EP2951339B1 - Low yarn-count high-strength viscous multifilament yarn - Google Patents

Low yarn-count high-strength viscous multifilament yarn Download PDF

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Publication number
EP2951339B1
EP2951339B1 EP14701524.2A EP14701524A EP2951339B1 EP 2951339 B1 EP2951339 B1 EP 2951339B1 EP 14701524 A EP14701524 A EP 14701524A EP 2951339 B1 EP2951339 B1 EP 2951339B1
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Prior art keywords
multifilament yarn
range
viscose
dtex
viscose multifilament
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German (de)
French (fr)
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EP2951339A1 (en
Inventor
Dennis MÖSSINGER
Holger Scheytt
Kurt Uihlein
David WUNDERLICH
Britta Zimmerer
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Cordenka GmbH and Co KG
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Cordenka GmbH and Co KG
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Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • 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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D10B2201/24—Viscose
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • Cellulose is the most common and important naturally occurring polymer in the world.
  • cellulosic moldings such as paper, blown film, cellophane and sponge cloths
  • cellulose fibers are among the important technical products that are used primarily for clothing, as insulating materials and as technical strength carriers.
  • Cellulosic fibers, filaments and multifilaments can be obtained in a variety of ways and in various forms, which are also known and familiar to the art.
  • the most common methods are the so-called Regenerat method in which cellulose is first reacted and dissolved chemically soluble labile or simply saponifiable derivatives.
  • soluble derivatives from which cellulose can be regenerated e.g. Cellulose acetate, cellulose formate or cellulose carbamate known.
  • the viscose process the labile derivative is a cellulose xanthate, and the viscose yarns are known as viscose or rayon yarns.
  • the solution is pumped through spinnerets, regenerated in a precipitation bath to give viscose filaments, washed and sized (and possibly functionally coated) in one or more post-treatment steps and finally either wound on endless coils or processed into fiber sections.
  • the present invention relates to high strength fibers of low total denier viscose multifilament yarn.
  • Viscose multifilament yarns for industrial applications often as technical viscose or rayon referred to, are known and are commonly used as a strength carrier for technical products, for example for the reinforcement of elastomeric components and products such as in the form of tire cords, as Schlaucharmtechnik, or as a reinforcing material in belts and conveyor belts.
  • High strength, low yarn count multifilament cellulosic yarns are known.
  • ultra-high strength low total denier yarns are known from cellulose formate and from a formaldehyde-modified viscose process.
  • So in the patent US 6,261,689 Cellulose formate fibers which have been conditioned according to the standard climate defined in EN ISO 20139 (currently DIN EN ISO 139) at a temperature of (20 ⁇ 2) ° C and a relative humidity of (65 ⁇ 2)% and a total titer of 460 dtex and a strength of 76 cN / tex.
  • the patent US 3,388,117 describes a formaldehyde-modified viscose process which produces a multifilament viscose yarn consisting of 500 monofilaments and having a total denier of 485 dtex. After conditioning in a climate of 20 ° C and 65% relative humidity, a strength of 78 cN / tex is measured, said strength was determined not on the multifilament yarn but on an undisclosed number of individual filaments, which were removed from the multifilament.
  • Patent GB 685,631 describes rayon yarns, ie 100 multifilament yarns of 100 individual filaments with a low total denier of 100 den (110 dtex) but with a conditioned tenacity of only 2.3 g / den (20.4 cN / tex). and with an oven-dry strength of 2.9 g / den (25.6 cN / tex).
  • GB 685,631 discloses yarns having a yarn count of 400 denier (440 dtex) with 260 filaments and moderate strengths of 4.1 g / den (36.2 cN / tex) in the conditioned and 5.3 g / den (respectively). 46.8 cN / tex) in the oven-dried viscose multifilament yarn.
  • the object of the present invention is to provide a viscose multifilament yarn which is produced without formaldehyde yet has high strength measured on the conditioned multifilament yarn.
  • a viscose multifilament yarn produced without the use of formaldehyde wherein the viscose multifilament yarn a degree of crystallinity in the range of 15% to 40% and after conditioning in standard atmosphere according to DIN EN ISO 139-1: 2005 at a temperature of 20 ⁇ 2 ° C and a relative humidity of 65 ⁇ 2% in a conditioning time of ⁇ 16 h to an equilibrium moisture content of 13 ⁇ 1% a yarn titer in the range of ⁇ 150 dtex to ⁇ 1100 dtex and a tensile strength in the range of ⁇ 45 cN / tex to ⁇ 55 cN / tex.
  • the viscose multifilament yarn according to the invention is produced without the use of formaldehyde and nevertheless shows a tensile strength measured on the viscose multifilament yarn in the range from ⁇ 45 cN / tex to ⁇ 55 cN / tex.
  • the viscose multifilament yarn according to the invention is for a person skilled in the art is shown by the fact that even the inventors can not explain why the viscose multifilament yarn according to the invention with its property combination consists of a yarn denier in the range of ⁇ 150 dtex to ⁇ 1100 dtex and Degree of crystallinity in the range of 15% to 40% has a measured on the viscose multifilament yarn tensile strength in the range of ⁇ 45 cN / tex to ⁇ 55 cN / tex.
  • the degree of crystallinity of the formaldehyde-made viscose multifilament yarn is US 3,388,117 at 45% and thus considerably higher.
  • the term "conditioned" means that the viscose multifilament yarn according to the invention is stored in the abovementioned standard climate until the yarn has reached its equilibrium moisture content corresponding to the standard climate, which is 13 ⁇ 1% by weight, and therefore its weight not changed anymore. For this purpose, a conditioning time in the above-mentioned standard climate of ⁇ 16 h is required.
  • the degree of crystallinity of the viscose multifilament yarn of the present invention is determined by wide angle X-ray diffraction (WAXS), as in Hermans, PH, Weidinger, A., Textile Research Journal 31 (1961) 558-571 described, wherein the determined values have an estimated maximum error of ⁇ 1.5% points.
  • WAXS wide angle X-ray diffraction
  • the viscose multifilament yarn according to the invention has a degree of crystallinity in the range from 20% to 35%, a yarn denier in the range from ⁇ 170 dtex to ⁇ 900 dtex and a tensile strength in the range from ⁇ 45 cN / tex to ⁇ 55 cN / tex on.
  • the viscose multifilament yarn according to the invention has a degree of crystallinity in the range of 24% to 30%, a yarn titer in the range of ⁇ 200 dtex to ⁇ 840 dtex and a tensile strength in the range of ⁇ 48 cN / tex to ⁇ 53 cN / tex on.
  • the viscose multifilament yarn according to the invention has a crystallite width in the range of 2.5 nm to 5.0 nm, more preferably in the range of 3.0 nm to 4.5 nm, and a crystal height in the range of 9.0 nm to 13.0 nm, more preferably in the range of 10 nm to 12 nm on.
  • the crystallite width is determined from the reflex of the L (1-10) crystal plane and the crystal height from the reflex of the L (004) crystal plane.
  • High-strength cellulosic fibers which can be spun from formaldehyde-modified viscoses / precipitation baths and correspondingly more highly drawn, show significantly larger L (004) reflections.
  • the discontinued product Cordenka EHM ® showed a crystallite height of 15.0 nm.
  • the viscose multifilament yarn according to the invention has a birefringence ⁇ n ⁇ 10 4 in the range from 300 to 450, particularly preferably in the range from 330 to 420.
  • the birefringence ⁇ n is measured with the aid of an interference microscope [ J. Lenz, J. Schurz, D. Eichinger, Lenzinger Reports 1994, 9, p.
  • the viscose multifilament yarn according to the invention has a filament titer in the range of 1.2 and 4.0 dtex.
  • the viscose multifilament yarn according to the invention has a filament titer in the range of 2.4 and 3.0 dtex.
  • the viscose multifilament yarn according to the invention has an elongation at break in the range of ⁇ 5% and ⁇ 20%.
  • the viscose multifilament yarn according to the invention has an elongation at break in the range of ⁇ 6% and ⁇ 15%.
  • the following table gives an exemplary overview of inventive viscose multifilament yarns with a conditioned yarn denier of 204 dtex to 1013 dtex.
  • the viscose multifilament yarns according to the invention were obtained by the abovementioned modifications of the preparation process described in Example 2 of GB 685,631 and in the normal climate according to DIN EN ISO 139-1: 2005, ie at a temperature of 20.0 ° C. and at a relative atmospheric humidity of 65%, conditioned and the textile data yarn count, maximum tensile strength, tensile strength and elongation at break in the conditioned state according to DIN EN ISO 2062: 2009 measured under the conditions already described.
  • the tensile strength is called denomination-related maximum tensile strength and elongation at break are referred to as maximum tensile elongation at break.
  • the table contains values for the degree of crystallinity determined by wide angle X-ray diffraction (WAXS), values for the crystallite width determined from the L (1-10) crystal plane reflex and values for the crystal height from the reflex of the L (004) crystal plane and a value for the birefringence ⁇ n ⁇ 10 4 measured by interference microscopy.
  • WAXS wide angle X-ray diffraction
  • the tensile strength of a selected number of individual filaments taken from a multifilament yarn is greater than the tensile strength measured on the multifilament yarn.
  • a tensile strength of 60.4 cN / tex and an elongation at break are obtained of 11.8%.
  • the tensile strength measured on the conditioned monofilaments is 20% higher and the elongation at break 28% higher than the corresponding values measured on the viscose multifilament yarn of Example 3.
  • the following table shows the difference between textile data of the same yarn example, which are obtained in conditioned (DIN EN ISO 139-1: 2005) or in oven-dry measurements: Measuring conditions / tested parameters Conditioning> 16 h at 20 ° C and 65% relative humidity Oven-dry (2 h at 105 ° C) Garntiter [dtex] 646 560 filament 240 240 Maximum tensile strength [N] 32.2 36.0 Tensile strength [cN / tex] 49.8 63.0 Elongation at break [%] 8.62 8.16
  • the viscose multifilament yarn according to the invention has a yarn count in the range of ⁇ 150 dtex to ⁇ 1100 dtex, preferably from ⁇ 170 dtex to ⁇ 900 dtex, and more preferably in front ⁇ 200 dtex to ⁇ 840 dtex.
  • the viscose multifilament yarns according to the invention have a yarn count in the range of ⁇ 150 dtex to ⁇ 1100 dtex or a yarn count in the range of ⁇ 170 dtex to ⁇ 900 dtex or a yarn count in the range of ⁇ 200 dtex to ⁇ 840 dtex and contain filaments having a filament denier between 1.2 and 4.0 dtex, more preferably between 2.4 and 3.0 dtex.
  • such viscose multifilament yarns according to the invention are not only suitable for the production of thin cords, but also give cords of very high fatigue resistance.
  • An example of this is high-tenacity viscose multifilament yarn of the invention having a conditioned dtex of 800 dtex with 300 filaments (800 dtex f300 rayon).
  • the nature or presentation of the cellulosic fibers is not limited.
  • the viscose multifilament yarn of the present invention be processed as such or as a fiber short to a cord, to a woven or knitted fabric, wherein the cord or the fabric can be used to reinforce eg tires.
  • the viscose multifilament yarn of the present invention can be used to make a cord.
  • the cord containing the viscose multifilament yarn of the present invention can be made into a fabric.
  • the fabric may be impregnated and the impregnated fabric used to make a tire. It is also possible to use the cord containing the viscose multifilament yarn according to the invention directly for the production of a tire.
  • the viscose multifilament yarn of the present invention may serve as a reinforcing material for synthetic and natural elastomers or for other synthetic or renewable raw materials based materials, for example, thermoplastic and thermosetting plastics.
  • materials which may be elastomeric, thermoplastic or duromeric materials include, for example, natural rubber, other poly (isoprene) s, poly (butadiene) s, polyisobutylenes, butyl rubber, poly (butadiene-co-styrene) s, poly (butadiene -coacrylonitrile) s, poly (ethylene-co-propylene) s, poly (isobutylene-co-isoprene) s, poly (chloroprene) s, polyacrylates, polyamide, polyesters, polylactic acid, polycarbonates, polyglucans, polyurethanes, polysulfides, silicones, polyvinyl chloride , Poly (ether-ester

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Description

Weltweit ist Cellulose das häufigste und bedeutendste natürlich vorkommende Polymer. Neben cellulosischen Formkörpern wie Papier, Blasfolien, Cellophan und Schwammtüchern, zählen Cellulosefasern zu den bedeutsamen technischen Produkten, die vor allem für Bekleidungszwecke, als Dämmmaterialien und als technische Festigkeitsträger Anwendung finden.Cellulose is the most common and important naturally occurring polymer in the world. In addition to cellulosic moldings such as paper, blown film, cellophane and sponge cloths, cellulose fibers are among the important technical products that are used primarily for clothing, as insulating materials and as technical strength carriers.

Cellulosische Fasern, Filamente und Multifilamente können auf vielfältigen Wegen und in unterschiedlichen Formen erhalten werden, die gleichfalls der Fachwelt bekannt und geläufig sind. Die gängigsten Verfahren sind die sog. Regenerat-Verfahren, bei denen Cellulose zunächst chemisch zu löslichen labilen oder einfach verseifbaren Derivaten umgesetzt und gelöst wird. Als lösliche Derivate, aus denen Cellulose regeneriert werden kann, sind z.B. Celluloseacetat, Celluloseformiat oder Cellulosecarbamat bekannt. Im bedeutendsten Verfahren, dem Viskose-Verfahren ist das labile Derivat eine Cellulosexanthogenat, und die mit dem Viskoseverfahren hergestellten Garne sind als Viskose- oder Rayon-Garne bekannt. Im Viskoseverfahren wird die Lösung durch Spinndüsen gepumpt, in einem Fällbad zu Viskose-Filamenten regeneriert, in einem oder mehreren Nachbehandlungsschritten gewaschen und geschlichtet (und ggf. funktional beschichtet) und abschließend entweder auf Endlosspulen gewickelt oder zu Faserschnitt verarbeitet.Cellulosic fibers, filaments and multifilaments can be obtained in a variety of ways and in various forms, which are also known and familiar to the art. The most common methods are the so-called Regenerat method in which cellulose is first reacted and dissolved chemically soluble labile or simply saponifiable derivatives. As soluble derivatives from which cellulose can be regenerated, e.g. Cellulose acetate, cellulose formate or cellulose carbamate known. In the most important process, the viscose process, the labile derivative is a cellulose xanthate, and the viscose yarns are known as viscose or rayon yarns. In the viscose process, the solution is pumped through spinnerets, regenerated in a precipitation bath to give viscose filaments, washed and sized (and possibly functionally coated) in one or more post-treatment steps and finally either wound on endless coils or processed into fiber sections.

Die vorliegende Erfindung betrifft hochfeste Fasern aus einem Viskose-Multifilamentgarn mit geringem Gesamttiter. Viskose-Multifilamentgarne für industrielle Anwendungen, oft auch als technische Viskose oder Rayon bezeichnet, sind bekannt und werden üblicherweise als Festigkeitsträger für technische Erzeugnisse eingesetzt, z.B. zur Verstärkung von elastomeren Bauteilen und Produkten wie beispielsweise in Form von Reifenkorden, als Schlaucharmierung, oder als Verstärkungsmaterial in Riemen und Förderbändern. In neuerer Zeit finden cellulosische Fasern in Form von Faserkurzschnitt aber auch vermehrt Anwendung in der Thermoplast-Verstärkung, z.B. in PP-Rayon-Verbundwerkstoffen, in Form uni- und bidirektionaler Gewebe auch zur Verstärkung von Duromeren wie z.B. Epoxidharzen.The present invention relates to high strength fibers of low total denier viscose multifilament yarn. Viscose multifilament yarns for industrial applications, often as technical viscose or rayon referred to, are known and are commonly used as a strength carrier for technical products, for example for the reinforcement of elastomeric components and products such as in the form of tire cords, as Schlaucharmierung, or as a reinforcing material in belts and conveyor belts. Recently, cellulosic fibers in the form of fiber short cut but also increasingly used in the thermoplastic reinforcement, for example in PP-rayon composites, in the form of unidirectional and bidirectional fabric also for reinforcing thermosets such as epoxy resins.

Hochfeste cellulosische Multifilamentgarne mit niedrigem Garntiter sind bekannt. Beispielsweise sind ultrahochfeste Garne mit geringem Gesamttiter aus Celluloseformiat und aus einem Formaldehyd-modifizierten Viskoseverfahren bekannt. So werden in der Patentschrift US 6,261,689 Celluloseformiat-Fasern beschrieben, die gemäß dem in EN ISO 20139 (aktuell: DIN EN ISO 139) definierten Normalklima bei einer Temperatur von (20 ± 2) °C und einer relativen Feuchte von (65 ± 2) % konditioniert wurden und einen Gesamttiter von 460 dtex und eine Festigkeit von 76 cN/tex aufweisen.High strength, low yarn count multifilament cellulosic yarns are known. For example, ultra-high strength low total denier yarns are known from cellulose formate and from a formaldehyde-modified viscose process. So in the patent US 6,261,689 Cellulose formate fibers which have been conditioned according to the standard climate defined in EN ISO 20139 (currently DIN EN ISO 139) at a temperature of (20 ± 2) ° C and a relative humidity of (65 ± 2)% and a total titer of 460 dtex and a strength of 76 cN / tex.

Die Patentschrift US 3,388,117 beschreibt ein mit Formaldehyd modifiziertes Viskoseverfahren, womit ein Viskose-Multifilamentgarn hergestellt wird, das aus 500 Einzelfilamenten besteht und einen Gesamttiter von 485 dtex aufweist. Nach Konditionierung in einem Klima von 20 °C und 65 % relativer Luftfeuchtigkeit wird eine Festigkeit von 78 cN/tex gemessen, wobei die genannte Festigkeit nicht am Multifilamentgarn sondern an einer nicht genannten Anzahl von Einzelfilamenten bestimmt wurde, welche dem Multifilament entnommen wurden. Da bekannt ist, dass die an einem Multifilamentgarn gemessene Festigkeit signifikant kleiner ist, als die Festigkeit, die an einer bestimmten Zahl von Einzelfilamenten gemessen wird, die dem Multifilamentgarn entnommen werden, ist die Festigkeit des in der US 3,388,117 beschriebenen Multifilamentgarns signifikant kleiner als 78 cN/tex. Grund hierfür sind die geringeren üblichen Einspannlängen von 20 mm bis 50 mm anstelle von 250 mm bis 500 mm bei Multifilamentgarnen. Ferner ist es bekannt, dass die Verwendung von Formaldehyd im Fällbad die Festigkeit der Viskosefasern außerordentlich erhöht, sodass das in der US 3,388,117 beschriebene Verfahren ohne Formaldehyd zu einer Festigkeit führt, die beträchtlich geringer ist als 78 cN/tex. Der Effekt der Festigkeitserhöhung durch Verwendung von Formaldehyd wird u.a. von den Autoren A. Kh. Khaki-mova, N.B. Sokolova und N.S. Nikolaeva in "Fiber Chemistry", ISSN 157-8493, ZDB-ID 2037141 X Band 1, (6.1971), Seiten 631-33 beschrieben. Ferner beschreiben die genannten Autoren, dass die Verwendung von Formaldehyd zu unlöslichen Reaktions-produkten von Formaldehyd mit Zersetzungsprodukten der Viskose führt. Die unlöslichen Reaktionsprodukte führen zu Problemen im Spinnbadkreislauf. Hinzu kommen die durch die Verwendung von Formaldehyd verursachten Nachteile für die Gesundheit der Produktionsarbeiter.The patent US 3,388,117 describes a formaldehyde-modified viscose process which produces a multifilament viscose yarn consisting of 500 monofilaments and having a total denier of 485 dtex. After conditioning in a climate of 20 ° C and 65% relative humidity, a strength of 78 cN / tex is measured, said strength was determined not on the multifilament yarn but on an undisclosed number of individual filaments, which were removed from the multifilament. Since it is known that the strength measured on a multifilament yarn is significantly smaller than the strength measured on a certain number of individual filaments taken from the multifilament yarn, the strength of the in US 3,388,117 described multifilament yarn significantly smaller than 78 cN / tex. This is due to the lower conventional clamping lengths of 20 mm to 50 mm instead of 250 mm to 500 mm in the case of multifilament yarns. It is also known that the use of formaldehyde in the precipitation bath greatly increases the strength of the viscose fibers, so that in the US 3,388,117 described method without formaldehyde to a strength that is considerably less than 78 cN / tex. The effect of increasing the strength by using formaldehyde is among others by the authors A. Kh. Khaki-mova, NB Sokolova and NS Nikolaeva in "Fiber Chemistry", ISSN 157-8493, ZDB-ID 2037141 X Volume 1, (6.1971), pages 631-33 described. Furthermore, the authors cited describe that the use of formaldehyde leads to insoluble reaction products of formaldehyde with viscose decomposition products. The insoluble reaction products lead to problems in the spinning bath cycle. Added to this are the disadvantages caused by the use of formaldehyde for the health of production workers.

Die Patentschrift GB 685,631 beschreibt zwar Rayon-Garne, also Viskose-Multifilamentgarne aus 100 Einzelfilamenten mit einem geringen Gesamttiter von 100 den (110 dtex), jedoch mit einer konditionierten Festigkeit von nur 2,3 g/den (20,4 cN/tex) und mit einer Festigkeit im ofentrockenen Zustand von 2,9 g/den (25,6 cN/tex). In einem weiteren Beispiel offenbart GB 685,631 Garne mit einem Garntiter von 400 den (440 dtex) mit 260 Filamenten und moderate Festigkeiten von 4,1 g/den (36,2 cN/tex) im konditionierten bzw. 5,3 g/den (46,8 cN/tex) im ofentrockenen Viskose-Multifilamentgarn.Patent GB 685,631 describes rayon yarns, ie 100 multifilament yarns of 100 individual filaments with a low total denier of 100 den (110 dtex) but with a conditioned tenacity of only 2.3 g / den (20.4 cN / tex). and with an oven-dry strength of 2.9 g / den (25.6 cN / tex). In another example, GB 685,631 discloses yarns having a yarn count of 400 denier (440 dtex) with 260 filaments and moderate strengths of 4.1 g / den (36.2 cN / tex) in the conditioned and 5.3 g / den (respectively). 46.8 cN / tex) in the oven-dried viscose multifilament yarn.

Daher stellt sich die vorliegende Erfindung die Aufgabe, ein Viskose-Multifilamentarn zur Verfügung zu stellen, welches ohne Formaldehyd hergestellt wird und dennoch eine am konditionierten Multifilamentgarn gemessene hohe Festigkeit aufweist.Therefore, the object of the present invention is to provide a viscose multifilament yarn which is produced without formaldehyde yet has high strength measured on the conditioned multifilament yarn.

Diese Aufgabe wird gelöst durch ein Viskose-Multifilamentgarn hergestellt ohne Verwendung von Formaldehyd, wobei das Viskose-Multifilamentgarn einen Kristallinitätsgrad im Bereich von 15 % bis 40 % und nach Konditionierung im Normklima gemäß DIN EN ISO 139-1:2005 bei einer Temperatur von 20 ± 2 °C und einer relativen Feuchte von 65 ± 2 % in einer Konditionierungszeit vorn ≥ 16 h auf eine Gleichgewichtsfeuchte von 13 ± 1 % einen Garntiter im Bereich von ≥ 150 dtex bis < 1100 dtex und eine Zugfestigkeit im Bereich von ≥ 45 cN/tex bis ≤ 55 cN/tex aufweist.This object is achieved by a viscose multifilament yarn produced without the use of formaldehyde, wherein the viscose multifilament yarn a degree of crystallinity in the range of 15% to 40% and after conditioning in standard atmosphere according to DIN EN ISO 139-1: 2005 at a temperature of 20 ± 2 ° C and a relative humidity of 65 ± 2% in a conditioning time of ≥ 16 h to an equilibrium moisture content of 13 ± 1% a yarn titer in the range of ≥ 150 dtex to <1100 dtex and a tensile strength in the range of ≥ 45 cN / tex to ≤ 55 cN / tex.

Das erfindungsgemäße Viskose-Multifilamentgarn wird ohne Verwendung von Formaldehyd hergestellt und zeigt dennoch eine am Viskose-Multifilamentgarn gemessene Zugfestigkeit im Bereich von ≥ 45 cN/tex bis ≤ 55 cN/tex.The viscose multifilament yarn according to the invention is produced without the use of formaldehyde and nevertheless shows a tensile strength measured on the viscose multifilament yarn in the range from ≥ 45 cN / tex to ≤ 55 cN / tex.

Wie überraschend das erfindungsgemäße Viskose-Multifilamentgarn für den Fachmann ist, zeigt die Tatsache, dass nicht einmal die Erfinder eine Erklärung dafür haben, warum das erfindungsgemäße Viskose-Multifilamentgarn mit seiner Eigenschaftskombination aus einem Garntiter im Bereich von ≥ 150 dtex bis < 1100 dtex und einem Kristallinitätsgrad im Bereich von 15 % bis 40 % eine am Viskose-Multifilamentgarn gemessene Zugfestigkeit im Bereich von ≥ 45 cN/tex bis ≤ 55 cN/tex aufweist. Zum Vergleich wird darauf hingewiesen, dass der Kristallinitätsgrad des mit Formaldehyd hergestellten Viskose-Multifilamentgarns der US 3,388,117 bei 45 % und somit beträchtlich höher liegt.How surprising the viscose multifilament yarn according to the invention is for a person skilled in the art is shown by the fact that even the inventors can not explain why the viscose multifilament yarn according to the invention with its property combination consists of a yarn denier in the range of ≥150 dtex to <1100 dtex and Degree of crystallinity in the range of 15% to 40% has a measured on the viscose multifilament yarn tensile strength in the range of ≥ 45 cN / tex to ≤ 55 cN / tex. For comparison, it should be noted that the degree of crystallinity of the formaldehyde-made viscose multifilament yarn is US 3,388,117 at 45% and thus considerably higher.

Im Rahmen der vorliegenden Erfindung bedeutet der Begriff "konditioniert", dass das erfindungsgemäße Viskose-Multifilamentgarn solange im vorstehend genannten Normklima gelagert wird, bis das Garn seine dem Normklima entsprechende Gleichgewichtsfeuchte erreicht hat, welche 13± 1 Gew.% beträgt, und daher sein Gewicht nicht mehr verändert. Dazu ist eine Konditionierungszeit im vorstehend genannten Normklima vorn ≥ 16 h erforderlich.In the context of the present invention, the term "conditioned" means that the viscose multifilament yarn according to the invention is stored in the abovementioned standard climate until the yarn has reached its equilibrium moisture content corresponding to the standard climate, which is 13 ± 1% by weight, and therefore its weight not changed anymore. For this purpose, a conditioning time in the above-mentioned standard climate of ≥ 16 h is required.

Im vorstehend beschriebenen konditionierten Zustand werden die textilen Daten des erfindungsgemäßen Viskose-Multifilamentgarns, d.h. Garntiter, Bruchkraft, Zugfestigkeit und Bruchdehnung, gemäß DIN EN ISO 2062:2009 unter folgenden Bedingungen gemessen:

  • CRE-Zugprüfmaschine mit pneumatischen Klemmen [CRE: constant rate of specimen extension = konstante Prüfkörperverformungsgeschwindigkeit],
  • Prüfung von Multifilamentgarnen mit Schutzdrall 100 t/m (t/m = turns/meter = Drehungen pro Meter)
  • Einspannlänge der Prüfstücke: 500 mm
  • Zuggeschwindigkeit (Traversengeschwindigkeit): 500 mm/min (100 %/min)
In the conditioned state described above, the textile data of the viscose multifilament yarn according to the invention, ie yarn denier, breaking strength, tensile strength and elongation at break, are measured in accordance with DIN EN ISO 2062: 2009 under the following conditions:
  • CRE tensile testing machine with pneumatic clamps [CRE: constant rate of specimen extension],
  • Testing of multifilament yarns with protective twist 100 t / m (t / m = turns / meter = turns per meter)
  • Clamping length of the test pieces: 500 mm
  • Traction Speed (Traverse Speed): 500 mm / min (100% / min)

Die in den vorstehend genannten Normen erwähnten Konditionierungs- und Prüfbedingungen sind vergleichbar mit der einschlägigen Norm der Chemiefaserindustrie ( BISFA "Testing methods for viscose, cupro, acetate, triacetate and lyocell filament yarns", 2007 Editi on) und den entsprechenden internationalen Normen (DIN EN ISO 6062, DIN EN 139, ASTM D885, ASTM D1776).The conditions of conditioning and testing mentioned in the standards mentioned above are comparable to the relevant standard of the chemical fiber industry ( BISFA "Testing methods for viscose, cupro, acetate, triacetate and lyocell filament yarns", 2007 Editi on) and the corresponding international standards (DIN EN ISO 6062, DIN EN 139, ASTM D885, ASTM D1776).

Der Kristallinitätsgrad des erfindungsgemäßen Viskose-Multifilamentgarns wird durch Weitwinkel-Röntgenbeugung (WAXS), wie in Hermans, P. H., Weidinger, A., Textil Research Journal 31 (1961) 558-571 beschrieben, bestimmt, wobei die ermittelten Werte einen geschätzten Größtfehler von ± 1,5 %-Punkten aufweisen.The degree of crystallinity of the viscose multifilament yarn of the present invention is determined by wide angle X-ray diffraction (WAXS), as in Hermans, PH, Weidinger, A., Textile Research Journal 31 (1961) 558-571 described, wherein the determined values have an estimated maximum error of ± 1.5% points.

In einer bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn einen Kristallinitätsgrad im Bereich von 20 % bis 35 %, einen Garntiter im Bereich von ≥ 170 dtex bis < 900 dtex und eine Zugfestigkeit im Bereich von ≥ 45 cN/tex bis ≤ 55 cN/tex auf.In a preferred embodiment, the viscose multifilament yarn according to the invention has a degree of crystallinity in the range from 20% to 35%, a yarn denier in the range from ≥ 170 dtex to <900 dtex and a tensile strength in the range from ≥ 45 cN / tex to ≤ 55 cN / tex on.

In einer besonders bevorzugteren Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn einen Kristallinitätsgrad im Bereich von 24 % bis 30 %, einen Garntiter im Bereich von ≥ 200 dtex bis < 840 dtex und eine Zugfestigkeit im Bereich von ≥ 48 cN/tex bis ≤ 53 cN/tex auf.In a particularly preferred embodiment, the viscose multifilament yarn according to the invention has a degree of crystallinity in the range of 24% to 30%, a yarn titer in the range of ≥ 200 dtex to <840 dtex and a tensile strength in the range of ≥ 48 cN / tex to ≤ 53 cN / tex on.

In einer bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn eine Kristallitbreite im Bereich von 2,5 nm bis 5,0 nm, besonders bevorzugt im Bereich von 3,0 nm bis 4,5 nm, und eine Kristallithöhe im Bereich von 9,0 nm bis 13,0 nm, besonders bevorzugt im Bereich von 10 nm bis 12 nm auf. Dabei werden die Kristallitbreite aus dem Reflex der L(1-10)-Kristallebene und die Kristallithöhe aus dem Reflex der L(004)-Kristallebene bestimmt. Hochfeste cellulosische Fasern, welche aus Formaldehyd-modifizierten Viskosen/Fällbädern gesponnen und entsprechend höher verstreckt werden können, zeigen deutlich größere L(004)-Reflexe. Das nicht mehr hergestellte Produkt Cordenka EHM® zeigte beispielsweise eine Kristallithöhe von 15,0 nm. [ M.G. Northolt, H. Berstoel, H. Maatman, R. Huisman, J. Veurink, H. Elzterman, Polymer 2001, 42, 8249-8264 .]In a preferred embodiment, the viscose multifilament yarn according to the invention has a crystallite width in the range of 2.5 nm to 5.0 nm, more preferably in the range of 3.0 nm to 4.5 nm, and a crystal height in the range of 9.0 nm to 13.0 nm, more preferably in the range of 10 nm to 12 nm on. The crystallite width is determined from the reflex of the L (1-10) crystal plane and the crystal height from the reflex of the L (004) crystal plane. High-strength cellulosic fibers, which can be spun from formaldehyde-modified viscoses / precipitation baths and correspondingly more highly drawn, show significantly larger L (004) reflections. For example, the discontinued product Cordenka EHM ® showed a crystallite height of 15.0 nm. [ MG Northolt, H. Berstoel, H. Maatman, R. Huisman, J. Veurink, H. Elzterman, Polymer 2001, 42, 8249-8264 .]

In einer bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn eine Doppelbrechung Δn·104 im Bereich von 300 bis 450, besonders bevorzugt im Bereich von 330 bis 420 auf. Die Doppelbrechung Δn wird mit Hilfe eines Interferenzmikroskops gemessen [ J. Lenz, J. Schurz, D. Eichinger, Lenzinger Berichte 1994, 9, S. 21 ; P. H. Hermans, Contribution to the Physics of Cellulose Fibres, Chapter 7, Elsevier, Amsterdam, New York, 1946 .] Zum Vergleich wird darauf hingewiesen, dass die Doppelbrechung Δn·104 des mit Formaldehyd hergestellten Viskose-Multifilamentgarns der US 3,388,117 im Bereich von > 530 bis 576 und somit deutlich höher liegt.In a preferred embodiment, the viscose multifilament yarn according to the invention has a birefringence Δn · 10 4 in the range from 300 to 450, particularly preferably in the range from 330 to 420. The birefringence Δn is measured with the aid of an interference microscope [ J. Lenz, J. Schurz, D. Eichinger, Lenzinger Reports 1994, 9, p. 21 ; PH Hermans, Contribution to the Physics of Cellulose Fibers, Chapter 7, Elsevier, Amsterdam, New York, 1946 .] For comparison, it should be noted that the birefringence Δn · 10 4 of the formaldehyde-made viscose multifilament yarn of US 3,388,117 in the range of> 530 to 576 and thus significantly higher.

In einer weiteren bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn einen Filament-Titer im Bereich von 1,2 und 4,0 dtex auf.In a further preferred embodiment, the viscose multifilament yarn according to the invention has a filament titer in the range of 1.2 and 4.0 dtex.

In einer weiteren bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn einen Filament-Titer im Bereich von 2,4 und 3,0 dtex auf.In a further preferred embodiment, the viscose multifilament yarn according to the invention has a filament titer in the range of 2.4 and 3.0 dtex.

In einer weiteren bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn eine Bruchdehnung im Bereich von ≥ 5 % und ≤ 20 % auf.In a further preferred embodiment, the viscose multifilament yarn according to the invention has an elongation at break in the range of ≥ 5% and ≦ 20%.

In einer weiteren bevorzugten Ausführungsform weist das erfindungsgemäße Viskose-Multifilamentgarn eine Bruchdehnung im Bereich von ≥ 6 % und ≤ 15 % auf.In a further preferred embodiment, the viscose multifilament yarn according to the invention has an elongation at break in the range of ≥ 6% and ≦ 15%.

Das erfindungsgemäße Viskose-Multifilamentgarn wird überraschenderweise dadurch erhalten, dass das in Beispiel 2 der GB 685,631 beschriebene Verfahren hinsichtlich mehrerer technischer Merkmale abgeändert wird, die im Folgenden beschrieben werden. An keiner Stelle des erfindungsgemäßen Verfahrens wird Formaldehyd eingesetzt.

  • Anstelle von Baumwoll-Linters wurden Zellstoffe aus Nadel- oder Laubholz (Weich- oder Hartholz) eingesetzt.
  • Es werden vor dem Spinnprozess Viskose-Modifikatoren (z.B. Aminethoxylate wie ethoxylierte Fettsäureamine oder Polyethylenglykole wie PEG 1500) in einer Konzentration im Bereich von 0,01 bis 1,0 Gew.-% bezogen auf Viskose zugesetzt.
  • Es werden Spinndüsen mit Lochdurchmesser < 100 µm verwendet, vorzugsweise mit einem Lochdurchmesser im Bereich von 40 bis 80 µm.
  • Die Spinngeschwindigkeit an der ersten Aufnahmerolle beträgt weniger als 50 m/min und liegt vorzugsweise im Bereich von 10 bis 40 m/min.
  • Der Transport des Fadens aus der Spinndüse in das Koagulationsbad erfolgt durch ein Spinnrohr, wobei der Transport des Fadens im Spinnrohr durch eine Strömung des Koagulationsbads in Richtung des Faserabzugs unterstützt wird.
  • Die Schwefelsäurekonzentration im Koagulationsbad ist größer als 15 g/Liter und liegt vorzugsweise im Bereich von 20 bis 120 g/Liter.
  • Dem Koagulationsbad werden Natriumsulfat und Zinksulfat zugesetzt, vorzugsweise in einer Konzentration von 25 bis 250 g/LiterKoagulationsbad.
  • Die Temperatur des Koagulationsbads beträgt mehr als 30 °C, jedoch weniger als 100 °C, und liegt vorzugsweise im Bereich von 40 bis 95 °C.
  • Das nachgelagerte Fixierbad enthält Schwefelsäure, vorzugsweise in einer Konzentration im Bereich von 20 bis 120 g/LiterFixierbad und dient auch als Zersetzungsbad für Cellulosexanthogenat.
  • Das ersponnene Garn wird stärker als auf 175 % verstreckt, vorzugsweise liegt die Verstreckung in einem Bereich von 180 bis 220 %.
  • Das erfindungsgemäße Viskose-Multifilamentgarn wird vorzugsweise in einem Zweistufenprozess hergestellt, wobei in der ersten Stufe das Garn ersponnen und aufgewickelt und in der zweiten Stufen das aufgewickelte Garn abgewickelt und gewaschen wird.
The viscose multifilament yarn according to the invention is surprisingly obtained by modifying the process described in Example 2 of GB 685,631 with regard to several technical features, which are described below. At no point in the process according to the invention is formaldehyde used.
  • Instead of cotton linters pulp from hardwood or hardwood (soft or hardwood) were used.
  • Viscose modifiers (eg, amine ethoxylates such as ethoxylated fatty acid amines or polyethylene glycols such as PEG 1500) are added in a concentration in the range from 0.01 to 1.0% by weight, based on viscose, before the spinning process.
  • Spinnerets with a hole diameter <100 .mu.m are used, preferably with a hole diameter in the range from 40 to 80 .mu.m.
  • The spinning speed at the first take-up roll is less than 50 m / min and is preferably in the range of 10 to 40 m / min.
  • The transport of the thread from the spinneret into the coagulation bath takes place through a spinning tube, wherein the transport of the thread in the spinning tube is assisted by a flow of the coagulation bath in the direction of the fiber withdrawal.
  • The sulfuric acid concentration in the coagulation bath is greater than 15 g / liter and is preferably in the range of 20 to 120 g / liter.
  • Sodium sulfate and zinc sulfate are added to the coagulation bath, preferably in a concentration of 25 to 250 g / liter coagulation bath .
  • The temperature of the coagulation bath is more than 30 ° C, but less than 100 ° C, and is preferably in the range of 40 to 95 ° C.
  • The downstream fixer contains sulfuric acid, preferably in a concentration ranging from 20 to 120 g / liter of fixer, and also serves as a cellulosic xanthogen decomposition bath .
  • The spun yarn is drawn more than 175%, preferably the stretch is in a range of 180 to 220%.
  • The viscose multifilament yarn according to the invention is preferably produced in a two-stage process, wherein in the first stage the yarn is spun and wound up and in the second stage the wound yarn is unwound and washed.

Die nachfolgende Tabelle gibt eine beispielhafte Übersicht über erfindungsgemäße Viskose-Multifilamentgarne mit einem konditionierten Garntiter von 204 dtex bis 1013 dtex. Die erfindungsgemäßen Viskose-Multifilamentgarne wurden durch die vorstehend aufgezählten Abänderungen des im Beispiel 2 der GB 685 631 beschriebenen Herstellungsverfahrens erhalten und im Normalklima gemäß DIN EN ISO 139-1:2005, d.h. bei einer Temperatur von 20,0 °C und bei einer relativen Luftfeuchtigkeit von 65 %, konditioniert und die textilen Daten Garntiter, Höchstzugkraft, Zugfestigkeit und Bruchdehnung im konditionierten Zustand gemäß DIN EN ISO 2062:2009 unter den bereits beschriebenen Bedingungen vermessen. In der DIN EN ISO 2062:2009 wird die Zugfestigkeit als feinheitsbezogene Höchstzugkraft und die Bruchdehnung als Höchstzugkraftdehnung bezeichnet.The following table gives an exemplary overview of inventive viscose multifilament yarns with a conditioned yarn denier of 204 dtex to 1013 dtex. The viscose multifilament yarns according to the invention were obtained by the abovementioned modifications of the preparation process described in Example 2 of GB 685,631 and in the normal climate according to DIN EN ISO 139-1: 2005, ie at a temperature of 20.0 ° C. and at a relative atmospheric humidity of 65%, conditioned and the textile data yarn count, maximum tensile strength, tensile strength and elongation at break in the conditioned state according to DIN EN ISO 2062: 2009 measured under the conditions already described. In DIN EN ISO 2062: 2009, the tensile strength is called denomination-related maximum tensile strength and elongation at break are referred to as maximum tensile elongation at break.

Ferner enthält die Tabelle für einige der beispielhaften erfindungsgemäßen Viskose-Multifilamentgarne Werte für den Kristallinitätsgrad, der durch Weitwinkel-Röntgenbeugung (WAXS) bestimmt wurden, Werte für die Kristallitbreite bestimmt aus dem Reflex der L(1-10)-Kristallebene und Werte für die Kristallithöhe aus dem Reflex der L(004)-Kristallebene und einen Wert für die per Interferenzmikroskopie gemessene Doppelbrechung Δn·104. Beispiel / Parameter 1 2 3 4 5 6 7 Garntiter [dtex] 204 425 640 643 801 815 1013 Filamentzahl 120 270 240 400 300 300 380 Höchstzugkraft [N] 9,2 19,9 32,1 31,3 41,0 42,3 51,9 Zugfestigkeit [cN/tex] 45,0 46,8 50,2 48,6 51,2 52,0 51,4 Bruchdehnung [%] 6,1 7,7 9,2 8,5 9,7 9,2 10,1 Kristallinitätsgrad [%] - - 26,5 - - 26,1 - Kristallit-Breite [nm] - - 3,8 - - 3,7 - Kristallit-Höhe [nm] - - 11,3 - - 11,0 - Doppelbrechung [Δn·104] - - - - - 390 - Further, for some of the exemplary viscose multifilament yarns of the present invention, the table contains values for the degree of crystallinity determined by wide angle X-ray diffraction (WAXS), values for the crystallite width determined from the L (1-10) crystal plane reflex and values for the crystal height from the reflex of the L (004) crystal plane and a value for the birefringence Δn · 10 4 measured by interference microscopy. Example / parameter 1 2 3 4 5 6 7 Garntiter [dtex] 204 425 640 643 801 815 1013 filament 120 270 240 400 300 300 380 Maximum tensile strength [N] 9.2 19.9 32.1 31.3 41.0 42.3 51.9 Tensile strength [cN / tex] 45.0 46.8 50.2 48.6 51.2 52.0 51.4 Elongation at break [%] 6.1 7.7 9.2 8.5 9.7 9.2 10.1 Degree of crystallinity [%] - - 26.5 - - 26.1 - Crystallite width [nm] - - 3.8 - - 3.7 - Crystallite height [nm] - - 11.3 - - 11.0 - Birefringence [Δn · 10 4 ] - - - - - 390 -

Wie bereits erwähnt, ist die Zugfestigkeit einer ausgewählten Zahl von Einzelfilamenten, die einem Multifilamentgarn entnommen wurden, größer als die Zugfestigkeit, die am Multifilamentgarn gemessen wird. Nimmt man willkürlich 20 Einzelfilamente des Viskose-Multifilamentgarns von Beispiel 3, konditioniert und vermisst jedes der 20 Einzelfilamente wie zuvor für das Viskose-Multifilamentgarn beschrieben und mittelt die 20 Einzelfilament-Werte, erhält man eine Zugfestigkeit von 60,4 cN/tex und eine Bruchdehnung von 11,8 %. Somit ist die an den konditionierten Einzelfilamenten gemessene Zugfestigkeit um 20 % und die Bruchdehnung um 28 % höher als die entsprechenden Werte, die am Viskose-Multifilamentgarn des Beispiels 3 gemessen werden.As already mentioned, the tensile strength of a selected number of individual filaments taken from a multifilament yarn is greater than the tensile strength measured on the multifilament yarn. Taking randomly 20 single filaments of the viscose multifilament yarn of Example 3, conditioning and measuring each of the 20 individual filaments as previously described for the viscose multifilament yarn and averaging 20 single filament values, a tensile strength of 60.4 cN / tex and an elongation at break are obtained of 11.8%. Thus, the tensile strength measured on the conditioned monofilaments is 20% higher and the elongation at break 28% higher than the corresponding values measured on the viscose multifilament yarn of Example 3.

In ofentrockenen Garnprüfungen, d.h. nach ≥ 2 h Trocknen des erfindungsgemäßen Viskose-Multifilamentgarns bei 105 °C und mit den vorstehend beschriebenen Einstellungen der Zugprüfmaschine, werden deutlich erhöhte Zugfestigkeiten gemessen. Die folgende Tabelle zeigt den Unterschied von textilen Daten desselben Garnbeispiels, welche in konditionierten (DIN EN ISO 139-1:2005) bzw. in ofentrockenen Messungen erhalten werden: Messbedingungen / geprüfte Parameter Konditionierung > 16 h bei 20 °C und 65 % relativer Feuchte Ofentrocken (2 h bei 105 °C) Garntiter [dtex] 646 560 Filamentzahl 240 240 Höchstzugkraft [N] 32,2 36,0 Zugfestigkeit [cN/tex] 49,8 63,0 Bruchdehnung [%] 8,62 8,16 In oven-dry yarn tests, ie after ≥ 2 h drying of the viscose multifilament yarn according to the invention at 105 ° C and with the above-described settings of the tensile testing machine, significantly increased tensile strengths are measured. The following table shows the difference between textile data of the same yarn example, which are obtained in conditioned (DIN EN ISO 139-1: 2005) or in oven-dry measurements: Measuring conditions / tested parameters Conditioning> 16 h at 20 ° C and 65% relative humidity Oven-dry (2 h at 105 ° C) Garntiter [dtex] 646 560 filament 240 240 Maximum tensile strength [N] 32.2 36.0 Tensile strength [cN / tex] 49.8 63.0 Elongation at break [%] 8.62 8.16

Wie bereits erwähnt, weist das erfindungsgemäße Viskose-Multifilamentgarn einen Garntiter im Bereich vorn ≥ 150 dtex bis < 1100 dtex, bevorzugt von ≥ 170 dtex bis < 900 dtex, und besonders bevorzugt vorn ≥ 200 dtex bis < 840 dtex auf.As already mentioned, the viscose multifilament yarn according to the invention has a yarn count in the range of ≥ 150 dtex to <1100 dtex, preferably from ≥ 170 dtex to <900 dtex, and more preferably in front ≥ 200 dtex to <840 dtex.

In einer weiteren bevorzugten Ausführungsform haben die erfindungsgemäßen Viskose-Multifilamentgarne einen Garntiter im Bereich vorn ≥ 150 dtex bis < 1100 dtex oder einen Garntiter im Bereich vorn ≥ 170 dtex bis < 900 dtex oder einen Garntiter im Bereich vorn ≥ 200 dtex bis < 840 dtex und enthalten Filamente mit einem Filamenttiter zwischen 1,2 und 4,0 dtex, noch mehr bevorzugt zwischen 2,4 und 3,0 dtex. Dadurch eignen sich solche erfindungsgemäßen Viskose-Multifilamentgarne nicht nur zur Herstellung von dünnen Korden, sondern ergeben auch Korde von sehr hoher Ermüdungsbeständigkeit. Ein Beispiel hierfür ist hochfestes erfindungsgemäßes Viskose-Multifilamentgarn mit einem konditionierten Garntiter von 800 dtex mit 300 Filamenten (Rayon 800 dtex f300).In a further preferred embodiment, the viscose multifilament yarns according to the invention have a yarn count in the range of ≥ 150 dtex to <1100 dtex or a yarn count in the range of ≥170 dtex to <900 dtex or a yarn count in the range of ≥ 200 dtex to <840 dtex and contain filaments having a filament denier between 1.2 and 4.0 dtex, more preferably between 2.4 and 3.0 dtex. As a result, such viscose multifilament yarns according to the invention are not only suitable for the production of thin cords, but also give cords of very high fatigue resistance. An example of this is high-tenacity viscose multifilament yarn of the invention having a conditioned dtex of 800 dtex with 300 filaments (800 dtex f300 rayon).

Abgesehen davon unterliegt die Art oder Aufmachung der cellulosischen Fasern keinen Beschränkungen. So kann das erfindungsgemäße Viskose-Multifilamentgarn als solches oder als Faserkurzschnitt zu einem Kord, zu einem Gewebe oder Gewirke verarbeitet werden, wobei der Kord bzw. das Gewebe zur Verstärkung z.B. von Reifen eingesetzt werden kann. So kann beispielsweise das erfindungsgemäße Viskose-Multifilamentgarn zur Herstellung eines Kords verwendet werden. Der das erfindungsgemäße Viskose-Multifilamentgarn enthaltende Kord kann zu einem Gewebe verarbeitet werden. Das Gewebe kann imprägniert werden, und das imprägnierte Gewebe kann zur Herstellung eines Reifens verwendet werden. Auch ist es möglich, den das erfindungsgemäße Viskose-Multifilamentgarn enthaltenden Kord direkt zur Herstellung eines Reifens einzusetzen.Apart from that, the nature or presentation of the cellulosic fibers is not limited. Thus, the viscose multifilament yarn of the present invention be processed as such or as a fiber short to a cord, to a woven or knitted fabric, wherein the cord or the fabric can be used to reinforce eg tires. For example, the viscose multifilament yarn of the present invention can be used to make a cord. The cord containing the viscose multifilament yarn of the present invention can be made into a fabric. The fabric may be impregnated and the impregnated fabric used to make a tire. It is also possible to use the cord containing the viscose multifilament yarn according to the invention directly for the production of a tire.

Ferner kann das erfindungsgemäße Viskose-Multifilamentgarn als Verstärkungsmaterial für synthetische und natürliche Elastomere oder für andere synthetische oder auf nachwachsenden Rohstoffen basierenden Materialien dienen, zum Beispiel für thermoplastische und thermofixierende Kunststoffe. Zu den genannten Materialien, die elastomere, thermoplastische oder duromere Materialien sein können, gehören zum Beispiel Naturkautschuk, andere Poly(isopren)e, Poly(butadien)e, Polyisobutylene, Butylkautschuk, Poly(butadien-co-styrol)e, Poly(butadien-coacrylnitril)e, Poly(ethylen-co-propylen)e, Poly(isobutylen-co-isopren)e, Poly(chloropren)e, Polyacrylate, Polyamid, Polyester, Polymilchsäure, Polycarbonate, Polyglucane, Polyurethane, Polysulfide, Silikone, Polyvinylchlorid, Poly(ether-ester), thermoplastische Polyester, vernetzte ungesättigte Polyester, Epoxidharze, oder Mischungen davon.Further, the viscose multifilament yarn of the present invention may serve as a reinforcing material for synthetic and natural elastomers or for other synthetic or renewable raw materials based materials, for example, thermoplastic and thermosetting plastics. Among the aforementioned materials which may be elastomeric, thermoplastic or duromeric materials include, for example, natural rubber, other poly (isoprene) s, poly (butadiene) s, polyisobutylenes, butyl rubber, poly (butadiene-co-styrene) s, poly (butadiene -coacrylonitrile) s, poly (ethylene-co-propylene) s, poly (isobutylene-co-isoprene) s, poly (chloroprene) s, polyacrylates, polyamide, polyesters, polylactic acid, polycarbonates, polyglucans, polyurethanes, polysulfides, silicones, polyvinyl chloride , Poly (ether-ester), thermoplastic polyester, crosslinked unsaturated polyester, epoxy resins, or mixtures thereof.

Claims (9)

  1. Viscose multifilament yarn produced without the use of formaldehyde, whereby the viscose multifilament yarn has a crystallinity in the range from 15% to 40%, and, after conditioning in the standard climate according to DIN EN ISO 139-1:2005 at a temperature of 20 ± 2°C and a relative humidity of 65 ± 2% in a conditioning time of ≥ 16 h to an equilibrium moisture of 13 ± 1 %, a yarn linear density in the range from ≥ 150 dtex to < 1100 dtex and a tensile strength in the range from ≥ 45 cN/tex to ≤ 55 cN/tex.
  2. Viscose multifilament yarn according to Claim 1, characterized in that the viscose multifilament yarn has a crystallinity in the range from 20% to 35%, a yarn linear density in the range from ≥ 170 dtex to < 900 dtex, and a tensile strength in the range from ≥ 45 cN/tex to ≤ 55 cN/tex.
  3. Viscose multifilament yarn according to Claim 2, characterized in that the viscose multifilament yarn has a crystallinity in the range from 24% to 30%, a yarn linear density in the range from ≥ 200 dtex to < 840 dtex, and a tensile strength in the range from ≥ 48 cN/tex to ≤ 53 cN/tex.
  4. Viscose multifilament yarn according to one or more of Claims 1 to 3, characterized in that the viscose multifilament yarn has a crystallite width in the range from 2.5 nm to 5 nm and a crystallite height in the range from 9 nm to 13 nm.
  5. Viscose multifilament yarn according to one or more of Claims 1 to 4, characterized in that the viscose multifilament yarn has a double refraction Δn·104 in the range from 300 to 450.
  6. Viscose multifilament yarn according to one or more of Claims 1 to 5, characterized in that the viscose multifilament yarn has a filament linear density in the range from 1.2 to 4.0 dtex.
  7. Viscose multifilament yarn according to Claim 6, characterized in that the viscose multifilament yarn has a filament linear density in the range from 2.4 to 3.0 dtex.
  8. Viscose multifilament yarn according to one or more of Claims 1 to 7, characterized in that the viscose multifilament yarn has an elongation at break in the range from ≥ 5% to ≤ 20%.
  9. Viscose multifilament yarn according to Claim 8, characterized in that the viscose multifilament yarn has an elongation at break in the range from ≥ 6% to ≤ 15%.
EP14701524.2A 2013-01-29 2014-01-24 Low yarn-count high-strength viscous multifilament yarn Active EP2951339B1 (en)

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EP14701524.2A EP2951339B1 (en) 2013-01-29 2014-01-24 Low yarn-count high-strength viscous multifilament yarn

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EP13152962 2013-01-29
PCT/EP2014/051374 WO2014118083A1 (en) 2013-01-29 2014-01-24 High strength viscose multifilament yarn having a low yarn count
EP14701524.2A EP2951339B1 (en) 2013-01-29 2014-01-24 Low yarn-count high-strength viscous multifilament yarn

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CN114347598B (en) * 2021-12-21 2022-09-02 北京普凡防护科技有限公司 Preparation method and application of flexible material for puncture prevention

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KR102183275B1 (en) 2020-11-26
BR112015017698B1 (en) 2021-09-14
EP2951339A1 (en) 2015-12-09
CN105102701B (en) 2017-10-03
JP2016505095A (en) 2016-02-18
CN105102701A (en) 2015-11-25
US9988744B2 (en) 2018-06-05
WO2014118083A1 (en) 2014-08-07
BR112015017698A2 (en) 2017-07-11
JP6395728B2 (en) 2018-09-26
KR20150112981A (en) 2015-10-07
US20150322595A1 (en) 2015-11-12

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