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EP0797696B2 - Process for producing cellulose fibres - Google Patents
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EP0797696B2 - Process for producing cellulose fibres - Google Patents

Process for producing cellulose fibres Download PDF

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Publication number
EP0797696B2
EP0797696B2 EP96932374A EP96932374A EP0797696B2 EP 0797696 B2 EP0797696 B2 EP 0797696B2 EP 96932374 A EP96932374 A EP 96932374A EP 96932374 A EP96932374 A EP 96932374A EP 0797696 B2 EP0797696 B2 EP 0797696B2
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European Patent Office
Prior art keywords
squeezing
filaments
fibers
water
points
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EP96932374A
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German (de)
French (fr)
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EP0797696A1 (en
EP0797696B1 (en
Inventor
Markus Eibl
Dieter Eichinger
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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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 producing cellulosic staple fibers by the amine oxide process.
  • amine oxide used here is primarily N-methylmorpholine-N-oxide (NMMO).
  • 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. from EP-A - 0 356 419.
  • the preparation of cellulosic moldings using tertiary amine oxides is generally referred to as the amine oxide process.
  • US-A-4,246,221 discloses an amine oxide process for producing cellulose solutions which are spun into filaments in a mold, e.g. a spinneret, and then passed through a precipitation bath in which the cellulose is precipitated and water-containing swollen filaments are obtained. These filaments can be processed into cellulosic fibers and staple fibers in a conventional manner, ie by washing and aftertreatment.
  • the cellulose fibers prepared from amine oxide solutions by the dry / wet spinning method unlike natural, crimped cellulose fibers, such as cotton, have an ungapped, round cross-section.
  • the round cross section and the relatively smooth surface can lead to problems in further processing into yarns and fabrics, such as e.g. in EP-A-0 574 870.
  • These problems are according to this Patentveröt Drung a poor fiber adhesion in the spinning of the staple fiber to yarns, insufficient thread closure in the filament yarns and too low slip resistance of the fabrics of these fiber and filament yarns.
  • it is proposed in this patent publication to extrude the amine oxide solution through spinning holes whose cross-section is not round but profiled, for example Y-shaped. In this way, the Lyocell fibers are given a Y-shaped cross section.
  • Fibers which have a crimp are advantageous for the processing of fibers, in particular staple fibers, for various reasons.
  • the carding of the fibers succeed better, since this requires a certain adhesion of the fibers to each other, so that a card sliver can be made at all.
  • a crimped fiber has a higher tape adhesion than a non-crimped fiber, which can increase the carding speed.
  • DE-C-868 042 describes a process for refining fibers of synthetic linear high polymers with amide groups in the chain, in particular polyamides and polyurethanes, wherein confused fiber layers are subjected to such a high pressure by compression at elevated temperature and in the presence of swelling agents that the fibers deform superficially at the intersections. This is intended to give the synthetic polymer lasers a surface structure in the form of a roughened surface.
  • the object of the invention is to provide a process for producing a lyocell staple fiber which can be more easily processed into yarns and fabrics than the conventional lyocell fiber.
  • the fiber should not be made by mechanical crimping according to WO 94/28220 or WO 94/27903.
  • the fiber should not be made with spinnerets whose spinning holes have a non-round cross-sectional shape.
  • the lyocell staple fiber produced according to the invention should rather be produced with conventional spinnerets whose spinning holes have a round cross section.
  • pinch points is also to be understood as meaning kinks, twists and other changes in the cross-sectional shape of the filaments and fibers.
  • the invention is based on the finding that a filament prepared according to the amine oxide method can be changed in the swollen state by squeezing in its cross-sectional shape, and that this pinch after drying is maintained when squeezed with a sufficiently large pressure.
  • cellulosic fibers can be produced whose cross-sectional shape is not circular at the crimping but, for example, oval deformed.
  • the pinch points are under the microscope as indentations. Broadening or kink recognizable.
  • the magnitude of the pressure to be applied during squeezing naturally depends on a number of factors, e.g. fiber titer, degree of swelling and extent of desired cross-sectional changes.
  • the inventors of the present invention have found that the pressure required to achieve the desired cross-sectional change can be easily determined by preliminary tests.
  • the squeezing of the fiber can be accomplished by passing the swollen filaments through a suitable forming tool, such as a platen press, with the surface of the platen press structured by ridges and depressions to expose the swollen filaments to a different high pressure in the longitudinal direction Way to deform the filaments differently strong.
  • a suitable forming tool such as a platen press
  • the squeezing is preferably carried out so that at least three, in particular at least six squeezing sites are present per millimeter of filament length.
  • the fibers produced according to the invention can be more easily carded, since the pinch points give the fibers a certain adhesion to each other, so that a card sliver can be produced more easily.
  • the fibers produced according to the invention have a higher band retention than a conventional lyocell fiber with a continuous round cross-section. This allows the carding speed to be increased.
  • a preferred embodiment of the invention Method is characterized in that from the cut, water-containing, swollen filaments before crushing a nonwoven fabric is formed, in which the cut filaments are randomly oriented, and that the nonwoven fabric is pressed. It has been found that in this case the Verpressungs Stability need not be structured, since the necessary for impressing an irregular surface, different high pressure is due to the fact that the fibers are superimposed due to their statistical orientation, whereby during pressing at those points, where the fibers overlap one another, naturally a higher pressure is exerted than in other places. This leads to a different cross-sectional deformation.
  • the pressing can be carried out in this embodiment of the method according to the invention within the known from the viscose process, conventional pressing of washing water from a staple fiber fleece.
  • This dewatering is usually carried out with one or more pairs of rolls through which the staple fiber fleece is guided on a wire belt.
  • the decisive factor is that a sufficiently high pressure is exerted on the nonwoven with the roller pair (s), which not only reduces the water content, but also sufficiently changes the cross-sectional shape of the cut, swollen filaments.
  • the invention also relates to a cellulosic staple fiber which can be prepared by the process according to the invention.
  • the fiber of the invention is characterized by the fact that the induced cross-sectional change of the fiber is retained, i. 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, nonwovens, knits and knits characterized by containing the fibers of the invention.
  • a spinnable solution of cellulose in water-containing NMMO was first prepared using the method described in EP-A-0 356 419.
  • This spinnable solution was spun into filaments according to the method described in WO 93/19230, using a nozzle with circular spinning holes.
  • the filaments were passed after delay in an air gap in an aqueous precipitation bath, in which the cellulose coagulated.
  • the resulting hydrous filaments which were in the swollen state and were hydroplastic, were cut into staple lengths of 4 cm.
  • the cut filaments were slurried in water in a mixer and the cut filaments spun in the water were applied to a screen belt on which a nonwoven web of cut fibers formed, with the fibers oriented in all directions.
  • the screen belt was passed through a pair of rollers with a pressure of 10 6 Pa applied to the web for a time of about 0.1 seconds. Subsequently, the fleece was washed and passed through another pair of rollers, with which again a pressure of 10 6 Pa was applied to the web. Thereafter, the obtained staple fibers were dried.
  • Yarns were produced from the fibers obtained and the bond lengths of the strips were measured in accordance with DIN 53834, Part 1.
  • the fibers produced according to the invention showed a greater bond length than fibers having a substantially circular cross-section which were not produced according to the invention.

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  • 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

PCT No. PCT/AT96/00188 Sec. 371 Date Aug. 22, 1997 Sec. 102(e) Date Aug. 22, 1997 PCT Filed Oct. 8, 1996 PCT Pub. No. WO97/14829 PCT Pub. Date Apr. 24, 1997A process for the production of cellulose fibers, comprising the following steps: (A) dissolving a cellulose-containing material in an aqueous, tertiary amine-oxide to obtain a spinnable cellulose solution; (B) spinning said cellulose solution and passing it through an aqueous precipitation bath, whereby water-containing, swollen filaments are obtained; (C) squeezing said water-containing, swollen filaments at various points, so that at least two squeezing points per millimeter of filament length on average are achieved and (D) drying said squeezed filaments to cellulose fibers, wherein squeezing is carried out using a pressure big enough so that said squeezing points produced on the filament are preserved also on the dried fibre and may be seen as color variations when observed under linearly polarized light.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung cellulosischer Stapelfasern nach dem Aminoxidverfahren.The invention relates to a process for producing cellulosic staple fibers by the amine oxide process.

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, there has been a search for processes for the production of cellulosic moldings intended to replace the viscose process used today on a large scale. As an interesting alternative, not least because of better environmental compatibility, it has crystallized out to dissolve cellulose without derivatization in an organic solvent and from this solution moldings, e.g. Fibers, films and membranes to extrude. Such extruded fibers were given the genus name Lyocell by BISFA (The International Bureau for the Standardization of Man Made Fibers). Organic solvent is understood by BISFA to mean 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, as organic solvent, in particular a mixture of a tertiary amine oxide and water is very well suited for the production of cellulosic moldings. The amine oxide used here is primarily N-methylmorpholine-N-oxide (NMMO). Other amine oxides are e.g. in EP-A-0 553 070. A method of making moldable cellulose solutions is e.g. from EP-A - 0 356 419. The preparation 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 wasserhältige, gequollene Filamente erhalten werden. Diese Filamente können auf herkömmliche Weise, also durch Waschen und Nachbehandeln, zu cellulosischen Fasern und Stapelfasern verarbeitet werden.US-A-4,246,221 discloses an amine oxide process for producing cellulose solutions which are spun into filaments in a mold, e.g. a spinneret, and then passed through a precipitation bath in which the cellulose is precipitated and water-containing swollen filaments are obtained. These filaments can be processed into cellulosic fibers and staple fibers in a conventional manner, ie by washing and aftertreatment.

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 Patentverötfentlichung 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 Pateniveröffentlichung 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 prepared from amine oxide solutions by the dry / wet spinning method, unlike natural, crimped cellulose fibers, such as cotton, have an ungapped, round cross-section. The round cross section and the relatively smooth surface can lead to problems in further processing into yarns and fabrics, such as e.g. in EP-A-0 574 870. These problems are according to this Patentverötffentlichung a poor fiber adhesion in the spinning of the staple fiber to yarns, insufficient thread closure in the filament yarns and too low slip resistance of the fabrics of these fiber and filament yarns. To solve these problems, it is proposed in this patent publication to extrude the amine oxide solution through spinning holes whose cross-section 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 Chemical Fibers International (CFI), Vol. 45, February 1995, pages 27 and 30, there is shown the microscopic picture of four cellulosic fibers, all prepared by the amine-oxide method. Notably, these fibers are not identical despite the fact that they are all made by the amine oxide process. The differences between the four fibers are even visible under the microscope. In the cited literature it is not stated how the skilled person can prepare the various cellulosic fibers, m.a.W. The person skilled in the art is not informed of how he can give the individual fibers their different appearance.

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.In Textilia Europe 6/94, pages 6ff is also described a cellulosic fiber which was prepared by the amine-oxide process, wherein the person skilled in the art again no details of the preparation are communicated. Among other things, it can be seen from this literature that the cellulosic fiber, the preparation of which is not indicated, has a permanent crimp, but it does not elaborate on what is meant by it 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 which have a crimp are advantageous for the processing of fibers, in particular staple fibers, for various reasons. Thus, for example, the carding of the fibers succeed better, since this requires a certain adhesion of the fibers to each other, so that a card sliver can be made at all. A crimped fiber has a higher tape adhesion than a non-crimped 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.In the prior art, so-called crimping methods are known with which fibers a crimp can be applied. However, the crimping applied in this way is usually lost after carding, but at the latest after yarn spinning, and is no longer found in the textile fabric. A crimp would give the textile fabric a voluminous, soft feel.

Die DE-C - 868 042 beschreibt ein Verfahren zur Veredelung von Fasern aus synthetischen linearen Hochpolymeren mit Amidgruppen in der Kette, insbesondere Polyamiden und Polyurethanen, wobei wirre Faserlagen durch Zusammenpressen bei erhöhter Temperatur und in Gegenwart von Quellmitteln einem so hohen Druck unterworfen werden, daß sich die Fasern an den Kreuzungsstellen gegenseitig oberflächlich verformen. Dadurch soll den synthetischen Polymerlasern eine Oberflächenstruktur in Form einer gerauhten Oberfläche gegeben werden.DE-C-868 042 describes a process for refining fibers of synthetic linear high polymers with amide groups in the chain, in particular polyamides and polyurethanes, wherein confused fiber layers are subjected to such a high pressure by compression at elevated temperature and in the presence of swelling agents that the fibers deform superficially at the intersections. This is intended to give the synthetic polymer lasers a surface structure in the form of a roughened surface.

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 Taulorm 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 Nachbearbeilungsschritten für die Faser wieder verlorengeht. Die WO 95124520 beschreibt ein modifiziertes Verfahren zur mechanischen Kräuselung von Lyocell-Fasern.From WO 94/28220 and WO 94/27903 a method is known with which lyocell fibers to mechanical Way a rippling can be imparted. According to this method, the freshly prepared filaments in Taulorm are first passed through a series of washing baths to remove the solvent. Then the rope is dried at about 165 ° C and stuffed in a dried state into a tube-like device in which the Filamenttau crumpled and in this way a kind of crimping is generated. In addition, the crimped fiber is treated with hot, dry steam and then cut into staple fibers. These fibers have the disadvantage that they can be produced only consuming, since the crimping a separate device is required, and that the crimping by a. Crumpling of the fibers is caused. In addition, it has been found that the crimping applied by this known method in a mechanical manner is lost again after a few further post-broaching steps for the fiber. WO95 / 124520 describes a modified process for the mechanical crimping of lyocell fibers.

Die Erfindung stellt sich die Aufgabe, ein Verfahren zur Herstellung einer Lyocell-Stapelfaser zur Verfügung zu stellen, welche leichter zu Garnen und Geweben weiterverarbeitet werden kann, als die herkömmliche Lyocell-Faser. Die 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-Stapelfaser soll vielmehr mit herkömmlichen Spinndüsen, deren Spinnlöcher einen runden Querschnitt aufweisen, hergestellt werden.The object of the invention is to provide a process for producing a lyocell staple fiber which can be more easily processed into yarns and fabrics than the conventional lyocell fiber. The fiber should not be made by mechanical crimping according to WO 94/28220 or WO 94/27903. The fiber should not be made with spinnerets whose spinning holes have a non-round cross-sectional shape. The lyocell staple fiber produced according to the invention should rather be produced with conventional spinnerets whose spinning holes have a round cross section.

Das erfindungsgemäße Verfahren zur Herstellung der cellulosischen Stapelfaser weist die folgenden Schritte auf:

  1. (A) Auflösen eines cellulosehältigen Materials in einem wäßrigen, tertiären Aminoxid, um eine spinnbare Celluloselösung zu erhalten;
  2. (B) Verspinnen der Celluloselösung und Führen durch ein wäßriges Fällbad, wobei wasserhältige, gequollene Filamente erhalten werden;
  3. (C) Quetschen der wasserhältigen, gequollenen Filamente an verschiedensten Stellen, sodaß pro Millimeter Filamentlänge durchschnittlich mindestens zwei Quetschstellen vorhanden sind, und
  4. (D) Trocknen der gequetschten Filamente zu cellulosischen Fasern,
wobei das Quetschen mit 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, und wobei die im Schritt (B) erhaltenen, wasserhältigen, gequollenen Filamente vor dem Quetschen geschnitten werden.The inventive method for producing the cellulosic staple fiber comprises the following steps:
  1. (A) dissolving a cellulosic-containing material in an aqueous tertiary amine oxide to obtain a spinnable cellulose solution;
  2. (B) spinning the cellulose solution and passing it through an aqueous coagulation bath to obtain water-containing swollen filaments;
  3. (C) squeezing the water-containing, swollen filaments at various points, so that on average at least two pinch sites per millimeter of filament length, and
  4. (D) drying the crimped filaments into cellulosic fibers,
the squeezing being carried out at a pressure sufficient to maintain the squeezing spots produced on the filament also on the dried fiber and visible as color changes when viewed under linearly polarized light, and the water-containing, swollen filaments obtained in step (B) be cut before bruising.

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 specification and claims, the term "pinch points" is also to be understood as meaning 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 einem ausreichend großen Druck 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 finding that a filament prepared according to the amine oxide method can be changed in the swollen state by squeezing in its cross-sectional shape, and that this pinch after drying is maintained when squeezed with a sufficiently large pressure. In this way, cellulosic fibers can be produced whose cross-sectional shape is not circular at the crimping but, for example, oval deformed. The pinch points are under the microscope as indentations. Broadening or kink recognizable.

Die Größe des Druckes, der 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 der zur Erreichung der gewünschten Querschnittsveränderung erforderliche Druck durch Vorversuche auf einfache Weise bestimmt werden kann.The magnitude of the pressure to be applied during squeezing naturally depends on a number of factors, e.g. fiber titer, degree of swelling and extent of desired cross-sectional changes. The inventors of the present invention have found that the pressure required to achieve the desired cross-sectional change can be easily determined by preliminary tests.

Das Quetschen der Faser kann erzielt werden, indem die gequollenen 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 squeezing of the fiber can be accomplished by passing the swollen filaments through a suitable forming tool, such as a platen press, with the surface of the platen press structured by ridges and depressions to expose the swollen filaments to a different high pressure in the longitudinal direction Way to deform the filaments differently strong.

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 at least three, in particular at least six squeezing sites are present 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 Bandhaltung als eine herkömmliche Lyocell-Faser mit durchgehend rundem Querschnitt. Dies ermöglicht, daß die Kardiergeschwindigkeit erhöht werden kann.It has been found that the fibers produced according to the invention can be more easily carded, since the pinch points give the fibers a certain adhesion to each other, so that a card sliver can be produced more easily. The fibers produced according to the invention have a higher band retention than a conventional lyocell fiber with a continuous round cross-section. This allows the carding speed to be increased.

Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, daß aus den geschnittenen, wasserhältigen, 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 preferred embodiment of the invention Method is characterized in that from the cut, water-containing, swollen filaments before crushing a nonwoven fabric is formed, in which the cut filaments are randomly oriented, and that the nonwoven fabric is pressed. It has been found that in this case the Verpressungsfläche need not be structured, since the necessary for impressing an irregular surface, different high pressure is due to the fact that the fibers are superimposed due to their statistical orientation, whereby during pressing at those points, where the fibers overlap one another, 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.The pressing can be carried out in this embodiment of the method according to the invention within the known from the viscose process, conventional pressing of washing water from a staple fiber fleece. This dewatering is usually carried out with one or more pairs of rolls through which the staple fiber fleece is guided on a wire belt. The decisive factor, however, is that a sufficiently high pressure is exerted on the nonwoven with the roller pair (s), which not only reduces the water content, but also sufficiently changes the cross-sectional shape of the cut, swollen filaments.

Die Erfindung betrifft auch 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 staple fiber which can be prepared by the process according to the invention. The fiber of the invention is characterized by the fact that the induced cross-sectional change of the fiber is retained, i. 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.It has also surprisingly been found that the fiber strength and fiber elongation of the fibers produced by the amine oxide process are not impaired by the change in cross-section.

Die Erfindung umfaßt ferner Garne, Gewebe, Non Wovens, Gestricke und Gewirke, die dadurch gekennzeichnet sind, daß sie die erfindungsgemäßen Fasern enthalten.The invention further includes yarns, fabrics, nonwovens, knits and knits characterized by containing the fibers of the invention.

Mit dem folgenden Beispiel wird die Erfindung noch näher erläutert.With the following example, the invention will be explained in more detail.

Beispiel 1example 1

Es wurde zunächst eine spinnbare Lösung von Cellulose in wasserhältigem 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 prepared using the method described in EP-A-0 356 419.

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 wasserhältigen Filamente, die in gequollenem Zustand vorlagen und hydroplastisch waren, wurden zu Stapellängen von 4 cm geschnitten.This spinnable solution was spun into filaments according to the method described in WO 93/19230, using a nozzle with circular spinning holes. The filaments were passed after delay in an air gap in an aqueous precipitation bath, in which the cellulose coagulated. The resulting hydrous filaments, which were in the swollen state and were hydroplastic, were cut into staple 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 spun in the water were applied to a screen belt on which a nonwoven web of cut fibers formed, with the fibers oriented in all directions.

Das Siebband wurde durch ein Walzenpaar geführt, wobei ein Druck von 106 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 106 Pa auf das Vlies ausgeübt wurde. Danach wurden die erhaltenen Stapelfasern getrocknet.The screen belt was passed through a pair of rollers with a pressure of 10 6 Pa applied to the web for a time of about 0.1 seconds. Subsequently, the fleece was washed and passed through another pair of rollers, with which again a pressure of 10 6 Pa was applied to the web. Thereafter, the obtained staple fibers were dried.

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.An examination of the fibers according to the invention under the polarizing microscope (magnification: 400 times) showed that on average 7 pinch points were present per millimeter of fiber length, at which a change in color of the polarized light was detectable. At the crimping points, the fibers had a cross-section which is 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 1, 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 bond lengths of the strips were measured in accordance with DIN 53834, Part 1. By comparison, the fibers produced according to the invention showed a greater bond length than fibers having a substantially circular cross-section which were not produced according to the invention.

Claims (8)

  1. A process for producing cellulosic staple fibres, which process comprises the following steps:
    (A) dissolving a cellulose-containing material in an aqueous tertiary amine oxide in order to obtain a spinnable cellulose solution;
    (B) spinning the cellulose solution and passing it through an aqueous precipitation bath, in which process water-containing, swollen filaments are obtained;
    (C) squeezing the water-containing, swollen filaments at various points so that on average at least two squeezing points are present per millimetre of filament length; and
    (D) drying the squeezed filaments to form cellulosic fibres,
    wherein the squeezing takes place under a pressure which is sufficient for the squeezing points produced on the filament to remain intact even on the dried fibre and to be visible as colour changes when viewed under linearly polarized light and
    wherein the water-containing, swollen filaments obtained in step (B) are cut prior to squeezing.
  2. A process according to claim 1, characterized in that the squeezing is performed in such a way that on average at least three squeezing points are present per millimetre of filament length.
  3. A process according to claim 1, characterized in that the squeezing is performed in such a way that on average at least six squeezing points are present per millimetre of filament length.
  4. A process for producing cellulosic staple fibres according to any of claims 1 to 3, characterized in that a nonwoven fabric in which the cut filaments are randomly oriented is formed from the cut, water-containing, swollen filaments prior to squeezing and that the nonwoven fabric is pressed.
  5. A cellulosic staple fibre, obtainable according to any of claims 1 to 4.
  6. A yarn, characterized in that it contains cellulosic staple fibres according to claim 5.
  7. A woven fabric, characterized in that it contains cellulosic staple fibres according to claim 5.
  8. Nonwovens, knitted fabrics and hosiery, characterized in that they contain cellulosic staple fibres according to claim 5.
EP96932374A 1995-10-13 1996-10-08 Process for producing cellulose fibres Expired - Lifetime EP0797696B2 (en)

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AT0170395A AT402741B (en) 1995-10-13 1995-10-13 METHOD FOR PRODUCING CELLULOSIC FIBERS
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