EP0784107A2 - Melt-spun, abrasion-resistant monofilaments - Google Patents

Melt-spun, abrasion-resistant monofilaments Download PDF

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Publication number
EP0784107A2
EP0784107A2 EP96120750A EP96120750A EP0784107A2 EP 0784107 A2 EP0784107 A2 EP 0784107A2 EP 96120750 A EP96120750 A EP 96120750A EP 96120750 A EP96120750 A EP 96120750A EP 0784107 A2 EP0784107 A2 EP 0784107A2
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EP
European Patent Office
Prior art keywords
monofilaments
polyamide
fabrics
forming
wire
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96120750A
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German (de)
French (fr)
Other versions
EP0784107B1 (en
EP0784107A3 (en
Inventor
Jürgen Büdenbender
Eckhard Gärtner
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Asahi Kasei Spandex Europe GmbH
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Bayer Faser GmbH
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Publication of EP0784107A2 publication Critical patent/EP0784107A2/en
Publication of EP0784107A3 publication Critical patent/EP0784107A3/en
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Publication of EP0784107B1 publication Critical patent/EP0784107B1/en
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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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • 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
    • D01F6/90—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 polyamides
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S162/00—Paper making and fiber liberation
    • Y10S162/90—Papermaking press felts
    • 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]
    • 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]
    • Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
    • 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
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/40—Knit fabric [i.e., knit strand or strip material]
    • Y10T442/444—Strand is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/601—Nonwoven fabric has an elastic quality
    • Y10T442/602—Nonwoven fabric comprises an elastic strand or fiber material
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • 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
    • Y10T83/00—Cutting
    • Y10T83/929—Tool or tool with support
    • Y10T83/9292—Wire tool

Definitions

  • the invention relates to melt-spun monofilaments made of polyamide, polyester or polypropylene as thread-forming polymers with improved abrasion resistance and their use for the production of technical fabrics or use as wire.
  • thermoplastic polymers The processes for producing monofilaments from thermoplastic polymers are known in principle and e.g. described in Handbuch der Kunststofftechnik II, C. Hauser Verlag, Kunststoff 1986, pages 295 to 319.
  • thermoplastic polymers can be improved by adding polyethylene / polypropylene rubber.
  • the polymer mixtures of thermoplastic polymers and modified polyethylene / polypropylene rubber are known to be compounded and granulated on twin-screw extruders and processed by injection molding.
  • the invention has for its object to improve the abrasion resistance and the alternating bending resistance of melt-spun monofilaments and their processability to technical fabrics or wire and thus e.g. to significantly extend the service life of technical fabrics.
  • the monofilaments according to the invention are distinguished by a permanently improved abrasion resistance, improved resistance to alternating bending stress and reduced thermal shrinking forces.
  • Another object is the use of the monofilaments according to the invention for the production of technical textiles, such as fabrics and felts for industry, e.g. Classifying fabrics, screen printing fabrics, shaped screen fabrics and press felts for paper and cellulose fiber production.
  • technical textiles such as fabrics and felts for industry, e.g. Classifying fabrics, screen printing fabrics, shaped screen fabrics and press felts for paper and cellulose fiber production.
  • the monofilaments according to the invention are produced by melt extrusion processes known per se.
  • the raw materials are either a mixture of granules or used as granules / powder mixture or as compounded granules. It is important to ensure that the components are mixed homogeneously in the melt and thus ultimately in the monofilaments. This is achieved using commercially available dynamic mixers after extrusion.
  • the aim was to increase the impact strength of the polymers and the transverse stability of the monofilaments obtained from the polymers.
  • Another object of the invention is the use of the monofilaments according to the invention for the production of technical textile fabrics or of technical wires, in particular lawn mower wire.
  • the monofilaments according to the invention are preferably used in so-called technical textiles such as fabrics and felts for industry, e.g. Classifying fabrics, screen printing fabrics, shaped screen fabrics and press felts for paper and cellulose fiber production.
  • the preferred thread-forming thermoplastic polymer for the production of the monofilaments is polyamide, in particular polyamide (PA) 6, 6.6, 6.10, 6.12, 11 and 12, mixtures of the polyamides or copolymers thereof.
  • Preferred polyesters are polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).
  • the mixture according to the invention can contain up to 15% by weight, based on the sum of components a), b) and c), plasticizers, for example caprolactam for polyamide, phenols, arylsulfonamides or phthalic acid esters, pigments, for example TiO 2 , carbon black, dyes, as additional additives internal lubricants, for example alkaline earth stearates, in particular of Ca or Mg, waxes to increase transparency, for example those based on fatty acid amides, can be added.
  • plasticizers for example caprolactam for polyamide, phenols, arylsulfonamides or phthalic acid esters
  • pigments for example TiO 2 , carbon black
  • dyes as additional additives internal lubricants, for example alkaline earth stearates, in particular of Ca or Mg, waxes to increase transparency, for example those based on fatty acid amides, can be added.
  • Examples 1 to 5 show monofilaments according to the invention, example 6 a comparative example.
  • a medium-viscosity semi-crystalline maleic anhydride modified PE / PP rubber was used as the modified rubber (component B).
  • Component C) is a commercially available aging stabilizer Irganox 1098 from Ciba Geigy, a sterically hindered phenol of the formula (I) N, N'-hexamethylene-bis- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide)
  • the concentrations of component A) were varied between 98.25% by weight and 84.5% by weight of component B) between 1.25% by weight and 15% by weight.
  • the concentration of component C) was kept constant at 0.5% by weight
  • the components A), B) and C) were degassed as granules or granule powder mixture in accordance with the desired concentration ratio on a single-screw extruder under vacuum, then melted at 270 ° C. and then mixed together in a dynamic mixer, so that components A), B ) and C) were homogeneously mixed finely dispersed.
  • the monofilament was then produced in a manner known per se on a monofilament spinning and drawing machine.
  • the filament-forming polymer melt was spun from a device for melt spinning monofilaments to cool in a water bath at 20 to 30 ° C, then stretched 3.5 times in hot water at 80 ° C and in hot air at 150 ° C and finally in Hot air fixed at 210 ° C.
  • the preparation is carried out analogously to the spinning process shown above.
  • the abrasion tests were carried out on the test bars produced from the monofilaments using the AT 2000 abrasion tester from Einlehner in calcium carbonate / water suspension.
  • a ceramic slat rotating body consisting of 16 circularly arranged round bars made of Al-oxide ceramic with a flat ground surface touching the screen was used as the wear body.
  • the arrangement corresponds approximately to the open and closed surfaces of a flat suction device in a paper machine.
  • the material loss of the respective test sieve is determined from the difference between the rubbed and non-rubbed sieve surface as a loss of weight and thickness.
  • Table 2 shows further Examples 7 to 10, in which a hydrolysis-stabilized high-molecular polyethylene terephthalate (PET) with a maleic anhydride-modified polyethylene / propylene rubber (Exxelor VA 1803) and a hydrolysis stabilizer (Stabaxol P100) was used instead of polyamide.
  • PET polyethylene terephthalate
  • Exxelor VA 1803 maleic anhydride-modified polyethylene / propylene rubber
  • Stabaxol P100 hydrolysis stabilizer
  • the loss of length after the concrete edge impact test was determined. The loss of length decreases with increasing proportion of rubber modified with maleic anhydride.

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

Abstract

Melt-spun monofilaments based on polyamide, polyester or polypropylene as fibre-forming polymer (I) are used for the production of technical wire, especially grass cutter wire or technical textiles. The novelty is that the monofilament contains (a) 99-70 wt.% (I), (b) 30-1 wt.% maleic anhydride-modified polyethylene/polypropylene rubber and also (c) NOTGREATER 3 wt.%, preferably 0.01-3 wt.% antioxidant with respect to the total amounts of (a) and (b). Also claimed are moulding screens or pressing blankets obtained from these monofilaments for processing cellulose fibres or paper manufacture.

Description

Die Erfindung betrifft schmelzgesponnene Monofile aus Polyamid, Polyester oder Polypropylen als fadenbildende Polymeren mit verbesserter Scheuerfestigkeit und deren Verwendung zur Herstellung von technischen Flächengebilden oder Verwendung als Draht.The invention relates to melt-spun monofilaments made of polyamide, polyester or polypropylene as thread-forming polymers with improved abrasion resistance and their use for the production of technical fabrics or use as wire.

Die Verfahren zur Herstellung von Monofilen aus thermoplastischen Polymeren sind grundsätzlich bekannt und z.B. beschrieben in Handbuch der Kunststofftechnik II, C. Hauser Verlag, München 1986, Seite 295 bis 319.The processes for producing monofilaments from thermoplastic polymers are known in principle and e.g. described in Handbuch der Kunststofftechnik II, C. Hauser Verlag, Munich 1986, pages 295 to 319.

Es ist weiterhin bekannt, daß die Kerbschlagzähigkeit von Formkörpern aus thermoplastischen Polymeren durch Zusatz von Polyethylen/Polypropylen-Kautschuk verbessert werden kann. Die Polymermischungen aus thermoplastischen Polymeren und modifizierten Polyethylen/Polypropylen-Kautschuk werden dabei bekannterweise auf Doppelwellenextrudern compoundiert und granuliert und im Spritzguß verarbeitet.It is also known that the notched impact strength of molded articles made of thermoplastic polymers can be improved by adding polyethylene / polypropylene rubber. The polymer mixtures of thermoplastic polymers and modified polyethylene / polypropylene rubber are known to be compounded and granulated on twin-screw extruders and processed by injection molding.

Zur Herstellung von Monofilen für technische Zwecke, beispielsweise zur Weiterverarbeitung zu Preßfilzen für die Papierindustrie, die insbesondere eine hohe mechanische Festigkeit gegenüber Abrieb haben müssen, sind bislang wenige geeignete Polymermischungen bekannt geworden. Aus der Patentschrift US 5 169 711 ist bekannt, daß die Scheuerfestigkeit von Monofilen aus Polyethylenterephthalat (PET) durch Zusatz von thermoplastischem Polyurethan (TPU) erhöht werden kann.Few suitable polymer mixtures have hitherto become known for producing monofilaments for technical purposes, for example for further processing into press felts for the paper industry, which in particular must have a high mechanical strength against abrasion. From US Pat. No. 5,169,711 it is known that the abrasion resistance of monofilaments made of polyethylene terephthalate (PET) can be increased by adding thermoplastic polyurethane (TPU).

Außerdem sind Monofile aus Polymermischungen von Polyamid, Polyphenylenether und einem funktionalisierten Elastomer für die Herstellung von Preßfilzen bekannt (siehe z.B. int. Patentanmeldung WO 93/1325).In addition, monofilaments made from polymer mixtures of polyamide, polyphenylene ether and a functionalized elastomer for the production of press felts are known (see, for example, int. Patent application WO 93/1325).

Die Abriebbeständigkeit der Monofile und damit der technischen Gewebe, die aus diesen hergestellt werden können, wird durch die oben beschriebenen bekannten Rohstoffmodifikationen nur unzureichend verbessert, außerdem wird dabei die Festigkeit der Monofile jeweils reduziert.The abrasion resistance of the monofilaments and thus the technical fabrics that can be produced from them is only insufficiently improved by the known raw material modifications described above, and the strength of the monofilaments is also reduced in each case.

Der Erfindung liegt die Aufgabe zugrunde, die Abriebbeständigkeit und die Wechselbiegebeständigkeit schmelzgesponnener Monofile und deren Verarbeitbarkeit zu technischen Geweben oder Draht zu verbessern und damit z.B. die Standzeit technischer Gewebe signifikant zu verlängern.The invention has for its object to improve the abrasion resistance and the alternating bending resistance of melt-spun monofilaments and their processability to technical fabrics or wire and thus e.g. to significantly extend the service life of technical fabrics.

Diese Aufgabe wird erfindungsgemäß gelöst durch schmelzgesponnene Monofile für die Herstellung von technischem Draht oder technischen textilen Flächengebilden, dadurch gekennzeichnet, daß diese

  • a) 99 bis 70 Gew.-%, bevorzugt von 80 bis 95 Gew.-% Polyamid, Polyester oder Polypropylen als fadenbildendes Polymer,
  • b) von 30 bis 1 Gew.-%, bevorzugt von 5 bis 20 Gew.-% eines Maleinsäureanhydrid modifizierten Polyethylen/Polypropylen-Kautschuks
    und zusätzlich
  • c) bis 3 Gew.-%, vorzugsweise von 0,01 bis 3 Gew.-%, bezogen auf die Summe von a) + b) Alterungsstabilisatoren, z.B. sterisch gehinderte Phenole (SGP), Carbodiimide oder aromatische Amine, Kupfersalze, insbesondere solche des einwertigen Kupfers, enthalten.
This object is achieved according to the invention by melt-spun monofilaments for the production of technical wire or technical textile fabrics, characterized in that these
  • a) 99 to 70% by weight, preferably 80 to 95% by weight, of polyamide, polyester or polypropylene as the thread-forming polymer,
  • b) from 30 to 1 wt .-%, preferably from 5 to 20 wt .-% of a maleic anhydride modified polyethylene / polypropylene rubber
    and additionally
  • c) up to 3% by weight, preferably from 0.01 to 3% by weight, based on the sum of a) + b) aging stabilizers, for example sterically hindered phenols (SGP), carbodiimides or aromatic amines, copper salts, in particular those of monovalent copper.

Die erfindungsgemäßen Monofile zeichnen sich durch eine permanent verbesserte Scheuerbeständigkeit, verbesserte Beständigkeit gegen Wechselbiegebeanspruchung und verringerte Thermo-Schrumpfkräfte aus.The monofilaments according to the invention are distinguished by a permanently improved abrasion resistance, improved resistance to alternating bending stress and reduced thermal shrinking forces.

Weiterer Gegenstand ist die Verwendung der erfindungsgemäßen Monofile zur Herstellung von technischen Textilien, wie Geweben und Filzen für die Industrie, z.B. Klassiergeweben, Siebdruckgeweben, Formsiebgeweben und Preßfilzen zur Papier- und Zellulosefaserherstellung.Another object is the use of the monofilaments according to the invention for the production of technical textiles, such as fabrics and felts for industry, e.g. Classifying fabrics, screen printing fabrics, shaped screen fabrics and press felts for paper and cellulose fiber production.

Die Standzeit der technischen Textilien, insbesondere der Formsiebgewebe und der Preßfilze zur Papier- und Zellulosefaserherstellung wird durch die Verwendung erfindungsgemäßer Monofile gegenüber bekannten Monofilen verlängert.The service life of technical textiles, in particular the forming fabric and the press felts for paper and cellulose fiber production is extended by the use of monofilaments according to the invention compared to known monofilaments.

Die erfindungsgemäßen Monofile werden nach an sich bekannten Schmelzextrusionsverfahren hergestellt. Die Rohstoffe werden dabei entweder als Granulatmischung bzw. als Granulat/Pulvermischung oder als compoundiertes Granulat eingesetzt. Hierbei ist auf eine homogene Durchmischung der Komponenten in der Schmelze und somit letztlich in den Monofilen zu achten. Dies wird durch handelsübliche dynamische Mischer nach dem Extrudieren erreicht.The monofilaments according to the invention are produced by melt extrusion processes known per se. The raw materials are either a mixture of granules or used as granules / powder mixture or as compounded granules. It is important to ensure that the components are mixed homogeneously in the melt and thus ultimately in the monofilaments. This is achieved using commercially available dynamic mixers after extrusion.

Ziel war es, die Kerbschlagzähigkeit der Polymere und die Querstabilität der aus den Polymeren erhaltenen Monofilen zu erhöhen.The aim was to increase the impact strength of the polymers and the transverse stability of the monofilaments obtained from the polymers.

Übertaschenderweise wurde bei Verschleißtests bei den erfindungsgemäßen Monofilen zusätzlich eine Verbesserung der Scheuerfestigkeit mit wachsendem Anteil an Maleinsäureanhydrid modifiziertem Polyethylen/Polypropylen-Kautschuk festgestellt.Surprisingly, an improvement in the abrasion resistance with increasing proportion of maleic anhydride-modified polyethylene / polypropylene rubber was additionally found in wear tests for the monofilaments according to the invention.

Außerdem wurde unerwartet eine Reduzierung der Thermoschrumpfkräfte schon bei geringem Zusatz von Maleinsäureanhydrid modifiziertem Polyethylen/Polypropylen-Kautschuk erreicht, was sich positiv auf die Formstabilität der aus den Monofilen hergestellten Geweben bei der Thermofixierung des Gewebes auswirkt.In addition, a reduction in the thermal shrinkage forces was unexpectedly achieved even with a small addition of maleic anhydride-modified polyethylene / polypropylene rubber, which has a positive effect on the dimensional stability of the fabrics produced from the monofilaments during the heat setting of the fabrics.

Weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemäßen Monofile zur Herstellung von technischen textilen Flächengebilden oder von technischen Drähten, insbesondere Rasenmäherdraht. Die erfindungsgemäßen Monofile finden vorzugsweise Verwendung in sogenannten technischen Textilien wie Geweben und Filzen für die Industrie, z.B. Klassiergeweben, Siebdruckgeweben, Formsiebgeweben und Preßfilzen zur Papier- und Zellulosefaserherstellung.Another object of the invention is the use of the monofilaments according to the invention for the production of technical textile fabrics or of technical wires, in particular lawn mower wire. The monofilaments according to the invention are preferably used in so-called technical textiles such as fabrics and felts for industry, e.g. Classifying fabrics, screen printing fabrics, shaped screen fabrics and press felts for paper and cellulose fiber production.

Bevorzugtes fadenbildendes thermoplastisches Polymer zur Herstellung der Monofile ist Polyamid, insbesondere Polyamid (PA) 6, 6.6, 6.10, 6.12, 11 und 12, Mischungen der Polyamide oder Copolymere aus diesen. Bevorzugte Polyester sind Polyethylenterephthalat (PET) oder Polybutylenterephthalat (PBT).The preferred thread-forming thermoplastic polymer for the production of the monofilaments is polyamide, in particular polyamide (PA) 6, 6.6, 6.10, 6.12, 11 and 12, mixtures of the polyamides or copolymers thereof. Preferred polyesters are polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).

Als zusätzliche Additive können der erfindungsgemäßen Mischung noch bis 15 Gew.-%, bezogen auf die Summe der Komponenten a), b) und c), Weichmacher z.B. Caprolactam für Polyamid, Phenole, Arylsulfonamide oder Phthalsäureester, Pigmente z.B. TiO2, Ruß, Farbstoffe, innere Gleitmittel z.B. Erdalkalistearate insbesondere von Ca oder Mg, Wachse zur Transparenzerhöhung beispielsweise solche auf Basis von Fettsäureamiden beigemischt werden.The mixture according to the invention can contain up to 15% by weight, based on the sum of components a), b) and c), plasticizers, for example caprolactam for polyamide, phenols, arylsulfonamides or phthalic acid esters, pigments, for example TiO 2 , carbon black, dyes, as additional additives internal lubricants, for example alkaline earth stearates, in particular of Ca or Mg, waxes to increase transparency, for example those based on fatty acid amides, can be added.

BeispieleExamples

Beispiele 1 bis 5 zeigen erfindungsgemäße Monofile, Beispiel 6 ein Vergleichsbeispiel. Als fadenbildendes Polymer (Komponente A) wurde ein Polyamid 6 mit einer relativen Lösungsviskosität von ηrel = 4,0 (gemessen in m-Kresol bei 25°C) verwendet. Als modifizierter Kautschuk (Komponente B) wurde ein mittelviskoser halb-kristalliner Maleinsäureanhydrid modifizierter PE/PP-Kautschuk verwendet.Examples 1 to 5 show monofilaments according to the invention, example 6 a comparative example. A polyamide 6 with a relative solution viscosity of η rel = 4.0 (measured in m-cresol at 25 ° C.) was used as the thread-forming polymer (component A). A medium-viscosity semi-crystalline maleic anhydride modified PE / PP rubber was used as the modified rubber (component B).

Bei den Beispielen wurde als PE/PP-Kautschuk ein Produkt der Fa. EXXON-Chemical GmbH mit dem Handelsnamen Exxelor VA 1803 eingesetzt. Die chemische Formel ist angegeben mit

        H(C2H4)X(CH2CH-CH3)Y(O=COC=OCH=CH)ZH

mit den Indices X= 0,5 - 0,6, Y = 0,5 - 0,4, Z = 0.002. Das Molekulargewicht ist angegebenen mit 20.000 bis 60.000.In the examples, a product from EXXON-Chemical GmbH with the trade name Exxelor VA 1803 was used as PE / PP rubber. The chemical formula is given with

H (C 2 H 4 ) X (CH 2 CH-CH 3 ) Y (O = COC = OCH = CH) Z H

with the indices X = 0.5 - 0.6, Y = 0.5 - 0.4, Z = 0.002. The molecular weight is specified as 20,000 to 60,000.

Komponente C) ist ein handelsüblicher Alterungsstabilisator Irganox 1098 von Ciba Geigy, ein sterisch gehindertes Phenol der Formel (I)

Figure imgb0001
N,N'-Hexamethylen-bis-(3,5-di-tert.-butyl-4-hydroxy-hydrozimtsäureamid)Component C) is a commercially available aging stabilizer Irganox 1098 from Ciba Geigy, a sterically hindered phenol of the formula (I)
Figure imgb0001
 N, N'-hexamethylene-bis- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide)

Es wurden die Konzentrationen der Komponente A) zwischen 98,25 Gew.-% und 84,5 Gew.-% der Komponente B) zwischen 1,25 Gew.-% und 15 Gew.-% variiert. Die Konzentration der Komponente C) wurde konstant bei 0,5 Gew.-% belassenThe concentrations of component A) were varied between 98.25% by weight and 84.5% by weight of component B) between 1.25% by weight and 15% by weight. The concentration of component C) was kept constant at 0.5% by weight

Die Komponente A), B) und C) wurden als Granulat bzw. Granulatpulvermischung entsprechend dem gewünschten Konzentrationsverhältnis auf einem Einschneckenextruder unter Vakuum entgast, dann bei 270°C aufgeschmolzen und anschließend in einem dynamischen Mischer miteinander vermischt, so daß die Komponenten A), B) und C) feindispers homogen miteinander vermischt waren.The components A), B) and C) were degassed as granules or granule powder mixture in accordance with the desired concentration ratio on a single-screw extruder under vacuum, then melted at 270 ° C. and then mixed together in a dynamic mixer, so that components A), B ) and C) were homogeneously mixed finely dispersed.

Anschließend wurde in an sich bekannter Weise die Monofile auf einer Monofil-Spinn-Streck-Anlage produziert. Dabei wurde aus einer Vorrichtung zum Schmelzspinnen von Monofilen die fadenbildende Polymerschmelze zum Abkühlen in ein Wasserbad bei 20 bis 30°C abgesponnen, anschließend in Heißwasser bei 80°C und in Heißluft bei 150°C um das 3,5-fache verstreckt und zuletzt in Heißluft bei 210°C fixiert.The monofilament was then produced in a manner known per se on a monofilament spinning and drawing machine. The filament-forming polymer melt was spun from a device for melt spinning monofilaments to cool in a water bath at 20 to 30 ° C, then stretched 3.5 times in hot water at 80 ° C and in hot air at 150 ° C and finally in Hot air fixed at 210 ° C.

Das Beispiel 6 zeigt ein Polyamid-Monofil ohne Maleinsäureanhydrid modifizierten PE/PP-Kautschuk nur aus stabilisiertem Polyamid 6 (ηrel = 4,0) zum Vergleich zu den erfindungsgemäßen Monofilen nach Beispielen 1 bis 5. Die Herstellung erfolgt analog zum oben dargestellten Spinnvorgang.Example 6 shows a polyamide monofil without modified maleic anhydride PE / PP rubber only from stabilized polyamide 6 (η rel = 4.0) for comparison to the monofilaments according to the invention according to Examples 1 to 5. The preparation is carried out analogously to the spinning process shown above.

Die Ergebnisse der Beispiele 1 bis 6 sind in Tabelle 1 zusammengefaßt.The results of Examples 1 to 6 are summarized in Table 1.

AbriebmeßverfahrenAbrasion measurement method

Die Abriebuntersuchungen wurden in den Beispielen an den aus den Monofilen hergestellten Prüfstäben mittels des Abrasionstester AT 2000 der Firma Einlehner in Calciumcarbonat/Wasser-Suspension durchgeführt.In the examples, the abrasion tests were carried out on the test bars produced from the monofilaments using the AT 2000 abrasion tester from Einlehner in calcium carbonate / water suspension.

Als Verschleißkörper wurde ein Keramikleisten-Drehkörper bestehend aus 16 kreisförmig angeordneten Rundstäben aus Al-Oxid-Keramik mit flächig angeschliffener siebberührender Außenseite eingesetzt. Die Anordnung entspricht annähernd den offenen und geschlossenen Flächen eines Flachsaugers in einer Papiermaschine. Der Materialverlust des jeweiligen Prüfsiebes wird aus der Differenz zwischen abgeriebener und nicht-abgeriebener Siebfläche als Gewichts- und Dickenverlust ermittelt.

Figure imgb0002
A ceramic slat rotating body consisting of 16 circularly arranged round bars made of Al-oxide ceramic with a flat ground surface touching the screen was used as the wear body. The arrangement corresponds approximately to the open and closed surfaces of a flat suction device in a paper machine. The material loss of the respective test sieve is determined from the difference between the rubbed and non-rubbed sieve surface as a loss of weight and thickness.
Figure imgb0002

Tabelle 2 zeigt weitere Beispiele 7 bis 10, in denen anstelle Polyamid ein hydrolysestabilisiertes hochmolekulares Polyethylenterephthalat (PET) mit einem Maleinsäureanhydrid modifizierten Polyethylen/Propylen-Kautschuk (Exxelor VA 1803) sowie einem Hydrolysestabilisator (Stabaxol P100) verwendet wurde.

Figure imgb0003
Table 2 shows further Examples 7 to 10, in which a hydrolysis-stabilized high-molecular polyethylene terephthalate (PET) with a maleic anhydride-modified polyethylene / propylene rubber (Exxelor VA 1803) and a hydrolysis stabilizer (Stabaxol P100) was used instead of polyamide.
Figure imgb0003

In Tabelle 3 sind die Eigenschaften von technischem Draht (Rasenmäherdraht) hergestellt aus unstabilisiertem Copolyamid (Anteil Polyamid 6 : Polyamid 6.6 = 82:18 Gew.-%) mit einem Maleinsäureanhydrid modifiziertem Polyethylen/Polypropylen-Kautschuk wiedergegeben. In praxisnahen Tests wurde z.B. der Längenverlust nach dem Betonkantenschlagtest bestimmt. Der Längenverlust fällt mit steigendem Anteil Maleinsäureanhydrid modifiziertem Kautschuk.

Figure imgb0004
Table 3 shows the properties of technical wire (lawn mower wire) made from unstabilized copolyamide (proportion of polyamide 6: polyamide 6.6 = 82:18% by weight) with a polyethylene / polypropylene rubber modified with a maleic anhydride. In practical tests, for example, the loss of length after the concrete edge impact test was determined. The loss of length decreases with increasing proportion of rubber modified with maleic anhydride.
Figure imgb0004

Claims (8)

Schmelzgesponnene Monofile aus Polyamid, Polyester oder Polypropylen als fadenbildende Polymere für die Herstellung von technischem Draht, insbesondere Rasenmäherdraht oder technischen textilen Flachengebilden, dadurch gekennzeichnet, daß die Monofile a) 99 bis 70 Gew.-% des fadenbildenden Polymer, b) von 30 bis 1 Gew.-% eines Maleinsäureanhydrid modifizierten Polyethylen/Polypropylen-Kautschuks
und zusätzlich c) bis 3 Gew.-%, vorzugsweise von 0,01 bis 3 Gew.-%, bezogen auf die Summe von a) + b) Alterungsstabilisatoren enthalten. Melt-spun monofilaments made of polyamide, polyester or polypropylene as thread-forming polymers for the production of technical wire, in particular lawn mower wire or technical textile flat structures, characterized in that the monofilaments a) 99 to 70% by weight of the thread-forming polymer, b) from 30 to 1 wt .-% of a maleic anhydride modified polyethylene / polypropylene rubber
and additionally c) up to 3 wt .-%, preferably from 0.01 to 3 wt .-%, based on the sum of a) + b) contain aging stabilizers. Monofil nach Anspruch 1, dadurch gekennzeichnet, daß das fadenbildende thermoplastische Polymer ein Polyamid, insbesondere Polyamid 6, PA 6.6, PA 6.10, PA 6.12, PA 11 oder PA 12 ist oder ein Copolyamid aus den genannten bevorzugten Polyamiden.Monofilament according to claim 1, characterized in that the thread-forming thermoplastic polymer is a polyamide, in particular polyamide 6, PA 6.6, PA 6.10, PA 6.12, PA 11 or PA 12 or a copolyamide from the preferred polyamides mentioned. Monofil nach Anspruch 1, dadurch gekennzeichnet, daß das fadenbildende thermoplastische Polymer ein Polyethylenterephthalat (PET) oder Polybutylenterephthalat (PBT) ist.Monofilament according to claim 1, characterized in that the thread-forming thermoplastic polymer is a polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). Verwendung der Monofile nach den Ansprüchen 1 bis 3 zur Herstellung von technischen textilen Flachengebilden.Use of the monofilaments according to claims 1 to 3 for the production of technical textile flat structures. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß die textilen Flächengebilde Klassiergewebe, Siebdruckgewebe, Transportbänder und Formsiebe oder Preßfilze für die Zellulosefaseraufbereitung oder Papierherstellung sind.Use according to claim 4, characterized in that the textile fabrics are classifying fabrics, screen printing fabrics, conveyor belts and forming screens or press felts for cellulose fiber processing or paper production. Formsiebe oder Preßfilze, erhältlich aus Monofilen nach Ansprüchen 1 bis 3, für die Zellulosefaseraufbereitung und Papierherstellung.Forming screens or press felts, obtainable from monofilaments according to claims 1 to 3, for cellulose fiber processing and paper production. Verwendung der Monofile nach den Ansprüchen 1 bis 3 als Rasenmäherdraht.Use of the monofilaments according to claims 1 to 3 as lawn mower wire. Monofile nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß der Anteil des Kautschuks B) von 5 bis 20 Gew.-% und der Anteil des Polymeren A) von 80 bis 95 Gew.-% beträgt.Monofilaments according to Claims 1 to 3, characterized in that the proportion of rubber B) is from 5 to 20% by weight and the proportion of polymer A) is from 80 to 95% by weight.
EP96120750A 1996-01-04 1996-12-23 Melt-spun, abrasion-resistant monofilaments Expired - Lifetime EP0784107B1 (en)

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