EP0967306A1 - Monofilament based on polyethylene-2.6-naphthalate - Google Patents

Monofilament based on polyethylene-2.6-naphthalate Download PDF

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Publication number
EP0967306A1
EP0967306A1 EP99112139A EP99112139A EP0967306A1 EP 0967306 A1 EP0967306 A1 EP 0967306A1 EP 99112139 A EP99112139 A EP 99112139A EP 99112139 A EP99112139 A EP 99112139A EP 0967306 A1 EP0967306 A1 EP 0967306A1
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Prior art keywords
monofilaments
contain
weight
production
polyethylene
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EP99112139A
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German (de)
French (fr)
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EP0967306B1 (en
Inventor
Joachim Stiller
Rex Dr. Delker
Hans-Joachim Dipl.-Ing. Brüning
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Teijin Monofilament Germany GmbH
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Johns Manville International Inc
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F1/00—Wet end of machines for making continuous webs of paper
    • D21F1/0027—Screen-cloths
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • 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
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

Definitions

  • the invention relates to monofilaments based on polyesters, namely Polyethylene-2,6-naphthalate, which liquid-crystalline polymers as admixtures contain, their manufacture and their use in particular for Manufacture of paper machine fabrics.
  • a monofilament in the sense of the invention is a continuous yarn consisting of one single continuous fiber, generally manufactured without twist, to understand which has a diameter of at least 0.08 mm. It differs of the single filaments or capillaries, which make up a multifilament yarn, especially due to the considerably larger diameter; they also differ Properties and techniques for processing monofilaments in many different ways Regarding the properties and processing methods of multifilament yarns.
  • Monofilaments are mainly used for the production of technical articles, in particular technically used fabrics, in contrast for multifilament yarns, which are mainly used in the textile industry.
  • EP-0 761 847 A2 describes paper machine sieves which contain monofilaments from copolymers which contain 85 to 99 mol% of the repeating structural unit of the formula I. and contain 1 to 15 mol% of the recurring structural unit of the formula II, -OC-R 2 -CO-OR 3 -O- wherein R 1 is a radical of a dihydric aliphatic or cycloaliphatic alcohol or is derived from mixtures of such alcohols, R 2 is a radical of an aliphatic, cycloaliphatic or mononuclear aromatic dicarboxylic acid or is derived from mixtures of such dicarboxylic acids, R 3 is one of the meanings defined for R 1 assumes, and the amounts are based on the total amount of the polymer.
  • the monofilaments described there are characterized by valuable properties off, however, they are regarding the splicing behavior and the transverse strengths still room for improvement.
  • the distribution of the liquid-crystalline polymers in the is problematic Polyethylene terephthalate, since the liquid crystalline polymers tend to to be distributed in a droplet shape in the matrix, which among other things in a reinforced Expresses tendency to splicing.
  • This has been known for a long time Problem among others tried to solve by a method such as that in the US PS 5,171,778, namely by processing a mixture of Polyalkylene terephthalate, a liquid crystalline polyester and a poly (O) - or - (N) -epoxyalkyl-substituted cyclic amide, imide or imidate, especially triglycidyl isocyanurate.
  • the object of the invention is therefore to provide monofilaments which in particular have an improved transverse strength and a high modulus own and are largely stable to hydrolysis.
  • Another object of the invention is a method for manufacturing such monofilaments according to claim 8.
  • Another object of the invention is the use of inventive monofilaments or monofilaments produced according to the invention claims 9 to 13.
  • the monofilaments according to the invention can be produced in the following way happen:
  • the starting products namely polyethylene-2,6-naphthalate and that liquid crystalline polymer and optionally polybutylene terephthalate and Locking agents and other additives are used immediately before spinning dried, preferably by heating in a dry atmosphere Vacuum.
  • These raw materials are mixed together homogeneously and then in an extruder at a melt temperature of 270 to 320 ° C, preferably 290 to 305 ° C, melted, filtered in a spin pack and through a Spinneret spun.
  • the emerging melt threads (Monofilaments) cooled in a spinning bath at a water temperature of approx. 70 ° C (quenched) and wound or pulled at a speed that is greater than the spray speed of the melt.
  • the spinning delay is 1: 1.5 to 1: 6.0, preferably 1: 3 to 1: 5, the spin draw speed 5 to 30 m / min, preferably 10 to 20 m / min.
  • the spun thread (monofilament) thus produced is subsequently stretched, preferably in several stages, in particular one, two or three stages post-stretched, with a total stretch ratio of 1: 4 to 1: 8, preferably 1: 5 to 1: 7 and then at temperatures of 190 to 250 ° C. heat-set, preferably 200 to 230 ° C.
  • the mechanical properties such as Initial module, maximum tensile force, maximum tensile force elongation, but also that Loop strength and knot strength as well as shrinkage are affected become.
  • the titer of the resulting monofilament also depends on of stretching.
  • the delivery rate and stretching are thus linked voted that the resulting monofilaments at the end a diameter of have at least 0.08 mm.
  • diameters of For example, 0.08 to 1.5 mm can be set.
  • the polyethylene-2,6-naphthalate used generally has one Molecular weight of 25,000 to 30,000 g / mol corresponding to a relative Viscosity from 1.80 to 1.90, measured as a 1 w / v% solution in di-chloroacetic acid.
  • sealing agents By adding sealing agents, it is possible to remove the end groups of the to use used polyester and thus stabilize the polymer. This is particularly advantageous if the monofilaments produced for the production of Paper machine screens or paper machine fabrics are used, so high demands are placed in particular on the hydrolysis stability.
  • polybutylene terephthalate makes it possible to improve the mechanical properties To improve properties such as knot strength even further.
  • the used Polyethylene terephthalate generally has a molecular weight of 25,000 to 30,000 g / mol corresponding to a relative viscosity of 2.0 to 2.3, measured as a 1 w / v% solution in di-chloroacetic acid.
  • the mixture to be spun can still contain other additives. So of course Catalyst residues resulting from polycondensation, such as antimony trioxide and tetraalkoxy titanates. Processing aids or Lubricants such as siloxanes can also be used.
  • the monofilaments can also be inorganic or organic pigments or Contain matting agents, stabilizers, especially flame retardants like corresponding phosphorus compounds.
  • the processing of the monofilaments according to the invention can be carried out in a conventional manner happen, so the monofilaments on conventional wide weaving machines too Paper machine screens are woven.
  • the monofilaments according to the invention can also with other monofilaments such as polyamide monofilaments or Polyethylene terephthalate monofilaments are processed together.
  • Example 1 Example 2
  • Example 3 Example 4 raw material 100% PEN 98% PEN 93% PEN 92.4% PEN Addition 1 + 2% LCP + 2% LCP + 2% LCP Addition 2 + 5% PBT + 5% PBT Addition 3 + 0.6% carbodiimide diameter [mm] 0.50 0.50 0.50 0.50 advancement [g / min] 261 261 260 260 Melt temperature [° C] 295 295 295 295 Spinning bath temperature [° C] 70 70 70

Abstract

Monofilaments based on polyethylene-2,6-naphthalate (PEN) contain 60-99.9 wt% PEN, 0.1-10 wt% liquid crystalline polymer(s) (LCP), 0-15 wt% polybutylene terephthalate (PBT), 0-3 wt% capping agent and optionally other additives. An Independent claim is also included for a process for the production of these monofils by mixing the above components, forming monofilaments from the melt and then cooling and stretching, using extrusion and stretching conditions matched to give monofils with a diameter of 0.08-1.5 mm.

Description

Die Erfindung betrifft Monofile auf der Basis von Polyestern, nämlich Polyethylen-2,6-naphthalat, welche flüssigkristalline Polymere als Beimengungen enthalten, deren Herstellung sowie deren Verwendung insbesondere für die Herstellung von Papiermaschinensieben bzw. Papiermaschinensiebgeweben.The invention relates to monofilaments based on polyesters, namely Polyethylene-2,6-naphthalate, which liquid-crystalline polymers as admixtures contain, their manufacture and their use in particular for Manufacture of paper machine fabrics.

Unter Monofil im Sinne der Erfindung ist ein Endlosgarn, bestehend aus einer einzelnen Endlosfaser, hergestellt im allgemeinen ohne Drehung, zu verstehen, das einen Durchmesser von mindestens 0,08 mm aufweist. Es unterscheidet sich von den Einzelfilamenten oder Kapillaren, welche ein multifiles Garn ausmachen, insbesondere durch den erheblich höheren Durchmesser; auch differieren die Eigenschaften und die Techniken zur Verarbeitung von Monofilen in vielerlei Hinsicht von den Eigenschaften und Verarbeitungsverfahren der multifilen Garne.A monofilament in the sense of the invention is a continuous yarn consisting of one single continuous fiber, generally manufactured without twist, to understand which has a diameter of at least 0.08 mm. It differs of the single filaments or capillaries, which make up a multifilament yarn, especially due to the considerably larger diameter; they also differ Properties and techniques for processing monofilaments in many different ways Regarding the properties and processing methods of multifilament yarns.

Monofile werden vor allem für die Herstellung von technischen Artikeln, insbesondere technisch eingesetzten Flächengebilden, verwendet, im Gegensatz zur Multifilamentgarnen, die vor allem in der Textilindustrie Einsatz finden.Monofilaments are mainly used for the production of technical articles, in particular technically used fabrics, in contrast for multifilament yarns, which are mainly used in the textile industry.

Monofile für technische Anwendungen sind in den meisten Fällen im Gebrauch hohen mechanischen Belastungen unterworfen. Hinzu kommen in vielen Fällen auch thermische Belastungen und Belastungen durch chemische oder andere Umgebungseinflüsse, denen das Material einen ausreichenden Widerstand entgegensetzen muß. Bei all diesen Belastungen muß das Material eine gute Dimensionsstabilität und Konstanz der Kraftdehnungseigenschaften über möglichst lange Benutzungszeiträume aufweisen.Monofilaments for technical applications are used in most cases subject to high mechanical loads. In addition there are in many cases also thermal and chemical or other loads Environmental influences to which the material has sufficient resistance must oppose. With all these loads, the material must be good Dimensional stability and constancy of the force expansion properties over possible have long periods of use.

Bei Einsatz von Monofilen in Papiermaschinensieben, insbesondere im Langsieb, der Preßpartie und der Trockenpartie, werden hohe Anforderungen an das monofile Material gestellt. Nicht nur hohe Anfangsmodule und hohe Reißfestigkeit, sondern auch gute Knoten- und Schlingenfestigkeit und hohe Abriebfestigkeit sind verlangt, sowie auch eine hohe Hydrolyseresistenz; ferner soll die Standzeit des Siebs möglichst lang sein.When using monofilaments in paper machine sieves, especially in four-wire, the press section and the dryer section, high demands are placed on the monofilament material. Not just high starting modules and high ones Tear resistance, but also good knot and loop strength and high Abrasion resistance is required, as well as high resistance to hydrolysis; further the service life of the sieve should be as long as possible.

Es ist bekannt, Papiermaschinensiebe aus Polyethylenterephthalatmonofilen in der Kette und einer Kombination von Polyethylenterephthalat- und Polyamid-6 oder Polyamid-6,6-Monofilamenten im Schuß herzustellen. Diese Siebe können jedoch den Nachteil haben, daß sie sich im Laufe des Sieblebens auf der Papiermaschine in Laufrichtung verlängern und daher ein Nachspannen stattfinden muß.It is known to manufacture paper machine screens from polyethylene terephthalate monofilaments in the Chain and a combination of polyethylene terephthalate and polyamide 6 or To produce polyamide-6,6 monofilaments in the weft. However, these sieves can have the disadvantage that they are in the course of sieving on the paper machine extend in the direction of travel and must therefore be retightened.

Es hat nicht an Versuchen gefehlt, synthetische Monofile herzustellen, die für die verschiedensten Einsatzzwecke geeignet sind, insbesondere auch für die Herstellung von Papiermaschinensieben. So wird in der US-PS 5,169,499 als Alternative zu Polyethylenterephthalat der Einsatz von Copolymeren auf der Basis von 1,4-Dimethylcyclohexan, Terephthalsäure und Isophthalsäure beschrieben. Diese Polymere besitzen zwar eine gute Hydrolysestabilität, zeigen aber vergleichsweise schlechte, Längs-, Knoten- und Schlingenfestigkeit.There has been no shortage of attempts to produce synthetic monofilaments for the are suitable for a wide variety of uses, in particular for Manufacture of paper machine screens. Thus, in US Pat. No. 5,169,499 An alternative to polyethylene terephthalate is the use of copolymers based described by 1,4-dimethylcyclohexane, terephthalic acid and isophthalic acid. Although these polymers have good hydrolysis stability, they do show comparatively poor, longitudinal, knot and loop strength.

In der EP- 0 761 847 A2 werden Papiermaschinensiebe beschrieben, welche Monofilamente aus Copolymeren enthalten, die 85 bis 99 Mol.-% der wiederkehrenden Struktureinheit der Formel I

Figure 00020001
und 1 bis 15 Mol.-% der wiederkehrenden Struktureinheit der Formel II enthalten, -OC-R2-CO-O-R3-O- worin R1 ein Rest eines zweiwertigen aliphatischen oder cycloaliphatischen Alkohols ist oder sich von Mischungen derartiger Alkohole ableitet, R2 einen Rest einer aliphatischen, cycloaliphatischen oder einkernigen aromatischen Dicarbonsäure darstellt oder sich von Mischungen derartiger Dicarbonsäuren ableitet, R3 eine der für R1 definierten Bedeutungen annimmt, und die Mengenangaben auf die Gesamtmenge des Polymeren bezogen sind.EP-0 761 847 A2 describes paper machine sieves which contain monofilaments from copolymers which contain 85 to 99 mol% of the repeating structural unit of the formula I.
Figure 00020001
and contain 1 to 15 mol% of the recurring structural unit of the formula II, -OC-R 2 -CO-OR 3 -O- wherein R 1 is a radical of a dihydric aliphatic or cycloaliphatic alcohol or is derived from mixtures of such alcohols, R 2 is a radical of an aliphatic, cycloaliphatic or mononuclear aromatic dicarboxylic acid or is derived from mixtures of such dicarboxylic acids, R 3 is one of the meanings defined for R 1 assumes, and the amounts are based on the total amount of the polymer.

Die dort beschriebenen Monofile zeichnen sich durch wertvolle Eigenschaften aus, jedoch sind sie hinsichtlich des Spleißverhaltens und der Querfestigkeiten noch verbesserungsfähig.The monofilaments described there are characterized by valuable properties off, however, they are regarding the splicing behavior and the transverse strengths still room for improvement.

In der US-PS 5,692,938 werden Monofile auf der Basis von Polyethylenterephthalat beschrieben, welche Beimengungen von flüssigkristallinen Polymeren enthalten. Die dort beschriebenen Monofile weisen eine verbesserte Abriebfestigkeit auf und sind insbesondere zur Herstellung von Papiermaschinensieben geeignet.US Pat. No. 5,692,938 describes monofilaments based on Polyethylene terephthalate described which admixtures of liquid crystalline Contain polymers. The monofilaments described there show an improved Abrasion resistance and are particularly suitable for the production of Suitable for paper machine screens.

Problematisch ist jedoch die Verteilung der flüssigkristallinen Polymere im Polyethylenterephthalat, da die flüssigkristallinen Polymere die Neigung haben, sich in der Matrix tröpfchenförmig zu verteilen, was sich u.a. in einer verstärkten Neigung zum Spleißen ausdrückt. Man hat dieses schon seit längerem bekannte Problem u.a. nach einer Methode zu lösen versucht, wie sie in der US-PS 5,171,778 beschrieben wird, nämlich durch Verarbeiten eines Gemischs von Polyalkylenterephthalat, eines flüssigkristallinen Polyesters sowie eines Poly(O)- oder -(N)-epoxyalkylsubstituierten cyclischen Amids, Imids oder Imidats, insbesondere Triglycidylisocyanurat.However, the distribution of the liquid-crystalline polymers in the is problematic Polyethylene terephthalate, since the liquid crystalline polymers tend to to be distributed in a droplet shape in the matrix, which among other things in a reinforced Expresses tendency to splicing. This has been known for a long time Problem among others tried to solve by a method such as that in the US PS 5,171,778, namely by processing a mixture of Polyalkylene terephthalate, a liquid crystalline polyester and a poly (O) - or - (N) -epoxyalkyl-substituted cyclic amide, imide or imidate, especially triglycidyl isocyanurate.

Abgesehen davon, daß die Verarbeitung derart reaktiver Gemische Probleme aufwirft, ist ein Hinweis, derartige Gemische zu Monofilen zu verarbeiten, in dieser Patentschrift nicht zu finden. Aside from the fact that the processing of such reactive mixtures has problems is an indication of processing such mixtures into monofilaments in not found in this patent.

Es besteht somit noch ein Bedürfnis nach Monofilen mit verbesserten Eigenschaften, die sich für vielfältige technische Einsatzzwecke verwenden lassen.There is therefore still a need for monofilaments with improved ones Properties that can be used for a wide range of technical purposes.

Aufgabe der Erfindung ist es deshalb, Monofile zur Verfügung zu stellen, welche insbesondere eine verbesserte Querfestigkeit besitzen und die einen hohen Modul besitzen und weitgehend hydrolysestabil sind.The object of the invention is therefore to provide monofilaments which in particular have an improved transverse strength and a high modulus own and are largely stable to hydrolysis.

Diese Aufgabe wird durch Monofile gemäß Patentanspruch 1 gelöst.This object is achieved by monofilaments according to claim 1.

In den Patentansprüchen 2 bis 7 sind besonders vorteilhafte Ausführungsformen der erfindungsgemäßen Monofile wiedergegeben.In the claims 2 to 7 are particularly advantageous embodiments reproduced the monofilament according to the invention.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung derartiger Monofile gemäß Patentanspruch 8.Another object of the invention is a method for manufacturing such monofilaments according to claim 8.

Ein weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemäßen Monofile bzw. erfindungsgemäß hergestellten Monofile gemäß den Ansprüchen 9 bis 13.Another object of the invention is the use of inventive monofilaments or monofilaments produced according to the invention claims 9 to 13.

Die Herstellung der erfindungsgemäßen Monofile kann auf folgende Weise geschehen:The monofilaments according to the invention can be produced in the following way happen:

Die Ausgangsprodukte, nämlich Polyethylen-2,6-naphthalat sowie das flüssigkristalline Polymer sowie gegebenenfalls Polybutylenterephthalat und Verschlußmittel sowie weitere Zusätze werden unmittelbar vor dem Verspinnen getrocknet, vorzugsweise durch Erwärmen in einer trockenen Atmosphäre unter Vakuum. Diese Rohstoffe werden homogen miteinander vermischt und dann in einem Extruder bei einer Schmelzetemperatur von 270 bis 320°C, vorzugsweise 290 bis 305°C, aufgeschmolzen, in einem Spinnpack filtriert und durch eine Spinndüse versponnen. The starting products, namely polyethylene-2,6-naphthalate and that liquid crystalline polymer and optionally polybutylene terephthalate and Locking agents and other additives are used immediately before spinning dried, preferably by heating in a dry atmosphere Vacuum. These raw materials are mixed together homogeneously and then in an extruder at a melt temperature of 270 to 320 ° C, preferably 290 to 305 ° C, melted, filtered in a spin pack and through a Spinneret spun.

Nach Verlassen der Spinndüse werden die heraustretenden Schmelzefäden (Monofile) in einem Spinnbad bei ca. 70°C Wassertemperatur abgekühlt (abgeschreckt) und mit einer Geschwindigkeit aufgewickelt oder abgezogen, die größer ist als die Spritzgeschwindigkeit der Schmelze. Der Spinnverzug beträgt 1:1,5 bis 1:6,0, vorzugsweise 1:3 bis 1:5, die Spinnabzugsgeschwindigkeit 5 bis 30 m/min, vorzugsweise 10 bis 20 m/min.After leaving the spinneret, the emerging melt threads (Monofilaments) cooled in a spinning bath at a water temperature of approx. 70 ° C (quenched) and wound or pulled at a speed that is greater than the spray speed of the melt. The spinning delay is 1: 1.5 to 1: 6.0, preferably 1: 3 to 1: 5, the spin draw speed 5 to 30 m / min, preferably 10 to 20 m / min.

Anschließend wird der so hergestellte Spinnfaden (Monofilament) nachverstreckt, vorzugsweise in mehreren Stufen, insbesondere ein-, zwei- oder dreistufig nachverstreckt, mit einem Gesamtverstreckverhältnis von 1:4 bis 1:8, vorzugsweise 1:5 bis 1:7 und anschließend bei Temperaturen von 190 bis 250°C thermofixiert, vorzugsweise 200 bis 230°C.The spun thread (monofilament) thus produced is subsequently stretched, preferably in several stages, in particular one, two or three stages post-stretched, with a total stretch ratio of 1: 4 to 1: 8, preferably 1: 5 to 1: 7 and then at temperatures of 190 to 250 ° C. heat-set, preferably 200 to 230 ° C.

Mittels der Verstreckung können die mechanischen Eigenschaften wie Anfangsmodul, Höchstzugkraft, Höchstzugkraftdehnung, aber auch noch die Schlingenfestigkeit und die Knotenfestigkeit sowie der Schrumpf beeinflußt werden. Selbstverständlich hängt auch der Titer des entstehenden Monofils von der Verstreckung ab. Fördermenge und Verstreckung werden so aufeinander abgestimmt, daß die entstehenden Monofile am Schluß einen Durchmesser von mindestens 0,08 mm aufweisen. Erfindungsgemäß können Durchmesser von beispielsweise 0,08 bis 1,5 mm eingestellt werden.The mechanical properties such as Initial module, maximum tensile force, maximum tensile force elongation, but also that Loop strength and knot strength as well as shrinkage are affected become. Of course, the titer of the resulting monofilament also depends on of stretching. The delivery rate and stretching are thus linked voted that the resulting monofilaments at the end a diameter of have at least 0.08 mm. According to the invention, diameters of For example, 0.08 to 1.5 mm can be set.

Das eingesetzte Polyethylen-2,6-naphthalat hat im allgemeinen ein Molekulargewicht von 25.000 bis 30.000 g/mol entsprechend einer relativen Viskosität von 1,80 bis 1,90, gemessen als 1 Gew.-/Vol.-%ige Lösung in Di-Chlor-Essigsäure.The polyethylene-2,6-naphthalate used generally has one Molecular weight of 25,000 to 30,000 g / mol corresponding to a relative Viscosity from 1.80 to 1.90, measured as a 1 w / v% solution in di-chloroacetic acid.

Durch den Zusatz von Verschlußmitteln ist es möglich, die Endgruppen des eingesetzten Polyesters zu verkappen und damit das Polymer zu stabilisieren. Dies ist besonders vorteilhaft, wenn die hergestellten Monofile zur Herstellung von Papiermaschinensieben bzw. Papiermaschinensiebgeweben eingesetzt werden, so insbesondere an die Hydrolysestabilität hohe Anforderungen gestellt werden. By adding sealing agents, it is possible to remove the end groups of the to use used polyester and thus stabilize the polymer. This is particularly advantageous if the monofilaments produced for the production of Paper machine screens or paper machine fabrics are used, so high demands are placed in particular on the hydrolysis stability.

Durch den Zusatz von Polybutylenterephthalat ist es möglich, die mechanischen Eigenschaften wie Knotenfestigkeit noch weiter zu verbessern. Das eingesetzte Polyethylenterephthalat hat im allgemeinen ein Molekulargewicht von 25.000 bis 30.000 g/mol entsprechend einer relativen Viskosität von 2,0 bis 2,3, gemessen als 1 Gew.-/Vol.-%ige Lösung in Di-Chlor-Essigsäure.The addition of polybutylene terephthalate makes it possible to improve the mechanical properties To improve properties such as knot strength even further. The used Polyethylene terephthalate generally has a molecular weight of 25,000 to 30,000 g / mol corresponding to a relative viscosity of 2.0 to 2.3, measured as a 1 w / v% solution in di-chloroacetic acid.

Neben den bereits erwähnten Bestandteilen kann das zu verspinnende Gemisch noch weitere Zusätze bzw. Additive enthalten. So können selbstverständlich Katalysatorrückstände von der Polykondensation herrührend, wie Antimontrioxid und Tetraalkoxytitanate, zugegen sein. Auch können Verarbeitungshilfsmittel oder Gleitmittel wie Siloxane mitverwendet werden.In addition to the components already mentioned, the mixture to be spun can still contain other additives. So of course Catalyst residues resulting from polycondensation, such as antimony trioxide and tetraalkoxy titanates. Processing aids or Lubricants such as siloxanes can also be used.

Die Monofile können auch anorganische oder organische Pigmente oder Mattierungsmittel enthalten, Stabilisatoren, insbesondere auch Flammfestmittel wie entsprechende Phosphorverbindungen.The monofilaments can also be inorganic or organic pigments or Contain matting agents, stabilizers, especially flame retardants like corresponding phosphorus compounds.

Das Verarbeiten der erfindungsgemäßen Monofile kann auf an sich übliche Weise geschehen, so können die Monofile auf herkömmlichen Breitwebmaschinen zu Papiermaschinensieben verwebt werden. Die erfindungsgemäßen Monofile können auch mit anderen Monofilen wie Polyamidmonofilen oder Polyethylenterephthalatmonofilen zusammen verarbeitet werden.The processing of the monofilaments according to the invention can be carried out in a conventional manner happen, so the monofilaments on conventional wide weaving machines too Paper machine screens are woven. The monofilaments according to the invention can also with other monofilaments such as polyamide monofilaments or Polyethylene terephthalate monofilaments are processed together.

In der folgenden Tabelle sind die Herstellungsparameter und Eigenschaften von vier Monofilen gemäß der Erfindung wiedergegeben. Beispiel 1 Beispiel 2 Beispiel 3 Beispiel 4 Rohstoff 100 % PEN 98 % PEN 93 % PEN 92,4 % PEN Zusatz 1 + 2 % LCP + 2 % LCP + 2 % LCP Zusatz 2 + 5 % PBT + 5 % PBT Zusatz 3 + 0,6 % Carbodiimid Durchmesser [mm] 0,50 0,50 0,50 0,50 Förderung [g/min] 261 261 260 260 Massetemperatur [°C] 295 295 295 295 Spinnbadtemperatur [°C] 70 70 70 70 Abzugsgeschwindigkeit [m/min] 15 15 15 15 Fördertemperatur [°C] 220 220 220 220 Reißfestigkeit [cN/tex] 41 44 43 43 Reißdehnung [%] 15 14 15 17 Modul [N/tex] 12 13 13 13 Schrumpf bei 180°C [%] 2,5 2,5 2,5 2,5 Knotenfestigkeit [cN/tex] 8 18 23 25 Schlingenfestigkeit [cN/tex] 5 7 8 14 Reißfestigkeit nach Hydrolyse (80 Stunden bei 135°C) [%] 75 78 66 77 The following table shows the production parameters and properties of four monofilaments according to the invention. example 1 Example 2 Example 3 Example 4 raw material 100% PEN 98% PEN 93% PEN 92.4% PEN Addition 1 + 2% LCP + 2% LCP + 2% LCP Addition 2 + 5% PBT + 5% PBT Addition 3 + 0.6% carbodiimide diameter [mm] 0.50 0.50 0.50 0.50 advancement [g / min] 261 261 260 260 Melt temperature [° C] 295 295 295 295 Spinning bath temperature [° C] 70 70 70 70 Take-off speed [m / min] 15 15 15 15 Delivery temperature [° C] 220 220 220 220 Tensile strength [cN / tex] 41 44 43 43 Elongation at break [%] 15 14 15 17th module [N / tex] 12th 13 13 13 Shrinkage at 180 ° C [%] 2.5 2.5 2.5 2.5 Knot strength [cN / tex] 8th 18th 23 25th Loop strength [cN / tex] 5 7 8th 14 Tear resistance after hydrolysis (80 hours at 135 ° C) [%] 75 78 66 77

Claims (13)

Monofile auf der Basis von Polyethylen-2,6-naphthalat enthaltend 60 bis 99,9 Gew.-% Polyethylen-2,6-naphthalat, 0,1 bis 10 Gew.-% eines oder mehrerer flüssigkristalliner Polymere, 0 bis 15 Gew.-% Polybutylenterephthalat und 0 bis 3 Gew.-% eines Verschlußmittels sowie gegebenenfalls weitere Zusätze.Monofilaments based on polyethylene-2,6-naphthalate containing 60 to 99.9% by weight of polyethylene-2,6-naphthalate, 0.1 to 10% by weight of one or several liquid crystalline polymers, 0 to 15% by weight Polybutylene terephthalate and 0 to 3 wt .-% of a closure agent and if necessary, other additives. Monofile nach Patentanspruch 1, dadurch gekennzeichnet, daß sie 0,5 bis 7, vorzugsweise 1 bis 5, Gew.-% flüssigkristalline Polymere, 3 bis 12, vorzugsweise 4 bis 11, Gew.-% Polybutylenterephthalat und 0,15 bis 2,25 Gew.-% Verschlußmittel enthalten.Monofilaments according to claim 1, characterized in that they contain 0.5 to 7, preferably 1 to 5,% by weight of liquid-crystalline polymers, 3 to 12, preferably 4 to 11,% by weight of polybutylene terephthalate and 0.15 to 2.25 Wt .-% contain closure. Monofile nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie 0,4 bis 1, vorzugsweise 0,45 bis 0,6, Gew.-% Monocarbodiimid als Verschlußmittel enthalten.Monofilaments according to claim 1 or 2, characterized in that they contain 0.4 to 1, preferably 0.45 to 0.6,% by weight of monocarbodiimide as a closing agent. Monofile nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß sie 0,15 bis 2,25, vorzugsweise 0,75 bis 1,8, Gew.-% Polycarbodiimid als Verschlußmittel enthalten.Monofilaments according to claim 1 or 2, characterized in that they contain 0.15 to 2.25, preferably 0.75 to 1.8,% by weight of polycarbodiimide as a closing agent. Monofile nach mindestens einem der Patentansprüche 1 bis 4, dadurch gekennzeichnet, daß sie ein Gemisch aus Monocarbodiimid und Polycarbodiimid als Verschlußmittel enthalten.Monofilaments according to at least one of Claims 1 to 4, characterized in that they contain a mixture of monocarbodiimide and polycarbodiimide as a closing agent. Monofile nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie als flüssigkristallines Polymer ein Polykondensationsprodukt auf der Basis p-Hydroxybenzoesäure und 2,6-Hydroxynaphthoesäure enthalten.Monofilaments according to at least one of Claims 1 to 5, characterized in that they contain a polycondensation product based on p-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid as the liquid-crystalline polymer. Monofile nach Anspruch 6, dadurch gekennzeichnet, daß das Polykondensationsprodukt aus 70 bis 80, vorzugsweise 72 bis 74, Mol-% p-Hydroxybenzoesäure und 20 bis 30, vorzugsweise 26 bis 28, Mol-% 2,6-Hydroxynaphthoesäure aufgebaut ist.Monofilaments according to claim 6, characterized in that the polycondensation product is composed of 70 to 80, preferably 72 to 74, mol% of p-hydroxybenzoic acid and 20 to 30, preferably 26 to 28, mol% of 2,6-hydroxynaphthoic acid. Verfahren zur Herstellung von Monofilen nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man Polyethylen-2,6-naphthalat, ein oder mehrere flüssigkristalline Polymere, sowie gegebenenfalls Polybutylenterephthalat, Verschlußmittel und weitere Zusätze miteinander vermischt, als Schmelze zu Monofilen verformt, die Monofile nach Verlassen der Spinndüse abkühlt und verstreckt, wobei Extrusion und Verstreckung so aufeinander abgestimmt sind, daß Monofile mit einem Durchmesser von 0,08 bis 1,5 mn entstehen.Process for the production of monofilaments according to one or more of Claims 1 to 7, characterized in that polyethylene-2,6-naphthalate, one or more liquid-crystalline polymers, and, if appropriate, polybutylene terephthalate, sealing agents and other additives are mixed together and shaped as a melt to form monofilaments , the monofilaments are cooled and drawn after leaving the spinneret, extrusion and drawing being matched to one another in such a way that monofilaments with a diameter of 0.08 to 1.5 mm are formed. Verwendung der Monofile nach mindestens einem der Ansprüche 1 bis 7 oder hergestellt nach einem Verfahren gemäß Anspruch 8 zur Herstellung von Sieben oder Filtern.Use of the monofilaments according to at least one of claims 1 to 7 or produced by a method according to claim 8 for the production of sieves or filters. Verwendung der Monofile nach mindestens einem der Ansprüche 1 bis 7 oder hergestellt nach einem Verführen gemäß Anspruch 8 zur Herstellung von Papiermaschinensieben bzw. Papiermaschinen- siebgeweben.Use of the monofilaments according to at least one of claims 1 to 7 or produced after a seduction according to claim 8 for production of paper machine screens or paper machine screen fabrics. Verwendung der Monofile nach mindestens einem der Ansprüche 1 bis 7 oder hergestellt nach einem Verfahren gemäß Anspruch 8 zur Verstärkung von Elastomeren.Use of the monofilaments according to at least one of claims 1 to 7 or produced by a method according to claim 8 for reinforcement of elastomers. Verwendung der Monofile nach mindestens einem der Ansprüche 1 bis 7 oder hergestellt nach einem Verfahren gemäß Anspruch 8 zur Herstellung von Förderbandgeweben.Use of the monofilaments according to at least one of claims 1 to 7 or produced by a method according to claim 8 for the production of conveyor belt fabrics. Verwendung nach Anspruch 9 oder 12 zur Herstellung von Förderbandgeweben, Sieben oder Filtern für die Lebensmittelindustrie.Use according to claim 9 or 12 for the production of Conveyor belt fabrics, sieves or filters for the food industry.
EP99112139A 1998-06-26 1999-06-24 Monofilament based on polyethylene-2.6-naphthalate Expired - Lifetime EP0967306B1 (en)

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DE19828517C2 (en) 2000-12-28
CA2276642A1 (en) 1999-12-26
EP0967306B1 (en) 2003-09-03
ES2210904T3 (en) 2004-07-01
DE19828517A1 (en) 1999-12-30
DK0967306T3 (en) 2003-11-03
ATE248938T1 (en) 2003-09-15
DE59906826D1 (en) 2003-10-09

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