EP0797696A1 - Process for producing cellulose fibres - Google Patents

Process for producing cellulose fibres

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Publication number
EP0797696A1
EP0797696A1 EP96932374A EP96932374A EP0797696A1 EP 0797696 A1 EP0797696 A1 EP 0797696A1 EP 96932374 A EP96932374 A EP 96932374A EP 96932374 A EP96932374 A EP 96932374A EP 0797696 A1 EP0797696 A1 EP 0797696A1
Authority
EP
European Patent Office
Prior art keywords
filaments
squeezing
cellulosic fibers
fibers
cellulosic
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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
EP96932374A
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German (de)
French (fr)
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EP0797696B1 (en
EP0797696B2 (en
Inventor
Markus Eibl
Dieter Eichinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to SI9630026T priority Critical patent/SI0797696T1/en
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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
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/26—Formation of staple fibres
    • 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
    • D04H1/42—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
    • D04H1/4258—Regenerated 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion

Definitions

  • the invention relates to a process for the production of cellulosic fibers by the amine oxide process, and to cellulosic fibers, in particular cellulosic staple fibers.
  • 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.
  • US Pat. No. 4,246,221 describes an amine oxide process for the production of cellulose solutions which are spun into filaments in a mold, for example a spinneret, and then passed through a precipitation bath in which the cellulose is precipitated and water-containing, swollen Filaments can be obtained. These filaments can be processed in a conventional manner, that is to say by washing and post-treatment, to give cellulosic fibers and staple fibers.
  • the cellulosic fiber the production of which is not specified, has a permanent crimp, but it is not explained in detail what is to be understood by this and how the crimp can be imparted to the fiber.
  • Fibers that have a crimp are advantageous for processing fibers, in particular staple fibers, for various reasons. For example, carding of the fibers is more successful, since this requires a certain degree of adhesion of the fibers to one another so that a card sliver can be produced at all.
  • a crimped fiber has a higher tape adhesion than an uncrimped fiber, which can increase the carding speed.
  • a method is known from WO 94/28220 and WO 94/27903 with which lyocell fibers can be given a crimp in a mechanical manner.
  • the freshly produced filaments are first passed through a series of washing baths in order to remove the solvent.
  • the rope is then dried at about 165 ° C. and, when dry, is stuffed into a tubular device in which the filament rope crumples and a kind of crimp is produced in this way.
  • the crimped fiber treated with hot, dry steam and then cut into staple fibers.
  • the object of the invention is to provide a method for producing a new lyocell fiber which can be processed into yarns and fabrics more easily than the conventional lyocell fiber.
  • the new fiber should not be produced by mechanical crimping according to WO 94/28220 or WO 94/27903.
  • the fiber should also not be produced with spinnerets whose spinning holes have a non-round cross-sectional shape. Rather, the lyocell fiber produced according to the invention is to be produced using conventional spinnerets, the spinning holes of which have a round cross section.
  • the method according to the invention for producing one of the cellulosic fibers has the following steps:
  • Fibers the squeezing being carried out with a force sufficient to ensure that the pinch points produced on the filament are also retained on the dried fiber and are visible as color changes when viewed under linearly polarized light.
  • pinch points is also to be understood to mean kinks, twists and other changes in the cross-sectional shape of the filaments and fibers.
  • the invention is based on the knowledge that a filament produced by the amine oxide process in the swollen state can be changed in its cross-sectional shape by squeezing, and that this squeezing is retained after drying if it is squeezed with a sufficiently large force.
  • cellulosic fibers can be produced whose cross-sectional shape at the pinch points is not circular but, for example, oval.
  • the pinch points can also be seen under the microscope as indentations, widenings or kinks.
  • the magnitude of the force to be used in squeezing naturally depends on several factors, such as the fiber titer, the degree of swelling and the extent of the desired cross-sectional changes.
  • the inventors of the present invention have found that the force required to achieve the desired cross-sectional change can be determined in a simple manner by preliminary tests.
  • the fiber can be squeezed by passing the swollen filaments through a suitable shaping tool, for example a plate press, the surface of the plate press being structured by means of elevations and depressions in order to hold the swollen filaments in Expose it to a different pressure in the longitudinal direction and in this way deform the filaments to different degrees.
  • a suitable shaping tool for example a plate press
  • the surface of the plate press being structured by means of elevations and depressions in order to hold the swollen filaments in Expose it to a different pressure in the longitudinal direction and in this way deform the filaments to different degrees.
  • the swollen filaments can also be squeezed by passing the filaments over a roller and exerting the force to squeeze the filaments with a counter-roller, the surface of which is structured accordingly.
  • the squeezing is preferably carried out so that there are at least three, in particular at least six, squeezing points per millimeter of filament length.
  • the fibers produced according to the invention can be carded more easily since the pinch points apparently give the fibers a certain amount of adhesion to one another, so that a card sliver can be produced more easily.
  • the fibers produced according to the invention have a higher tape adhesion than a conventional lyocell fiber with a continuously round cross section. This enables the carding speed to be increased.
  • a preferred embodiment of the method according to the invention is characterized in that the water-containing, swollen filaments obtained in step (B) above are cut before pressing.
  • a further preferred embodiment of the method according to the invention is characterized in that a fleece is formed from the cut, water-containing, swollen filaments before being squeezed, in which the cut filaments are statistically oriented, and that the fleece is pressed. It has been shown that in this case the pressing surface does not need to be structured, since the differently high pressure required to impress an irregular surface is caused by the fact that the fibers lie one above the other due to their statistical orientation, which means that at the pressing, where the fibers lie on top of each other, naturally a higher pressure is exerted than in other places. This leads to a different cross-sectional deformation.
  • the pressing can be carried out as part of the usual pressing of washing water from a staple fiber fleece known from the viscose method.
  • This dewatering is usually carried out with one or more pairs of rollers through which the staple fiber fleece is guided on a screen belt. It is crucial, however, that the roller pair (s) exert a sufficiently high pressure on the fleece that not only reduces the water content, but also changes the cross-sectional shape of the cut, swollen filaments sufficiently.
  • the invention also relates to a cellulosic fiber, in particular a cellulosic staple fiber, which can be produced by the method according to the invention.
  • the fiber according to the invention is characterized in that the change in cross-section of the fiber is retained, i.e. does not disappear after carding or after yarn production. This facilitates the further processing of the Lyocell fiber according to the invention.
  • the invention further includes yarns, fabrics, non-wovens, knitted fabrics and knitted fabrics which are characterized in that they contain the fibers according to the invention.
  • a spinnable solution of cellulose in water-containing NMMO was first produced, the method described in EP-A - 0 356 419 being used.
  • This spinnable solution was spun into filaments in accordance with the process described in WO 93/19230, using a nozzle with circular spinning holes. After being drawn, the filaments were passed into an air gap in an aqueous precipitation bath in which the cellulose coagulated. The water-containing filaments obtained, which were in the swollen state and were hydroplastic, were cut into stack lengths of 4 cm.
  • the cut filaments were slurried in water in a mixer, and the cut filaments whirled in the water were applied to a screen belt on which a fleece of cut fibers formed, the fibers being oriented in all directions.
  • the screen belt was passed through a pair of rollers, with a pressure of about 10 Pa being applied to the nonwoven for a time of about 0.1 seconds.
  • the fleece was then washed and passed through a further pair of rollers, with which a pressure of about 10 was again exerted on the fleece.
  • the staple fibers obtained were then dried.
  • An examination of the fibers according to the invention under a polarizing microscope (magnification: 400 times) showed that there were an average of 7 pinch points per millimeter of fiber length, at which a change in color of the polarized light was recognizable. At the pinch points, the fibers had a cross-section that was not circular but more or less irregularly deformed. The change in color of the transmitted light is due to the different thickness of the fibers at the respective pinch points.
  • Yarns were produced from the fibers obtained and the adhesive lengths of the tapes were measured in accordance with DIN 53834, Part 1.
  • the fibers produced according to the invention showed a greater adhesive length than fibers with a substantially circular cross section that were not produced according to the invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Nonwoven Fabrics (AREA)
  • Woven Fabrics (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a process for producing cellulose fibres comprising the steps (A) dissolving a cellulose-containing material in an aqueous tertiary amine oxide to obtain a spinnable cellulose solution; (B) spinning the cellulose solution and taking it through an aqueous precipitation bath, giving water-containing swollen filaments; (C) crushing the water-containing swollen filaments at different points so that there are at least two crushed points per millimetre of filament length, and (D) drying the crushed filaments to obtain cellulose fibres; in which the filaments are crushed under sufficient pressure so that the crushed points also remain on the dried fibre and are visible as colour changes when observed under linearly polarised light.

Description

Verfahren zur Herstellung cellulosischer FasernProcess for the production of cellulosic fibers
Die Erfindung betrifft ein Verfahren zur Herstellung cellulosischer Fasern nach dem Aminoxidverfahren, sowie cellulosische Fasern, insbesondere cellulosische Stapelfasern.The invention relates to a process for the production of cellulosic fibers by the amine oxide process, and to cellulosic fibers, in particular cellulosic staple fibers.
Seit einigen Jahrzehnten wird nach Verfahren zur Herstellung cellulosischer Formkörper 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 Lösungsmittel aufzulösen und aus dieser Lösung Formkörper, z.B. Fasern, Folien und Membranen, 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 organischen Chemikalie und Wasser verstanden.For several decades, processes for the production of cellulosic molded articles have been sought which are 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 in the process of dissolving cellulose in an organic solvent without derivatization and molding, e.g. Extrude fibers, foils and membranes. Such extruded fibers were given the generic name Lyocell by BISFA (The International Bureau for the Standardization of man made fibers). BISFA defines an organic solvent as a mixture of an organic chemical and water.
Es hat sich herausgestellt, daß sich als organisches Lösungsmittel insbesondere ein Gemisch aus einem tertiären Aminoxid und Wasser sehr gut zur Herstellung von cellulosischen Formkörpern 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 US-A - 4,246,221 ist ein Aminoxidverfahren zur Herstellung von Celluloselösungen beschrieben, die in einem Formwerkzeug, z.B einer Spinndüse, zu Filamenten versponnen und anschließend durch ein Fällbad geführt werden, in welchem die Cellulose gefällt wird und wasserhaltige, gequollene Filamente erhalten werden. Diese Filamente können auf herkömmliche Weise, also durch Waschen und Nachbehandeln, zu cellulosischen Fasern und Stapelfasern verarbeitet werden.US Pat. No. 4,246,221 describes an amine oxide process for the production of cellulose solutions which are spun into filaments in a mold, for example a spinneret, and then passed through a precipitation bath in which the cellulose is precipitated and water-containing, swollen Filaments can be obtained. These filaments can be processed in a conventional manner, that is to say by washing and post-treatment, to give cellulosic fibers and staple fibers.
Es ist bekannt, daß die aus Aminoxidlösungen nach dem Trocken/Naß-Spinnverfahren hergestellten Cellulosefasern im Gegensatz zu natürlichen, gekräuselten Cellulosefasern, wie Baumwolle, einen ungelappten, runden Querschnitt aufweisen. Der runde Querschnitt und die relativ glatte Oberfläche können bei der Weiterverarbeitung zu Garnen und Flächengebilden zu Problemen führen, wie z.B. in der EP-A - 0 574 870 beschrieben wird. Diese Probleme sind gemäß dieser Patentveröffentlichung eine mangelhafte Faserhaftung bei der Verspinnung der Spinnfaser zu Garnen, ein unzureichender Fadenschluß bei den Filamentgarnen und eine zu geringe Schiebefestigkeit der Flächengebilde aus diesen Faser- und Filamentgarnen. Zur Lösung dieser Probleme wird in dieser Patentveröffentlichung vorgeschlagen, die Aminoxidlösung durch Spinnlöcher zu extrudieren, deren Querschnitt nicht rund, sondern profiliert, beispielsweise Y-förmig, ist. Auf diese Weise wird den Lyocell-Fasern ein Y-förmiger Querschnitt verliehen.It is known that the cellulose fibers produced from amine oxide solutions by the dry / wet spinning process, in contrast to natural, crimped cellulose fibers such as cotton, have an unlobed, round cross section. The round cross-section and the relatively smooth surface can lead to problems during further processing into yarns and fabrics, e.g. is described in EP-A-0 574 870. According to this patent publication, these problems are inadequate fiber adhesion in the spinning of the staple fiber into yarns, inadequate thread closure in the filament yarns and insufficient sliding resistance of the flat structures made from these fiber and filament yarns. In order to solve these problems, it is proposed in this patent publication to extrude the amine oxide solution through spinning holes, the cross-section of which is not round, but profiled, for example Y-shaped. In this way, the Lyocell fibers are given a Y-shaped cross section.
In Chemical Fibers International (CFI), Band 45, Februar 1995, Seiten 27 und 30 ist das mikroskopische Bild von vier cellulosischen Fasern gezeigt, die alle nach dem Aminoxidverfahren hergestellt wurden. Bemerkenswert ist, daß diese Fasern trotz der Tatsache, daß sie alle nach dem Aminoxidverfahren hergestellt wurden, nicht identisch sind. Die Unterschiede zwischen den vier Fasern sind sogar unter dem Mikroskop erkennbar. In der genannten Literatur ist nicht angegeben, auf welche Weise der Fachmann die verschiedenen cellulosischen Fasern herstellen kann, m.a.W. wird dem Fachmann nicht mitgeteilt, auf welche Weise er den einzelnen Fasern ihr verschiedenes Aussehen verleihen kann. In Textilia Europe 6/94, Seiten 6ff ist ebenfalls eine cellulosische Faser beschrieben, die nach dem Aminoxidverfahren hergestellt wurde, wobei dem Fachmann erneut keine Einzelheiten über die Herstellung mitgeteilt werden. Unter anderem ist dieser Literatur zu entnehmen, daß die cellulosische Faser, deren Herstellung nicht angegeben wird, eine permanente Kräuselung aufweist, wobei jedoch nicht näher darauf eingegangen wird, was darunter zu verstehen ist und auf welche Weise der Faser die Kräuselung verliehen werden kann.Chemical Fibers International (CFI), Volume 45, February 1995, pages 27 and 30 shows the microscopic image of four cellulosic fibers, all of which were produced by the amine oxide process. It is noteworthy that, despite the fact that they were all made by the amine oxide process, these fibers are not identical. The differences between the four fibers can even be seen under the microscope. The literature mentioned does not state how the person skilled in the art can produce the various cellulosic fibers; maW is not informed to the person skilled in the art how he can give the individual fibers their different appearance. Textilia Europe 6/94, pages 6ff also describes a cellulosic fiber which was produced by the amine oxide process, again no details of the production being given to the person skilled in the art. Among other things, it can be seen from this literature that the cellulosic fiber, the production of which is not specified, has a permanent crimp, but it is not explained in detail what is to be understood by this and how the crimp can be imparted to the fiber.
Fasern, die eine Kräuselung aufweisen, sind aus verschiedenen Gründen für die Verarbeitung von Fasern, insbesondere Stapelfasern, vorteilhaft. So gelingt beispielsweise das Kardieren der Fasern besser, da hierfür eine gewisse Haftung der Fasern aneinander notwendig ist, damit ein Kardenband überhaupt hergestellt werden kann. Eine gekräuselte Faser hat eine höhere Bandhaftung als eine nicht gekräuselte Faser, wodurch die Kardiergeschwindigkeit erhöht werden kann.Fibers that have a crimp are advantageous for processing fibers, in particular staple fibers, for various reasons. For example, carding of the fibers is more successful, since this requires a certain degree of adhesion of the fibers to one another so that a card sliver can be produced at all. A crimped fiber has a higher tape adhesion than an uncrimped fiber, which can increase the carding speed.
Im Stand der Technik sind sogenannte Crimpverfahren bekannt, mit welchen Fasern eine Kräuselung aufgebracht werden kann. Die auf diese Weise aufgebrachte Kräuselung geht jedoch meist schon nach der Kardierung, spätestens jedoch nach dem Garnspinnen, wieder verloren und findet sich im textilen Gewebe nicht mehr. Eine Kräuselung würde dem textilen Gewebe einen voluminösen, weichen Griff verleihen.So-called crimping methods are known in the prior art, with which fibers a crimp can be applied. However, the crimp applied in this way is usually lost again after carding, but at the latest after yarn spinning, and is no longer found in the textile fabric. A ripple would give the textile fabric a voluminous, soft feel.
Aus der WO 94/28220 und der WO 94/27903 ist ein Verfahren bekannt, mit welchem Lyocell-Fasern auf mechanische Weise eine Kräuselung verliehen werden kann. Gemäß diesem Verfahren werden die frisch hergestellten Filamente in Tauform zunächst durch eine Reihe von Waschbäder geführt, um das Lösungsmittel zu entfernen. Dann wird das Tau bei etwa 165'C getrocknet und in getrocknetem Zustand in eine rohrartige Vorrichtung gestopft, in welcher das Filamenttau zerknittert und auf diese Weise eine Art Kräuselung erzeugt wird. Zusätzlich wird die gekräuselte Faser mit heißem, trockenem Dampf behandelt und danach zur Stapelfasern geschnitten. Diese Fasern haben den Nachteil, daß sie nur aufwendig hergestellt werden können, da für die Kräuselung eine eigene Vorrichtung erforderlich ist, und daß die Kräuselung durch ein Zerknittern der Fasern hervorgerufen wird. Außerdem hat sich gezeigt, daß die nach diesem vorbekannten Verfahren auf mechanische Weise aufgebrachte Kräuselung nach einigen weiteren Nachbearbeitungsschritten für die Faser wieder verlorengeht.A method is known from WO 94/28220 and WO 94/27903 with which lyocell fibers can be given a crimp in a mechanical manner. According to this method, the freshly produced filaments are first passed through a series of washing baths in order to remove the solvent. The rope is then dried at about 165 ° C. and, when dry, is stuffed into a tubular device in which the filament rope crumples and a kind of crimp is produced in this way. In addition, the crimped fiber treated with hot, dry steam and then cut into staple fibers. These fibers have the disadvantage that they can only be produced with great effort, since a separate device is required for the crimping, and that the crimping is caused by crumpling of the fibers. It has also been shown that the crimp applied mechanically by this previously known method is lost again after a few further post-processing steps for the fiber.
Die Erfindung stellt sich die Aufgabe, ein Verfahren zur Herstellung einer neuen Lyocell-Faser zur Verfügung zu stellen, welche leichter zu Garnen und Geweben weiterverarbeitet werden kann, als die herkömmliche Lyocell-Faser. Die neue Faser soll nicht durch eine mechanische Kräuselung gemäß der WO 94/28220 oder der WO 94/27903 hergestellt werden. Die Faser soll auch nicht mit Spinndüsen hergestellt werden, deren Spinnlöcher eine nicht-runde Querschnittsform aufweisen. Die erfindungsgemäß hergestellte Lyocell-Faser soll vielmehr mit herkömmlichen Spinndüsen, deren Spinnlöcher einen runden Querschnitt aufweisen, hergestellt werden.The object of the invention is to provide a method for producing a new lyocell fiber which can be processed into yarns and fabrics more easily than the conventional lyocell fiber. The new fiber should not be produced by mechanical crimping according to WO 94/28220 or WO 94/27903. The fiber should also not be produced with spinnerets whose spinning holes have a non-round cross-sectional shape. Rather, the lyocell fiber produced according to the invention is to be produced using conventional spinnerets, the spinning holes of which have a round cross section.
Das erfindungsgemäße Verfahren zur Herstellung einer der cellulosischen Faser weist die folgenden Schritte auf:The method according to the invention for producing one of the cellulosic fibers has the following steps:
(A) Auflösen eines cellulosehältigen Materials in einem wäßrigen, tertiären Aminoxid, um eine spinnbare Celluloselösung zu erhalten;(A) dissolving a cellulosic material in an aqueous tertiary amine oxide to obtain a spinnable cellulose solution;
(B) Verspinnen der Celluloselösung und Führen durch ein wäßriges Fällbad, wobei wasserhaltige, gequollene Filamente erhalten werden;(B) spinning the cellulose solution and passing it through an aqueous coagulation bath, water-containing, swollen filaments being obtained;
(C) Quetschen der wasserhaltigen, gequollenen Filamente an verschiedensten Stellen, sodaß pro Millimeter Filamentlänge durchschnittlich mindestens zwei Quetschstellen vorhanden sind, und (D) Trocknen der gequetschten Filamente zu cellulosischen(C) squeezing the water-containing, swollen filaments at various places, so that on average there are at least two squeeze points per millimeter of filament length, and (D) drying the crushed filaments to cellulosic
Fasern, wobei das Quetschen mit einer Kraft erfolgt, die ausreicht, daß die am Filament erzeugten Quetschstellen auch an der getrockneten Faser erhalten bleiben und bei Betrachtung unter linear polarisiertem Licht als Farbänderungen sichtbar sind.Fibers, the squeezing being carried out with a force sufficient to ensure that the pinch points produced on the filament are also retained on the dried fiber and are visible as color changes when viewed under linearly polarized light.
Unter dem Ausdruck "Quetschstellen" sind für die Zwecke der vorliegenden Beschreibung und Patentansprüche auch Knicke, Verdrillungen und andere Änderungen der Querschnittsform der Filamente und Fasern zu verstehen.For the purposes of the present description and claims, the term “pinch points” is also to be understood to mean kinks, twists and other changes in the cross-sectional shape of the filaments and fibers.
Die Erfindung beruht auf der Erkenntnis, daß ein nach dem Aminoxidverfahren hergestelltes Filament in gequollenem Zustand durch Quetschen in seiner Querschnittsform verändert werden kann, und daß diese Quetschung nach dem Trocknen erhalten bleibt, wenn mit einer ausreichend großen Kraft gequetscht wird. Auf diese Weise können cellulosische Fasern hergestellt werden, deren Querschnittsform an den Quetschstellen nicht kreisrund sondern beispielsweise oval verformt ist. Die Quetschstellen sind unter dem Mikroskop auch als Einbuchtungen, Verbreiterungen oder Knicke erkennbar.The invention is based on the knowledge that a filament produced by the amine oxide process in the swollen state can be changed in its cross-sectional shape by squeezing, and that this squeezing is retained after drying if it is squeezed with a sufficiently large force. In this way, cellulosic fibers can be produced whose cross-sectional shape at the pinch points is not circular but, for example, oval. The pinch points can also be seen under the microscope as indentations, widenings or kinks.
Die Größe der Kraft, die beim Quetschen anzuwenden ist, hängt naturgemäß von mehreren Faktoren ab, wie z.B. vom Fasertiter, vom Quellungsgrad und vom Ausmaß der gewünschten Querschnittsveränderungen. Die Erfinder der vorliegenden Erfindung haben festgestellt, daß die zur Erreichung der gewünschten Querschnittsveränderung erforderliche Kraft durch Vorversuche auf einfache Weise bestimmt werden kann.The magnitude of the force to be used in squeezing naturally depends on several factors, such as the fiber titer, the degree of swelling and the extent of the desired cross-sectional changes. The inventors of the present invention have found that the force required to achieve the desired cross-sectional change can be determined in a simple manner by preliminary tests.
Das Quetschen der Faser kann erzielt werden, indem die geqollenen Filamente durch ein entsprechendes Formwerkzeug, beispielsweise eine Plattenpresse, geführt werden, wobei die Oberfläche der Plattenpresse durch Erhöhungen und Vertiefungen strukturiert ist, um die gequollenen Filamente in Längsrichtung einem verschieden hohen Druck auszusetzen und auf diese Weise die Filamente unterschiedlich stark zu verformen.The fiber can be squeezed by passing the swollen filaments through a suitable shaping tool, for example a plate press, the surface of the plate press being structured by means of elevations and depressions in order to hold the swollen filaments in Expose it to a different pressure in the longitudinal direction and in this way deform the filaments to different degrees.
Die gequollenen Filamente können auch gequetscht werden, indem die Filamente über eine Walze geführt werden und mit einer Gegenwalze, deren Oberfläche entsprechend strukturiert ist, die Kraft zum Quetschen auf die Filamente ausgeübt wird.The swollen filaments can also be squeezed by passing the filaments over a roller and exerting the force to squeeze the filaments with a counter-roller, the surface of which is structured accordingly.
Es ist ferner möglich, die gequollenen Filamente zu einem Tau, welches aus tausenden Filamenten besteht, zusammenzufassen, in Längsrichtung zu verdrehen und in diesem Zustand durch ein Walzenpaar zu führen, welches die Kraft zum Quetschen ausübt.It is also possible to combine the swollen filaments into a rope consisting of thousands of filaments, to twist them in the longitudinal direction and, in this state, to pass them through a pair of rollers which exert the force for squeezing.
Das Quetschen wird vorzugsweise so vorgenommen, daß pro Millimeter Filamentlänge mindestens drei, insbesondere mindestens sechs Quetschstellen vorhanden sind.The squeezing is preferably carried out so that there are at least three, in particular at least six, squeezing points per millimeter of filament length.
Es hat sich gezeigt, daß die erfindungsgemäß hergestellten Fasern leichter kardiert werden können, da die Quetschstellen den Fasern offenbar eine gewisse Haftung aneinander verleihen, sodaß ein Kardenband leichter hergestellt werden kann. Die erfindungsgemäß hergestellten Fasern haben eine höhere Bandhaftung als eine herkömmliche Lyocell-Faser mit durchgehend rundem Querschnitt. Dies ermöglicht, daß die Kardiergeschwindigkeit erhöht werden kann.It has been shown that the fibers produced according to the invention can be carded more easily since the pinch points apparently give the fibers a certain amount of adhesion to one another, so that a card sliver can be produced more easily. The fibers produced according to the invention have a higher tape adhesion than a conventional lyocell fiber with a continuously round cross section. This enables the carding speed to be increased.
Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß die oben im Schritt (B) erhaltenen, wasserhaltigen, gequollenen Filamente vor dem Verpressen geschnitten werden.A preferred embodiment of the method according to the invention is characterized in that the water-containing, swollen filaments obtained in step (B) above are cut before pressing.
Eine weitere bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß aus den geschnittenen, wasserhaltigen, gequollenen Filamente vor dem Quetschen ein Vlies gebildet wird, in welchem die geschnittenen Filamente statistisch orientiert sind, und daß das Vlies verpreßt wird. Es hat sich gezeigt, daß in diesem Fall die Verpressungsfläche nicht strukturiert zu sein braucht, da der zur Aufprägung einer unregelmäßigen Oberfläche notwendige, unterschiedlich hohe Druck dadurch zustande kommt, daß die Fasern infolge ihrer statistischen Orientierung übereinander liegen, wodurch beim Verpressen an denjenigen Stellen, wo die Fasern übereinander liegen, naturgemäß ein höherer Druck ausgeübt wird, als an anderen Stellen. Dies führt zu einer unterschiedlichen Querschnittsverformung.A further preferred embodiment of the method according to the invention is characterized in that a fleece is formed from the cut, water-containing, swollen filaments before being squeezed, in which the cut filaments are statistically oriented, and that the fleece is pressed. It has been shown that in this case the pressing surface does not need to be structured, since the differently high pressure required to impress an irregular surface is caused by the fact that the fibers lie one above the other due to their statistical orientation, which means that at the pressing, where the fibers lie on top of each other, naturally a higher pressure is exerted than in other places. This leads to a different cross-sectional deformation.
Das Verpressen kann bei dieser Ausführungsform des erfindungsgemäßen Verfahrens im Rahmen des aus dem Viskoseverfahren bekannten, üblichen Abpressens von Waschwasser aus einem Stapelfaservlies vorgenommen werden. Dieses Entwässern wird üblicherweise mit einem oder mehreren Walzenpaaren vorgenommen, durch welche das Stapelfaservlies auf einem Siebband geführt wird. Entscheidend ist jedoch, daß mit dem(n) Walzenpaar(en) ein genügend hoher Druck auf das Vlies ausgeübt wird, der nicht nur den Wassergehalt verringert, sondern auch die Querschnittsform der geschnittenen, gequollenen Filamente ausreichend verändert.In this embodiment of the method according to the invention, the pressing can be carried out as part of the usual pressing of washing water from a staple fiber fleece known from the viscose method. This dewatering is usually carried out with one or more pairs of rollers through which the staple fiber fleece is guided on a screen belt. It is crucial, however, that the roller pair (s) exert a sufficiently high pressure on the fleece that not only reduces the water content, but also changes the cross-sectional shape of the cut, swollen filaments sufficiently.
Die Erfindung betrifft auch eine cellulosische Faser, insbesondere eine cellulosische Stapelfaser, die nach dem erfindungsgemäßen Verfahren hergestellt werden kann. Die erfindungsgemäße Faser zeichnet sich dadurch aus, daß die hervorgerufene Querschnittsveränderung der Faser erhalten bleibt, d.h. nach dem Kardieren oder nach der Garnherstellung nicht verschwindet. Dies erleichtert die Weiterverarbeitung der erfindungsgemäßen Lyocell-Faser.The invention also relates to a cellulosic fiber, in particular a cellulosic staple fiber, which can be produced by the method according to the invention. The fiber according to the invention is characterized in that the change in cross-section of the fiber is retained, i.e. does not disappear after carding or after yarn production. This facilitates the further processing of the Lyocell fiber according to the invention.
Es hat sich ferner überraschenderweise gezeigt, daß die Faserfestigkeit und die Faserdehnung der nach dem Aminoxidverfahren hergestellten Fasern durch die Querschnittsveränderung nicht beeinträchtigt werden. Die Erfindung umfaßt ferner Garne, Gewebe, Non Wovens, Gestricke und Gewirke, die dadurch gekennzeichnet sind, daß sie die erfindungsgemäßen Fasern enthalten.It has also surprisingly been found that the fiber strength and the fiber elongation of the fibers produced by the amine oxide process are not impaired by the change in cross section. The invention further includes yarns, fabrics, non-wovens, knitted fabrics and knitted fabrics which are characterized in that they contain the fibers according to the invention.
Mit dem folgenden Beispiel wird die Erfindung noch näher erläutert.The invention is explained in more detail with the following example.
Beispiel lExample 1
Es wurde zunächst eine spinnbare Lösung von Cellulose in wasserhaltigem NMMO hergestellt, wobei das in der EP-A - 0 356 419 beschriebene Verfahren angewendet wurde.A spinnable solution of cellulose in water-containing NMMO was first produced, the method described in EP-A - 0 356 419 being used.
Diese spinnbare Lösung wurde gemäß dem in der WO 93/19230 beschriebenen Verfahren zu Filamenten gesponnen, wobei eine Düse mit kreisrunden Spinnlöchern verwendet wurde. Die Filamente wurden nach Verzug in einem Luftspalt in ein wäßriges Fällbad geführt, in welchem die Cellulose koagulierte. Die erhaltenen wasserhaltigen Filamente, die in gequollenem Zustand vorlagen und hydroplastisch waren, wurden zu Stapellängen von 4 cm geschnitten.This spinnable solution was spun into filaments in accordance with the process described in WO 93/19230, using a nozzle with circular spinning holes. After being drawn, the filaments were passed into an air gap in an aqueous precipitation bath in which the cellulose coagulated. The water-containing filaments obtained, which were in the swollen state and were hydroplastic, were cut into stack lengths of 4 cm.
Die geschnittenen Filamente wurden in einem Mischer in Wasser aufgeschlämmt, und die im Wasser aufgewirbelten, geschnittenen Filamente wurden auf ein Siebband aufgebracht, auf welchem sich ein Vlies aus geschnittenen Fasern bildete, wobei die Fasern nach allen Richtungen orientiert waren.The cut filaments were slurried in water in a mixer, and the cut filaments whirled in the water were applied to a screen belt on which a fleece of cut fibers formed, the fibers being oriented in all directions.
Das Siebband wurde durch ein Walzenpaar geführt, wobei ein Druck von etwa 10 Pa während einer Zeit von etwa 0,1 Sekunden auf das Vlies ausgeübt wurde. Anschließend wurde das Vlies gewaschen und noch durch ein weiteres Walzenpaar geführt, mit welchem neuerlich ein Druck von etwa 10 auf das Vlies ausgeübt wurde. Danach wurden die erhaltenen Stapelfasern getrocknet. Eine Untersuchung der erfindungsgemäßen Fasern unter dem Polarisationsmikroskop (Vergrößerung: 400fach) zeigte, daß pro Millimeter Faserlänge im Durchschnitt 7 Quetschstellen vorhanden waren, an denen eine Farbänderung des polarisierten Lichtes erkennbar war. An den Quetschstellen besaßen die Fasern einen Querschnitt, der nicht kreisrund, sondern mehr oder weniger unregelmäßig verformt ist. Die Farbänderung des durchstrahlten Lichtes ist auf die unterschiedliche Dicke der Fasern an den jeweiligen Quetschstellen zurückzuführen.The screen belt was passed through a pair of rollers, with a pressure of about 10 Pa being applied to the nonwoven for a time of about 0.1 seconds. The fleece was then washed and passed through a further pair of rollers, with which a pressure of about 10 was again exerted on the fleece. The staple fibers obtained were then dried. An examination of the fibers according to the invention under a polarizing microscope (magnification: 400 times) showed that there were an average of 7 pinch points per millimeter of fiber length, at which a change in color of the polarized light was recognizable. At the pinch points, the fibers had a cross-section that was not circular but more or less irregularly deformed. The change in color of the transmitted light is due to the different thickness of the fibers at the respective pinch points.
Aus den erhaltenen Fasern wurden Garne hergestellt und die Haftlängen der Bänder gemäß DIN 53834, Teil l, gemessen. Die erfindungsgemäß hergestellten Fasern zeigten im Vergleich eine größere Haftlänge als nicht erfindungsgemäß hergestellte Fasern mit im wesentlichen kreisrundem Querschnitt. Yarns were produced from the fibers obtained and the adhesive lengths of the tapes were measured in accordance with DIN 53834, Part 1. In comparison, the fibers produced according to the invention showed a greater adhesive length than fibers with a substantially circular cross section that were not produced according to the invention.

Claims

Patentansprüche:Claims:
1. Verfahren zur Herstellung cellulosischer Fasern, welches Verfahren folgende Schritte aufweist:1. A process for producing cellulosic fibers, the process comprising the following steps:
(A) Auflösen eines cellulosehältigen Materials in einem wäßrigen, tertiären Aminoxid, um eine spinnbare Celluloselösung zu erhalten;(A) dissolving a cellulosic material in an aqueous tertiary amine oxide to obtain a spinnable cellulose solution;
(B) Verspinnen der Celluloselösung und Führen durch ein wäßriges Fällbad, wobei wasserhaltige, gequollene Filamente erhalten werden;(B) spinning the cellulose solution and passing it through an aqueous coagulation bath, water-containing, swollen filaments being obtained;
(C) Quetschen der wasserhaltigen, gequollenen Filamente an verschiedensten Stellen, sodaß pro Millimeter Filamentlänge durchschnittlich mindestens zwei Quetschstellen vorhanden sind, und(C) squeezing the water-containing, swollen filaments at various places, so that on average there are at least two squeeze points per millimeter of filament length, and
(D) Trocknen der gequetschten Filamente zu cellulosischen Fasern, wobei das Quetschen unter einem Druck erfolgt, der ausreicht, daß die am Filament erzeugten Quetschstellen auch an der getrockneten Faser erhalten bleiben und bei Betrachtung unter linear polarisiertem Licht als Farbänderungen sichtbar sind.(D) drying the squeezed filaments to cellulosic fibers, the squeezing being carried out under a pressure which is sufficient for the pinch points produced on the filament to remain intact on the dried fiber and are visible as color changes when viewed under linearly polarized light.
Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Quetschen so durchgeführt wird, daß pro Millimeter Filamentlänge durchschnittlich mindestens drei Quetschstellen vorhanden sind.Method according to claim 1, characterized in that the squeezing is carried out in such a way that on average there are at least three squeezing points per millimeter of filament length.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Quetschen so durchgeführt wird, daß pro Millimeter Filamentlänge durchschnittlich mindestens sechs Quetschstellen vorhanden sind. 4. Verfahren zur Herstellung cellulosischer Fasern nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die im Schritt (B) erhaltenen, wasserhaltigen, gequollenen Filamente vor dem Quetschen geschnitten werden.3. The method according to claim 1, characterized in that the squeezing is carried out so that there are an average of at least six squeezing points per millimeter of filament length. 4. A process for the production of cellulosic fibers according to one of claims 1 to 3, characterized in that the water-containing, swollen filaments obtained in step (B) are cut before being squeezed.
Verfahren zur Herstellung cellulosischer Fasern nach Anspruch 4, dadurch gekennzeichnet, daß aus den geschnittenen, wasserhaltigen, gequollenen Filamente vor dem Quetschen ein Vlies gebildet wird, in welchem die geschnittenen Filamente statistisch orientiert sind, und daß das Vlies verpreßt wird.Process for the production of cellulosic fibers according to Claim 4, characterized in that, before being squeezed, a cut is formed from the cut, water-containing, swollen filaments, in which the cut filaments are statistically oriented, and in that the fleece is pressed.
6. Cellulosische Faser, erhältlich nach einem Verfahren gemäß einem der Ansprüche 1 bis 3.6. Cellulosic fiber, obtainable by a process according to any one of claims 1 to 3.
Cellulosische Stapelfaser, erhältlich nach einem der Ansprüche 4 oder 5.Cellulosic staple fiber, obtainable according to one of claims 4 or 5.
8. Garn, dadurch gekennzeichnet, daß es cellulosische Fasern nach einem der Ansprüche 6 und 7 enthält.8. Yarn, characterized in that it contains cellulosic fibers according to one of claims 6 and 7.
Gewebe, dadurch gekennzeichnet, daß es cellulosische Fasern nach einem der Ansprüche 6 und 7 enthält.Fabric, characterized in that it contains cellulosic fibers according to one of claims 6 and 7.
10. Non Wovens, Gestricke und Gewirke, dadurch gekennzeichnet, daß sie cellulosische Fasern nach einem der Ansprüche 6 und 7 enthalten. 10. Non-wovens, knitted fabrics and knitted fabrics, characterized in that they contain cellulosic fibers according to one of claims 6 and 7.
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GB2310630A (en) 1997-09-03
TW421677B (en) 2001-02-11
ATA170395A (en) 1996-12-15
BG101688A (en) 1998-03-31
JP2007016381A (en) 2007-01-25
ZA968515B (en) 1997-05-20
MY113879A (en) 2002-06-29
SI0797696T1 (en) 1998-12-31
PL188136B1 (en) 2004-12-31
CN1070543C (en) 2001-09-05
HUP9800831A3 (en) 1998-12-28
CA2206250A1 (en) 1997-04-24
GB2310630B (en) 1999-02-17
AU705530B2 (en) 1999-05-27
NO972440D0 (en) 1997-05-28
NO972440L (en) 1997-05-28
GR3027605T3 (en) 1998-11-30
DK0797696T3 (en) 1999-05-03
DE59600380D1 (en) 1998-09-03
DE19680883D2 (en) 1998-04-16
SK284228B6 (en) 2004-11-03
ATE169063T1 (en) 1998-08-15
HUP9800831A2 (en) 1998-07-28
NO309490B1 (en) 2001-02-05
CZ161497A3 (en) 1998-06-17
PL320740A1 (en) 1997-10-27
CN1173901A (en) 1998-02-18
AT402741B (en) 1997-08-25
CZ290849B6 (en) 2002-10-16
WO1997014829A1 (en) 1997-04-24
ES2120286T5 (en) 2008-04-16
CA2206250C (en) 2003-12-09

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