EP0811086A1 - Cellulose moulded article and method of producing same - Google Patents

Cellulose moulded article and method of producing same

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Publication number
EP0811086A1
EP0811086A1 EP96942178A EP96942178A EP0811086A1 EP 0811086 A1 EP0811086 A1 EP 0811086A1 EP 96942178 A EP96942178 A EP 96942178A EP 96942178 A EP96942178 A EP 96942178A EP 0811086 A1 EP0811086 A1 EP 0811086A1
Authority
EP
European Patent Office
Prior art keywords
pulp
bleached
fibers
chlorine
cellulose
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
EP96942178A
Other languages
German (de)
French (fr)
Other versions
EP0811086B1 (en
Inventor
Hartmut Rüf
Dieter Eichinger
Gabriele Schild
Wilhelm Feilmair
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Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/50—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs by irradiation or ozonisation

Definitions

  • the invention relates to a cellulose molding, in particular a cellulose fiber, and a method for its production.
  • NMMO N-Methylmorpholine-N-oxide
  • Other amine oxides are e.g. in EP-A - 0 553 070.
  • a method of making moldable cellulose solutions is e.g. known from EP-A-0 356 419.
  • the production of cellulosic moldings using tertiary amine oxides is generally referred to as the amine oxide process.
  • EP-A-0 356 419 describes an amine oxide process for the preparation of spinnable cellulose solutions which uses, among other things, a suspension of cellulose in liquid, aqueous N-methylmorpholine-N-oxide (NMMO) as the starting material.
  • NMMO N-methylmorpholine-N-oxide
  • This method consists in that the suspension in a thin film treatment apparatus in one stage and continuously in a malleable solution is transferred.
  • the moldable solution is finally spun into filaments in a molding tool, for example a spinneret, which are passed through an air gap in which they are stretched into a precipitation bath, where the cellulose is precipitated.
  • the cellulose fibers obtained are then washed.
  • the raw pulp is blended with a range of bleaching agents, e.g. elemental chlorine, chlorine compounds, such as hypochlorite and chlorine dioxide, oxygen, peroxide and ozone, are implemented, the reaction being carried out with a combination of these chemicals in a specific sequence, which is referred to as the bleaching sequence.
  • bleaching agents e.g. elemental chlorine, chlorine compounds, such as hypochlorite and chlorine dioxide, oxygen, peroxide and ozone
  • Bleaching agents containing chlorine produce chlorinated products to varying degrees during pulp bleaching, which are difficult to degrade and for the most part end up in wastewater. These processes are therefore questionable for environmental reasons, and the use of chlorine-containing bleaches and especially elemental chlorine is being increasingly suppressed. However, the quality of the Bleaching off, since elemental chlorine has a high bleaching power.
  • hypochlorite Of the chlorine compounds, chlorine dioxide bleaches better than hypochlorite, but is more expensive than the more commonly used hypochlorite.
  • ECF pulp bleached with hypochlorite is referred to as ECF hypochlorite pulp.
  • the so-called whiteness is a measure of the intensity of the bleaching. It is known from the viscose process that there is a relationship between the whiteness of a bleached pulp and the whiteness of the cellulose products made from this pulp in such a way that pulps with a higher whiteness can generally be processed into fibers with a likewise higher whiteness.
  • the aim of the invention is to provide a process by means of which cellulosic shaped articles can be produced which, with the same initial degree of whiteness of the cellulose used and other similar procedures, have a higher degree of whiteness than cellulosic ones Shaped bodies that were made from an ECF hypochlorite pulp.
  • Pulp is bleached with a bleach with which
  • the bleach is not chlorine or a
  • the process according to the invention can be used in particular to produce cellulose fibers with a high degree of whiteness, as well as cellulose films by the dry / wet spinning process.
  • TCF pulps achieve higher fiber whiteness than ECF hypochlorite pulps with the same whiteness of the starting pulp, and that there is the positive side effect that the fibers can be produced in a particularly environmentally friendly manner in this way.
  • the invention also relates to the bleaching of fibers which have been produced by the amine oxide process with chlorine-free bleaches, such as oxygen, ozone and in particular hydrogen peroxide.
  • a preferred variant of the process according to the invention is characterized in that the fibers or the films produced according to the invention are bleached with a bleaching agent, with the proviso that the bleaching agent does not contain chlorine or a chlorine compound.
  • N-methyl morpholine-N-oxide has proven particularly useful as the tertiary amine oxide.
  • the invention also relates to cellulosic moldings, in particular cellulose fibers and films, with a high degree of whiteness, which can be produced by the process according to the invention.
  • the invention further relates to the use of a pulp bleached with a bleaching agent for the production of cellulosic shaped articles by the amine oxide process, with the proviso that the bleaching agent does not contain chlorine or a chlorine compound.
  • the pulp (beech sulfite pulp type) was first bleached using an alkaline, peroxide-enhanced oxygen extraction, then with ozone and finally with peroxide according to known processes.
  • the individual bleaching processes are described, for example, in R.P. Singh; The Bleaching of Pulp, TAPPI Press, Atlanta, USA, and in EP-A - 0 426 652.
  • the whiteness of the TCF pulp obtained which was determined in accordance with ISO 3688, was 90.6.
  • the pulp had a rapid copper viscosity according to Zellcheming ZM IV / 30/62 of 19.8 Pa.s and an ⁇ content of 90.9.
  • This TCF pulp was then processed in a known manner in a stirred kettle to give a spinning composition of 12% cellulose, 77% NMMO and 11% water.
  • the viscosity the spinning mass was 1630 Pa.s (Temp .: 90 ° C, shear rate: 0.1 s).
  • the spinning mass was spun into fibers at 120 ° C. through a spinneret with spinning holes, the diameter of which was 100 ⁇ m, in accordance with the known wet / dry spinning process (see, for example, EP-A - 0 584 318).
  • the degree of whiteness of the fibers produced according to the invention was around 50.
  • Oxygen extraction then bleached with hypochlorite and finally with peroxide.
  • the whiteness of the ECF hypochlorite pulp obtained was 91.6 and thus practically the same as the TCF pulp produced in the example.
  • a spinning mass and fibers were then produced analogously to the example above.
  • the fibers produced had a CIELAB degree of whiteness of about 39. This makes it clear that the TCF pulp bleached according to the invention without any chlorine compound can be processed into fibers with a higher degree of whiteness than that of i.a. ECF pulp bleached with hypochlorite.
  • the fibers produced were then bleached as described in the example above.
  • the bleached fibers had a CIELAB whiteness of about 54.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Artificial Filaments (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a process for producing cellulose moulded articles of high brightness, the process being characterised by the following combination of measures: pulp is bleached with a bleaching agent which must not contain chlorine or any chlorine compound; the pulp once bleached is dissolved in an aqueous tertiary amine oxide to produce a mouldable cellulose solution; and the mouldable cellulose solution is worked into moulded articles.

Description

Celluloseformkörper und Verfahren zu seiner Herstellung Molded cellulose body and process for its production
Die Erfindung betrifft einen Celluloseformkörper, insbesondere eine Cellulosefaser, und ein Verfahren zu seiner Herstellung.The invention relates to a cellulose molding, in particular a cellulose fiber, and a method for its production.
Seit einigen Jahrzehnten wird nach Verfahren zur Herstellung von Cellulosefasern gesucht, welche das heute in großem Maßstab angewendete Viskoseverfahren ersetzen sollen. Als eine nicht zuletzt wegen einer besseren Umweltverträglichkeit interessante Alternative hat sich dabei herauskristallisiert, Cellulose ohne Derivatisierung in einem organischen Lösungs¬ mittel aufzulösen und aus dieser Lösung Formkörper, z.B. Fasern, Folien und anderen Formkörpern, zu extrudieren. Solcherart extrudierte Fasern erhielten von der BISFA (The International Bureau for the Standardization of man made fibers) den Gattungsnamen Lyocell. Unter einem organischen Lösungsmittel wird von der BISFA ein Gemisch aus einer organi¬ schen Chemikalie und Wasser verstanden.For several decades, processes for the production of cellulose fibers have been sought to replace the viscose process which is used today on a large scale. An alternative, not least because of its better environmental compatibility, has emerged here: dissolving cellulose in an organic solvent without derivatization and molding, e.g. Fibers, foils and other moldings to extrude. Such extruded fibers were given the generic name Lyocell by BISFA (The International Bureau for the Standardization of man made fibers). BISFA understands an organic solvent to be a mixture of an organic chemical and water.
Es hat sich herausgestellt, daß sich als organisches Lösungs¬ mittel insbesondere ein Gemisch aus einem tertiären Aminoxid und Wasser sehr gut zur Herstellung von cellulosischen Form¬ körpern eignet. Als Aminoxid wird dabei in erster Linie N-Methylmorpholin-N-oxid (NMMO) verwendet. Andere Aminoxide sind z.B. in der EP-A - 0 553 070 beschrieben. Ein Verfahren zur Herstellung formbarer Celluloselösungen ist z.B. aus der EP-A - 0 356 419 bekannt. Die Herstellung cellulosischer Formkörper unter Anwendung tertiärer Aminoxide wird allgemein als Aminoxidverfahren bezeichnet.It has been found that a mixture of a tertiary amine oxide and water is particularly suitable as an organic solvent for the production of cellulosic moldings. N-Methylmorpholine-N-oxide (NMMO) is primarily used as the amine oxide. Other amine oxides are e.g. in EP-A - 0 553 070. A method of making moldable cellulose solutions is e.g. known from EP-A-0 356 419. The production of cellulosic moldings using tertiary amine oxides is generally referred to as the amine oxide process.
In der EP-A - 0 356 419 ist ein Aminoxidverfahren zur Herstel¬ lung spinnbarer Celluloselösungen beschrieben, welches als Ausgangsmaterial u.a. eine Suspension von Cellulose in flüssi¬ gem, wäßrigem N-Methylmorpholin-N-oxid (NMMO) verwendet. Dieses Verfahren besteht darin, daß die Suspension in einem Dünnschichtbehandlungsapparat einstufig und kontinuierlich in eine formbare Lösung übergeführt wird. Die formbare Lösung wird schließlich in einem Formwerkzeug, z.B einer Spinndüse, zu Filamenten versponnen, die über einen Luftspalt, in welchem sie verstreckt werden, in ein Fällbad geführt werden, wo die Cellulose ausgefällt wird. Anschließend werden die erhaltenen Cellulosefasern gewaschen.EP-A-0 356 419 describes an amine oxide process for the preparation of spinnable cellulose solutions which uses, among other things, a suspension of cellulose in liquid, aqueous N-methylmorpholine-N-oxide (NMMO) as the starting material. This method consists in that the suspension in a thin film treatment apparatus in one stage and continuously in a malleable solution is transferred. The moldable solution is finally spun into filaments in a molding tool, for example a spinneret, which are passed through an air gap in which they are stretched into a precipitation bath, where the cellulose is precipitated. The cellulose fibers obtained are then washed.
Um eine unerwünschte Verfärbung der Fasern, die vor allem auf Lignin und auf gefärbte organische Verbindungen zurückzuführen ist, zu verhindern, ist es bekannt, den Zellstoff vor der Verarbeitung zu bleichen. Dazu wird der Rohzellstoff unter genau definierten Bedingungen mit einer Reihe von Bleichmitteln, wie z.B. elementarem Chlor, Chlorverbindungen, wie Hypochlorit und Chlordioxid, Sauerstoff, Peroxid und Ozon, umgesetzt, wobei die Umsetzung mit einer Kombination dieser Chemikalien in einer bestimmten Reihenfolge erfolgt, die als Bleichsequenz bezeichnet wird.In order to prevent undesirable discoloration of the fibers, which is primarily due to lignin and colored organic compounds, it is known to bleach the pulp before processing. For this purpose, the raw pulp is blended with a range of bleaching agents, e.g. elemental chlorine, chlorine compounds, such as hypochlorite and chlorine dioxide, oxygen, peroxide and ozone, are implemented, the reaction being carried out with a combination of these chemicals in a specific sequence, which is referred to as the bleaching sequence.
Klassische Bleichverfahren beginnen mit elementarem Chlor, welches je nach pH-Wert in unterschiedlichem Ausmaß chloriert oder oxydiert. Hypochlorit und Chlordioxid oxydieren das Lignin und gefärbte Verbindungen. Zwiεchen die einzelnen Reaktionsstufen dieser Bleichmittel wird gewöhnlich eine alkalische Extraktion geschaltet, um das in Lösung gebrachte Lignin und die anderen Verbindungen aus dem Reaktionsmedium zu entfernen. Für einen Überblick über die Technik der Zellstoffbleiche wird R.P. Singh; The Bleaching of Pulp, TAPPI Press, Atlanta, USA, genannt.Classic bleaching processes begin with elemental chlorine, which chlorinates or oxidizes to varying degrees depending on the pH. Hypochlorite and chlorine dioxide oxidize the lignin and colored compounds. An alkaline extraction is usually carried out between the individual reaction stages of these bleaching agents in order to remove the lignin and the other compounds brought into solution from the reaction medium. For an overview of the technique of pulp bleaching, R.P. Singh; The Bleaching of Pulp, TAPPI Press, Atlanta, USA.
Chlor enthaltende Bleichmittel erzeugen in unterschiedlichem Ausmaß bei der Zellstoffbleichung chlorierte Produkte, die schwer abbaubar sind und zum größten Teil ins Abwasser gelangen. Diese Verfahren sind daher aus Umweltschutzgründen bedenklich, und die Verwendung von chlorhaltigen Bleichmitteln und vor allem von elementarem Chlor wird in zunehmendem Maße zurückgedrängt. Allerdings nimmt damit auch die Qualität der Bleichung ab, da elementares Chlor eine hohe Bleichkraft besitzt.Bleaching agents containing chlorine produce chlorinated products to varying degrees during pulp bleaching, which are difficult to degrade and for the most part end up in wastewater. These processes are therefore questionable for environmental reasons, and the use of chlorine-containing bleaches and especially elemental chlorine is being increasingly suppressed. However, the quality of the Bleaching off, since elemental chlorine has a high bleaching power.
Von den Chlorverbindungen bleicht Chlordioxid zwar besser als Hypochlorit, ist jedoch teurer als das häufiger verwendete Hypochlorit.Of the chlorine compounds, chlorine dioxide bleaches better than hypochlorite, but is more expensive than the more commonly used hypochlorite.
Im Stand der Technik werden auch Bleichverfahren angewandt, die völlig ohne Chlorverbindungen auskommen. Dabei werden Kombinationen von Sauerstoff/Peroxid bzw. Ozon eingesetzt. Der so gebleichte Zellstoff wird als TCF-(total chlorine free)-Zellstoff bezeichnet, da er weder mit elementarem Chlor noch mit Chlorverbindungen gebleicht wird. Demgegenüber wird in der Literatur ein Zellstoff, der zwar nicht mit elementarem Chlor, jedoch mit Chlorverbindungen gebleicht wird, als ECF-(elementar chlorine free)-Zellstoff bezeichnet.In the prior art, bleaching processes are also used which do completely without chlorine compounds. Combinations of oxygen / peroxide or ozone are used. The pulp bleached in this way is called TCF (total chlorine free) pulp because it is not bleached with either elemental chlorine or chlorine compounds. In contrast, in the literature a pulp that is not bleached with elemental chlorine, but with chlorine compounds, is referred to as ECF (elemental chlorine free) pulp.
Für die Zwecke dieser Beschreibung wird ein ECF-Zellstoff, der mit Hypochlorit gebleicht wurde, als ECF-Hypochlorit- Zellstoff bezeichnet.For the purposes of this description, ECF pulp bleached with hypochlorite is referred to as ECF hypochlorite pulp.
Im Stand der Technik ist der sogenannte Weißgrad ein Maß für die Intensität der Bleichung. Es ist aus dem Viskoseverfahren bekannt, daß zwischem dem Weißgrad eines gebleichten Zellstoffes und dem Weißgrad der aus diesem Zellstoff hergestellten Celluloseprodukte eine Beziehung besteht derart, daß sich Zellstoffe mit einem höheren Weißgrad im allgemeinen zu Fasern mit einem ebenfalls höheren Weißgrad verarbeiten lassen.In the prior art, the so-called whiteness is a measure of the intensity of the bleaching. It is known from the viscose process that there is a relationship between the whiteness of a bleached pulp and the whiteness of the cellulose products made from this pulp in such a way that pulps with a higher whiteness can generally be processed into fibers with a likewise higher whiteness.
Die Erfindung setzt sich zum Ziel, ein Verfahren zur Verfügung zu stellen, mit welchem cellulosische Formkörper hergestellt werden können, die bei gleichem Ausgangsweißgrad der eingesetzten Zellstoffe und sonstiger gleicher Verfahrensweise einen höheren Weißgrad aufweisen als cellulosische Formkörpern, die aus einem ECF-Hypochlorit-Zellstoff hergestellt wurden.The aim of the invention is to provide a process by means of which cellulosic shaped articles can be produced which, with the same initial degree of whiteness of the cellulose used and other similar procedures, have a higher degree of whiteness than cellulosic ones Shaped bodies that were made from an ECF hypochlorite pulp.
Dieses Ziel wird mit einem Verfahren zur Herstellung cellulosischer Formkörper erreicht, das gekennzeichnet ist durch die Kombination der Maßnahmen, daßThis goal is achieved with a process for the production of cellulosic shaped articles, which is characterized by the combination of the measures that
Zellstoff mit einem Bleichmittel gebleicht wird, mit derPulp is bleached with a bleach with which
Maßgabe, daß das Bleichmittel nicht Chlor oder eineProvided that the bleach is not chlorine or a
Chlorverbindung enthält, der mit dem Bleichmittel gebleichte Zellstoff in einem wäßrigen tertiären Aminoxid gelöst wird, wobei eine formbare Cellulosellösung erhalten wird, und die formbare Celluloselösung zu Formkörpern verarbeitet wird.Contains chlorine compound, the pulp bleached with the bleach is dissolved in an aqueous tertiary amine oxide, whereby a moldable cellulose solution is obtained, and the moldable cellulose solution is processed into moldings.
Mit dem erfindungsgemäßen Verfahren lassen sich insbesondere Cellulosefasern mit hohem Weißgrad, sowie Cellulosefolien nach dem Trocken/Naßspinnverfahren herstellen.The process according to the invention can be used in particular to produce cellulose fibers with a high degree of whiteness, as well as cellulose films by the dry / wet spinning process.
Es ist für den Fachmann überraschend, daß TCF-Zellstoffe bei gleichem Weißgrad des Ausgangszellstoffes höhere Weißgrade der Fasern als ECF-Hypochlorit-Zellstoffe erzielen, und daß der positive Nebeneffekt auftritt, daß auf diese Weise die Fasern besonders umweltfreundlich hergestellt werden können.It is surprising to the person skilled in the art that TCF pulps achieve higher fiber whiteness than ECF hypochlorite pulps with the same whiteness of the starting pulp, and that there is the positive side effect that the fibers can be produced in a particularly environmentally friendly manner in this way.
Die Erfindung betrifft auch die Bleichung von Fasern, die nach dem Aminoxidverfahren hergestellt wurden, mit chlorfreien Bleichmitteln, wie Sauerstoff, Ozon und insbesondere Wasserstoffperoxid.The invention also relates to the bleaching of fibers which have been produced by the amine oxide process with chlorine-free bleaches, such as oxygen, ozone and in particular hydrogen peroxide.
Eine bevorzugte Variante des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß die erfindungsgemäß hergestellten Fasern bzw. die Folien mit einem Bleichmittel gebleicht werden, mit der Maßgabe, daß das Bleichmittel nicht Chlor oder eine Chlorverbindung enthält. Als tertiäres Aminoxid hat sich insbesondere N-Methyl¬ morpholin-N-oxid bewährt.A preferred variant of the process according to the invention is characterized in that the fibers or the films produced according to the invention are bleached with a bleaching agent, with the proviso that the bleaching agent does not contain chlorine or a chlorine compound. N-methyl morpholine-N-oxide has proven particularly useful as the tertiary amine oxide.
Die Erfindung betrifft auch cellulosische Formkorper, insbesondere Cellulosefasern und -folien, mit hohem Weißgrad, die nach dem erfindungsgemäßen Verfahren herstellbar sind.The invention also relates to cellulosic moldings, in particular cellulose fibers and films, with a high degree of whiteness, which can be produced by the process according to the invention.
Die Erfindung betrifft ferner die Verwendung eines mit einem Bleichmittel gebleichten Zellstoffs zur Herstellung cellulosischer Formkörper nach dem Aminoxidverfahren, mit der Maßgabe, daß das Bleichmittel nicht Chlor oder eine Chlorverbindung enthält.The invention further relates to the use of a pulp bleached with a bleaching agent for the production of cellulosic shaped articles by the amine oxide process, with the proviso that the bleaching agent does not contain chlorine or a chlorine compound.
Mit dem nachfolgenden Beispiel und Vergleichsbeispiel wird die Erfindung noch näher erläutert.The invention is explained in more detail with the following example and comparative example.
Beispielexample
Zur Herstellung eines TCF-Zellstoffes wurde der Zellstoff (Type Buchensulfitzellstoff) zuerst mittels einer alkalischen, peroxidverstärkten Sauerstoffextraktion, dann mit Ozon und schließlich mit Peroxid gemäß bekannten Verfahren gebleicht. Die einzelnen Bleichverfahren sind beispielsweise in R.P. Singh; The Bleaching of Pulp, TAPPI Press, Atlanta, USA, sowie in der EP-A - 0 426 652 beschrieben.To produce a TCF pulp, the pulp (beech sulfite pulp type) was first bleached using an alkaline, peroxide-enhanced oxygen extraction, then with ozone and finally with peroxide according to known processes. The individual bleaching processes are described, for example, in R.P. Singh; The Bleaching of Pulp, TAPPI Press, Atlanta, USA, and in EP-A - 0 426 652.
Der Weißgrad des erhaltenen TCF-Zellstoffes, welcher nach ISO 3688 ermittelt wurde, war 90,6. Der Zellstoff wies eine Schnellkupferviskosität nach Zellcheming ZM IV/30/62 von 19,8 Pa.s sowie einen α-Gehalt von 90,9 auf.The whiteness of the TCF pulp obtained, which was determined in accordance with ISO 3688, was 90.6. The pulp had a rapid copper viscosity according to Zellcheming ZM IV / 30/62 of 19.8 Pa.s and an α content of 90.9.
Anschließend wurde dieser TCF-Zellstoff in bekannter Weise in einem Rührkessel zu einer Spinnmasse der Zusammensetzung 12% Cellulose, 77% NMMO und 11% Wasser verarbeitet. Die Viskosität der Spinnmasse betrug 1630 Pa.s (Temp.: 90°C, Schergeschwindigkeit: 0,1 s ).This TCF pulp was then processed in a known manner in a stirred kettle to give a spinning composition of 12% cellulose, 77% NMMO and 11% water. The viscosity the spinning mass was 1630 Pa.s (Temp .: 90 ° C, shear rate: 0.1 s).
Die Spinnmasse wurde bei 120°c durch eine Spinndüse mit Spinnlöchern, deren Durchmesser 100 μm war, gemäß dem bekannten Naß/Trocken-Spinnverfahren (siehe z.B. EP-A - 0 584 318) zu Fasern versponnen. Der Weißgrad der erfindungsgemäß hergestellten Fasern war rund 50.The spinning mass was spun into fibers at 120 ° C. through a spinneret with spinning holes, the diameter of which was 100 μm, in accordance with the known wet / dry spinning process (see, for example, EP-A - 0 584 318). The degree of whiteness of the fibers produced according to the invention was around 50.
Der CIELAB-Weißgrad der Fasern wurde nach folgender Methode bestimmt: An den Fasern wurden die Farbkoordinaten nach R , R , Rz nach DIN 6174 und DIN 5033 mit der Lichtart D65 und bei 10" Beobachtungswinkel bestimmt. Aus diesen Farbkoordinaten berechnet sich nach DIN 55981 (=Farbtonabweichung nach Gärtner/Griesser) der CIE-Weißgrad und die Farbstichigkeit in der rot/grün-Achse wie folgt:The CIELAB whiteness of the fibers was determined according to the following method: The color coordinates according to R, R, R z according to DIN 6174 and DIN 5033 with the illuminant D65 and at 10 "observation angle were determined on the fibers. These color coordinates are calculated according to DIN 55981 (= Shade deviation according to Gärtner / Griesser) the CIE whiteness and the color cast in the red / green axis as follows:
CIE-Weißgrad : W = Y + 800* (xO-x) + 1700(y0-y) Farbstich (=Tint): T = 900 (xO-x) -650 (yθ-y)CIE whiteness: W = Y + 800 * (xO-x) + 1700 (y0-y) color cast (= tint): T = 900 (xO-x) -650 (yθ-y)
(Anm. : T negativ = Rot-Stich, T positiv = Grün-Stich)(Note: T negative = red stitch, T positive = green stitch)
Y... Normfarbwert für die Grünempfindlichkeit (=Y ... standard color value for green sensitivity (=
Ry...Remissionswert grün) xO, yO... Normfarbwertanteile des Unbuntpunkts (bei D65/10* gilt xo = 0,3138; y0 = 0,3310) x, y... Normfarbwertanteile der Proben; zu berechnen nach: x = X/(X + Y + Z) y = Y/(X + Y + Z) z = 1 - x - yRy ... reflectance value green) xO, yO ... standard color value components of the achromatic point (with D65 / 10 * applies xo = 0.3138; y0 = 0.3310) x, y ... standard color value components of the samples; to be calculated according to: x = X / (X + Y + Z) y = Y / (X + Y + Z) z = 1 - x - y
Die Normfarbwerte X, Y, Z, welche in diesen Formeln aufscheinen, berechnen sich wiederum aus den RemissionswertenThe standard color values X, Y, Z, which appear in these formulas, are in turn calculated from the reflectance values
(=Filterwerten) Rx, Ry, Rz bei der Lichtart D65 und 10°(= Filter values) Rx, Ry, Rz with illuminant D65 and 10 °
Beobachtungswinkel nach den Formeln:Viewing angle according to the formulas:
X = 0,94811 * RxX = 0.94811 * Rx
Y = RyY = Ry
Z = 1,07304 * RZ Anschließend wurden diese Fasern mit Wasserstoffperoxid gebleicht (1,5 g H202; Stabilisator: 0,2 g/1 MgS04; pH 10,5; Flottenverhältnis 1:20; 70°C; Bleichdauer: 3 Minuten). Der CIELAB-Weißgrad der gebleichten Fasern betrug 57.Z = 1.07304 * RZ These fibers were then bleached with hydrogen peroxide (1.5 g H 2 O 2 ; stabilizer: 0.2 g / 1 MgSO 4 ; pH 10.5; liquor ratio 1:20; 70 ° C; bleaching time: 3 minutes). The CIELAB whiteness of the bleached fibers was 57.
VergleichsbeispielComparative example
Zur Herstellung eines ECF-Hypochlorit-Zellstoffes wurde der gleiche Ausgangszellstoff wie im obigen Beispiel zuerst mittels einer peroxidverstärkten, alkalischenTo produce an ECF hypochlorite pulp, the same starting pulp as in the above example was first made using a peroxide-reinforced, alkaline
Sauerstoffextraktion, dann mit Hypochlorit und schließlich mit Peroxid gebleicht.Oxygen extraction, then bleached with hypochlorite and finally with peroxide.
Der Weißgrad des erhaltenen ECF-Hypochlorit-Zellstoffes war 91,6 und somit praktisch gleich wie der im Beispiel hergestellte TCF-Zellstoff.The whiteness of the ECF hypochlorite pulp obtained was 91.6 and thus practically the same as the TCF pulp produced in the example.
Anschließend wurden analog dem obigen Beispiel eine Spinnmasse und Fasern hergestellt. Die hergestellten Fasern hatten einen CIELAB-Weißgrad von etwa 39. Damit wird deutlich, daß der erfindungsgemäß ohne irgendeine Chlorverbindung gebleichte TCF-Zellstoff zu Fasern mit einem höheren Weißgrad verarbeitet werden kann, als der u.a. mit Hypochlorit gebleichte ECF-Zellstoff.A spinning mass and fibers were then produced analogously to the example above. The fibers produced had a CIELAB degree of whiteness of about 39. This makes it clear that the TCF pulp bleached according to the invention without any chlorine compound can be processed into fibers with a higher degree of whiteness than that of i.a. ECF pulp bleached with hypochlorite.
Anschließend wurden die hergestellten Fasern wie im obigen Beispiel beschrieben gebleicht. Die gebleichten Fasern hatten einen CIELAB-Weißgrad von etwa 54. The fibers produced were then bleached as described in the example above. The bleached fibers had a CIELAB whiteness of about 54.

Claims

Patentansprüche: Claims:
1. Verfahren zur Herstellung cellulosischer Fasern mit hohem Weißgrad, gekennzeichnet durch die Kombination der Maßnahmen, daß1. A process for producing cellulosic fibers with high whiteness, characterized by the combination of the measures that
Zellstoff mit einem Bleichmittel gebleicht wird, mit der Maßgabe, daß das Bleichmittel nicht Chlor oder eine Chlorverbindung enthält, der mit dem Bleichmittel gebleichte Zellstoff in einem wäßrigen tertiären Aminoxid gelöst wird, wobei eine formbare Cellulosellösung erhalten wird, und die formbare Celluloselösung zu Fasern verarbeitet wird.The pulp is bleached with a bleaching agent, provided that the bleaching agent does not contain chlorine or a chlorine compound, the pulp bleached with the bleaching agent is dissolved in an aqueous tertiary amine oxide, whereby a moldable cellulose solution is obtained, and the moldable cellulose solution is processed into fibers .
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die formbare Celluloselösung nach dem Trok- ken/Naßspinnverfahren zur Fasern verarbeitet wird.2. The method according to claim 1, characterized in that the moldable cellulose solution is processed into fibers after the dry / wet spinning process.
Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Fasern mit einem Bleichmittel gebleicht werden, mit der Maßgabe, daß das Bleichmittel nicht Chlor oder eine Chlorverbindung enthält.Process according to claim 2, characterized in that the fibers are bleached with a bleaching agent, with the proviso that the bleaching agent does not contain chlorine or a chlorine compound.
4. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß als tertiäres Aminoxid N-Methyl¬ morpholin-N-oxid eingesetzt wird.4. The method according to any one of claims 1 or 2, characterized in that N-methyl¬ morpholine-N-oxide is used as the tertiary amine oxide.
5. Verwendung eines mit einem Bleichmittel gebleichten5. Use a bleached one
Zellstoffs zur Herstellung cellulosischer Formkörper nach dem Aminoxidverfahren, mit der Maßgabe, daß das Bleichmittel nicht Chlor oder eine Chlorverbindung enthält. Pulp for the production of cellulosic moldings by the amine oxide process, with the proviso that Bleach does not contain chlorine or a chlorine compound.
EP96942178A 1995-12-22 1996-12-19 Method for Producing a Cellulose moulded Article Expired - Lifetime EP0811086B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0209995A AT402827B (en) 1995-12-22 1995-12-22 CELLULOSE MOLDED BODY AND METHOD FOR THE PRODUCTION THEREOF
AT2099/95 1995-12-22
PCT/AT1996/000257 WO1997023666A1 (en) 1995-12-22 1996-12-19 Cellulose moulded article and method of producing same

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EP0811086A1 true EP0811086A1 (en) 1997-12-10
EP0811086B1 EP0811086B1 (en) 1998-06-10

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JP (1) JP4326023B2 (en)
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US6605350B1 (en) * 1996-08-23 2003-08-12 Weyerhaeuser Company Sawdust alkaline pulp having low average degree of polymerization values and method of producing the same
DE19948401C1 (en) * 1999-10-07 2001-05-03 Alceru Schwarza Gmbh Process for the production of cellulose moldings
JP4645093B2 (en) * 2003-08-13 2011-03-09 王子製紙株式会社 Method for producing bleached pulp
DE102004024028B4 (en) * 2004-05-13 2010-04-08 Lenzing Ag Lyocell method and apparatus with press water return
CN100359050C (en) * 2004-11-16 2008-01-02 唐山三友集团化纤有限公司 High whiteness and strength adhesive short fiber and process for making same
CN1302160C (en) * 2005-01-04 2007-02-28 陈建旭 Production of fibre from plant stem

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NL97796C (en) * 1958-05-29
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
US4246221A (en) * 1979-03-02 1981-01-20 Akzona Incorporated Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent
AU636173B2 (en) * 1989-10-30 1993-04-22 Lenzing Aktiengesellschaft Method for the chlorine-free bleaching of pulps
AT395028B (en) * 1990-02-07 1992-08-25 Chemiefaser Lenzing Ag METHOD FOR CHLORINE-FREE BLEACHING OF FIBER FIBER
GB9103297D0 (en) * 1991-02-15 1991-04-03 Courtaulds Plc Fibre production method
SE9301160L (en) * 1992-08-28 1994-03-01 Sunds Defibrator Ind Ab Process for treating process water

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Title
See references of WO9723666A1 *

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DE59600279D1 (en) 1998-07-16
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CA2212995C (en) 2006-09-19
CN1182460A (en) 1998-05-20
HK1018082A1 (en) 1999-12-10
JPH11501090A (en) 1999-01-26
ZA9610469B (en) 1997-06-24
WO1997023666A1 (en) 1997-07-03
CN1079848C (en) 2002-02-27
MY113146A (en) 2001-11-30
ATE167242T1 (en) 1998-06-15
AT402827B (en) 1997-09-25
CA2212995A1 (en) 1997-07-03
AU708427B2 (en) 1999-08-05
NO310665B1 (en) 2001-08-06
ATA209995A (en) 1997-01-15
NO973720D0 (en) 1997-08-13
ES2119576T3 (en) 1998-10-01
EP0811086B1 (en) 1998-06-10
JP4326023B2 (en) 2009-09-02
NO973720L (en) 1997-08-13
AU1132597A (en) 1997-07-17

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