2 82,0 80 0,08 1,302 82.0 80 0.08 1.30
3 82,0 70 0,17 0,943 82.0 70 0.17 0.94
4 80,6 70 0,50 1,204 80.6 70 0.50 1.20
5 80,6 80 0,08 1,425 80.6 80 0.08 1.42
6 80,6 80 0,50 1,666 80.6 80 0.50 1.66
7 78,2 70 1,00 1,297 78.2 70 1.00 1.29
8 76,2 70 0,50 1,008 76.2 70 0.50 1.00
9 76,2 80 0,17 1,329 76.2 80 0.17 1.32
10 73,9 70 4,00 0,8110 73.9 70 4.00 0.81
11 74,2 80 0,50 1,0711 74.2 80 0.50 1.07
12 74,2 90 0,17 1,3912 74.2 90 0.17 1.39
13 71,9 90 2,00 1,0213 71.9 90 2.00 1.02
14 71,9 100 0,17 1,1614 71.9 100 0.17 1.16
15 70,0 100 0,50 0,49 Die Beispiele l 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.15 70.0 100 0.50 0.49 Examples 1 to 15 are according to the invention, since the values resulting from the above-mentioned relationship with the NMMO concentration, the temperature and the impregnation time are in the range specified according to the invention. All of the nonwovens proved to be consolidated after the treatment according to the invention.
Ähnlich gute Ergebnisse konnten mit einem Faservlies erhalten werden, welches aus Fasern bestand, die nach dem Aminoxidverfahren hergestellt worden waren.Similar good results could be obtained with a non-woven fabric which consisted of fibers which had been produced by the amine oxide process.
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.For comparison, further tests were carried out in accordance with the general working instructions, but the parameters were chosen such that the relationship was not fulfilled. These examples are given in Table 2.
Tabelle 2Table 2
Bsp. NMMO-Konzentration Temperatur Zeit WertEg NMMO concentration temperature time value
16 82,0 90 0,17 1,8616 82.0 90 0.17 1.86
17 80,6 80 1,00 1,7517 80.6 80 1.00 1.75
18 80,6 90 0,08 1,8818 80.6 90 0.08 1.88
19 78,2 80 2,00 1,8419 78.2 80 2.00 1.84
20 78,2 90 0,08 1,8820 78.2 90 0.08 1.88
21 76,2 90 0,50 1,9221 76.2 90 0.50 1.92
22 76,2 100 0,08 2,1422 76.2 100 0.08 2.14
23 74,2 100 0,08 1,7523 74.2 100 0.08 1.75
24 72,2 70 4,00 0,2924 72.2 70 4.00 0.29
25 72,2 120 4,00 2,5925 72.2 120 4.00 2.59
26 70,0 80 12,0 -0,1026 70.0 80 12.0 -0.10
27 70,0 90 2,00 0,2127 70.0 90 2.00 0.21
28 70,0 100 0,08 0,2528 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. 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 16 to 23 and 25, the parameters of which give a value greater than 1.70, the fleece dissolved in the NMMO solution. In the case of Examples 24 and 26 to 28, the parameters of which give a value of less than 0.30, it was not possible to achieve nonwoven bonding.

Claims

Patentansprüche :Claims:
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 ,Process for the production of 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 subsequent washing of the fiber composite,
dadurch gekennzeichnet, daßcharacterized in that
das Kontaktieren so ausgeführt wird, daß die Beziehungcontacting is carried out so that the relationship
-947 + 0,30xlog,10, t + 0,046xT - 3,53xC + 645xlog/1Q.C-947 + 0.30xlog, 10 , t + 0.046xT - 3.53xC + 645xlog / 1Q .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 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.in which t means the time in minutes that the fiber composite is contacted with the aqueous NMMO solution, T means the temperature of the aqueous NMMO solution in ° C., and C the concentration of the NMMO in mass%, based on the aqueous NMMO Solution means a number in the range of 0.30 and 1.70, 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.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Parameter t, T und C so gewählt werden, daß die Beziehung eine Zahl im Bereich von 0,5 bis 1,5 ergibt.2. The method according to claim 1, characterized in that the parameters t, T and C are chosen so that the relationship gives a number in the range from 0.5 to 1.5.
Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Parameter t, T und C so gewählt werden, daß die Beziehung eine Zahl im Bereich von 0,8 bis 1,2 ergibt. Method according to Claim 2, characterized in that the parameters t, T and C are chosen so that the relationship gives a number in the range from 0.8 to 1.2.
4. Verfahren nach einem der Ansprüche 1 bis 3 , dadurch gekennzeichnet, daß die Temperatur T kleiner als 100° C ist.4. The method according to any one of claims 1 to 3, characterized in that the temperature T is less than 100 ° C.
5. Verfahren nach einem der Ansprüche 1 bis 4 , dadurch gekennzeichnet, daß der Faserverbund vor dem Waschen verpreßt wird.5. The method according to any one of claims 1 to 4, characterized in that the fiber composite is pressed before washing.
Verfahren nach einem der Ansprüche 1 bis 5 , dadurch gekennzeichnet, daß zur Verfestigung ein Faserverbund eingesetzt wird, dessen Fasern zumindest teilweise nach dem Aminoxidverfahren hergestellt wurden.Method according to one of claims 1 to 5, characterized in that a fiber composite is used for consolidation, the fibers of which were at least partially produced by the amine oxide process.
Verfahren nach einem der Ansprüche l bis 5, dadurch gekennzeichnet, daß zur Verfestigung ein Faserverbund eingesetzt wird, dessen Fasern zumindest teilweise nach dem Viskoseverfahren hergestellt wurden. Method according to one of claims 1 to 5, characterized in that a fiber composite is used for consolidation, the fibers of which were at least partially produced by the viscose process.
EP98903942A 1997-02-25 1998-02-25 Method for producing a reinforced fiber composite Expired - Lifetime EP0901533B1 (en)

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AT319/97 1997-02-25
AT0031997A AT404368B (en) 1997-02-25 1997-02-25 METHOD FOR PRODUCING A FASTENED FIBER COMPOSITE
AT31997 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 EP0901533B1 (en) 2000-09-13

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