EP1004691B1 - Core-sheath bicomponent fibres for papermaking clothing - Google Patents

Core-sheath bicomponent fibres for papermaking clothing Download PDF

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Publication number
EP1004691B1
EP1004691B1 EP19990810970 EP99810970A EP1004691B1 EP 1004691 B1 EP1004691 B1 EP 1004691B1 EP 19990810970 EP19990810970 EP 19990810970 EP 99810970 A EP99810970 A EP 99810970A EP 1004691 B1 EP1004691 B1 EP 1004691B1
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EP
European Patent Office
Prior art keywords
core
sheath
bicomponent fibre
fibre according
polyamide
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Expired - Lifetime
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EP19990810970
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German (de)
French (fr)
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EP1004691A1 (en
Inventor
Jürgen SPINDLER
Thomas Weller
Gunther Schäch
Simon Sutter
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EMS Chemie AG
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EMS Chemie AG
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F7/00—Other details of machines for making continuous webs of paper
    • D21F7/08—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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • 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
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2924—Composite
    • 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.]

Definitions

  • the present invention relates to the field of synthetic fibers as they are usually for the production of paper machine felts, especially of Paper machine felts for use in the press area of paper machines be used. It concerns a core-sheath bicomponent fiber which too essential parts made of polyamide. It also affects use of such a fiber for the production of paper machine felts.
  • Press felts serve to support the paper mass in paper machines and absorb water from the paper pulp during the pressing process. This usually happens in the paper making process immediately after Headbox and the Fourdrinier section, and before the paper web in the dryer section is completely dried.
  • press felts are made almost exclusively of polyamide 6 (PA 6) or PA 66 fibers and monofilaments, but felts made from PA 11 are also used in the literature Fibers (EP 0 372 769), and PA 12 fibers (EP 0 287 297) etc.
  • PEEK polyether ether ketone
  • PTFE polytetrafluoroethylene
  • EP 0 741 204 describes the use of core-jacket bicomponent adhesive fibers described for press felts, which are mainly designed to the surface quality, the running properties of the felt, the recovery and improve drainage. This happens through sticking, which by Melting the jacket component are generated.
  • the invention is therefore based on the object of providing a fiber which, processed into a paper machine felt, for example Has abrasion resistance and at the same time high temperatures, in particular under the conditions that occur with Impulse Pressing, withstands without to be compacted and glued.
  • a fiber of the type mentioned by the Fiber is designed as a core-jacket bicomponent fiber, which has a core and has a jacket at least partially enclosing the core, and in that the sheath consists of 45-98% by weight of a first polyamide, which has a melting point of more than 280 ° C, and 2 - 20% by weight of one Contains layered silicates.
  • the core also consists of a second polyamide.
  • the coat also contains up to 35% by weight of this second Polyamide.
  • the essence of the invention is therefore the fiber as a core-jacket bicomponent fiber build up, and by a layered silicate containing and refractory mantle both to prevent the compaction as well as a Achieve high abrasion resistance by storing the silicates caused reduction in the strength of the fiber but by preventing a solid core is present. Because the core is made of a second polyamide and the sheath also contains up to 35% by weight of this second polyamide contains an intimate connection between the core material and the Jacket material ensured.
  • a preferred embodiment has the feature that at least the core or the jacket or both parts contains up to 1% by weight of heat stabilizers, and that especially these heat stabilizers hindered phenols, Phosphonic acid derivatives, phosphites or combinations of these stabilizers are. This is another effective measure to increase heat stability and thus to prevent the two-component fiber from compacting.
  • the invention claims the use of such fiber according to the invention for producing a paper machine felt, especially a needled paper machine felt, which is still preferred for use in the press area, especially for impulse pressing or is designed for hot pressing.
  • the core is preferably made of PA 6 or PA 66 with a relative solution viscosity from 2.4 - 5.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) or from Mixtures of appropriate PA 6 and PA 66 qualities in a ratio of 1:99 to 99: 1 manufactured.
  • Polyamides of the types PA 11, PA 12, PA 69, PA 610, PA 612 or PA 1212 with a relative solution viscosity of 1.6 - 2.8 (0.5 g polymer per 100 ml m-cresol at 25 ° C) are used.
  • the core should preferably contain 0-1% by weight of heat stabilizers, e.g. based sterically hindered phenols, phosphonic acid derivatives or phosphites or Combinations of these stabilizers.
  • the core thus provides the necessary strength the fibers, for example when they are processed into felts.
  • the jacket should be made of a polyamide with a melting point of at least 280 ° C, and it should also contain 2-20% by weight of layered silicates (e.g. MICROMICA® MK 100 from CO-OP Chemical CO., LTD. Japan) and 0-35 % By weight of the type of polyamide from which the core is constructed.
  • suitable Polyamides with a melting point of at least 280 ° C are e.g. PA 46, PA 46 / 4T, PA 66 / 6T, PA6T / 6I, PA 9T, PA 10T, PA 12T and 2-methyl-1,5 pentanediamine T / 61 (MPMD T / 61), these polyamides up to 20% by weight of other monomers such as.
  • Caprolactam or Laurinlactam can contain.
  • the coat contains each also 0-1% by weight of heat stabilizers, e.g. sterically based hindered phenols, phosphonic acid derivatives or phosphites or combinations of these stabilizers.
  • the layered silicates can either be compounded can be incorporated into the polymer by means of a twin-screw extruder or but in the polymerization of one of the PA components right from the start Polymerization can be added, which enables better distribution. to Can improve the adhesion between polyamide and layered silicate particles of course additional adhesion promoters such as Amino silanes are used.
  • the core can be surrounded concentrically or non-concentrically by the jacket: at A non-concentric core-shell distribution can be achieved by suitable spinning and Stretching conditions a helical crimp can be generated.
  • the mass ratio of core to cladding is between 30:70 and 70:30, but other component ratios are also possible.
  • Example 1 (Comparative example) A fleece with a basis weight of 200 g / m 2 was produced from 17 dtex PA 6 fibers of the type TM 4000 from EMS Chemie AG. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • Example 2 17 dtex fibers were produced as follows: 89.5% by weight PA 6 with relative viscosity 3.4 (1 g polymer per 100 ml 96% Sulfuric acid at 25 ° C), 10% by weight layered silicate type MICROMICA® MK 100, 0.5 % By weight heat stabilizer Irganox® 1098 (Clariant, formerly Ciba-Geigy) was also used a twin screw extruder compounded at 280 ° C after all components had been pre-dried. The compounded material was dried and opened spun into fibers in a spinning system, stretched, crimped and cut.
  • Machine settings melt temperature at the extruder head: 300 ° C; Temperature spinning beam and nozzle pack: 300 ° C spinneret 279 holes Hole diameter 0.6 mm throughput 1066 g / min spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets Air-jet texturing 170 ° C Dryer temperature 170 ° C cutting length 80 mm
  • a fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • Example 3 17 dtex fibers were produced as follows: 89.5% by weight of PA 6T / 66 type Arlen® C2300 (PA 66 / 6T, from MITSUI, melting point 290-295 ° C), 10% by weight layered silicate type MICROMICA® MK 100 and 0.5% by weight Heat stabilizers Irganox® 1098 were used with a twin-screw extruder at 315 ° C compounded after all components had been pre-dried. The Compounded material was dried and added to the spinning system mentioned Spun fibers.
  • Machine settings melt temperature at the extruder head: 315 ° C; Temperature spinning beam and nozzle pack: 315 ° C spinneret 279 holes Hole diameter 0.6 mm throughput 1066 g / min spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets air jet texturing 190 ° C Dryer temperature 190 ° C cutting length 80 mm
  • a fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • Machine settings melt temperature of the core component at the extruder head: 300 ° C; Melt temperature of the jacket component at the extruder head: 315 ° C; Temperature spinning beam and nozzle pack: 315 ° C spinneret 210 holes Hole diameter 0.7 mm Throughput per component 401 g / min spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets Air-jet texturing 180 ° C Dryer temperature 190 ° C cutting length 80 mm
  • a fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • Example 5 17 dtex core-sheath bicomponent fibers with a core-sheath ratio 50/50 were manufactured as follows: Core component: PA 6 with relative viscosity 4.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098.
  • Sheath component 25% by weight PA 6 with relative viscosity 2.8 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C), 10% by weight layered silicate type MICROMICA® MK 100, 64.5% by weight PA 6T / 66 (Arlen® C 2300) and 0.5% by weight heat stabilizer Irganox® 1098 were mixed with a Twin-shaft extruder at 315 ° C compounded after all components had been pre-dried. Both components were dried and on the Bicomponent spinning system spun into core-sheath fibers.
  • Machine settings melt temperature of the core component at the extruder head: 300 ° C; Melt temperature of the jacket component at the extruder head: 315 ° C; Temperature spinning beam and nozzle pack: 315 ° C. spinneret 210 holes Hole diameter 0.7 mm Throughput per component 401 g / min. spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets air jet texturing 180 ° C Dryer temperature 190 ° C cutting length 80 mm
  • a fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • Example 6 17 dtex core-sheath bicomponent fibers with a core-sheath ratio 50/50 were manufactured as follows: Core component: PA 66 with relative viscosity 3.4 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098.
  • Sheath component 25% by weight PA 66 with relative viscosity 2.8 (1 g polymer per 100 ml 96% sulfuric acid 25 ° C), 10% by weight layered silicate type MICROMICA® MK 100, 64.5% by weight PA 6T / 66 (Arlen® C 2300) and 0.5% by weight heat stabilizer Irganox® 1098 were mixed with a Twin-shaft extruder at 315 ° C compounded after all components had been pre-dried. Both components were dried and on the Bicomponent spinning system with the same settings as in example 4 Core-sheath fibers spun.
  • a fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • Example 7 17 dtex core-sheath bicomponent fibers with a core-sheath ratio 50/50 were manufactured as follows: Core component: PA 6 with relative viscosity 4.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098. Sheath component: 10% by weight Layered silicate type MICROMICA® MK 100, 89.5% by weight PA 6T / 66 (Arlen® C 2300) and 0.5 wt.% Irganox® 1098 heat stabilizer was used with a twin-screw extruder 315 ° C compounded after all components had been pre-dried. Both components were dried and on the bicomponent spinning system spun the same settings as in Example 4 to core-sheath fibers.
  • Core component PA 6 with relative viscosity 4.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilize
  • a fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.
  • the fiber loss is given to assess the abrasion. The lower the Fiber loss is the better the abrasion resistance.
  • the felt runs through a felt length of 2 m and a speed of 30 m / min the calender every 4 Seconds.
  • the dwell time is approx. 40 milliseconds in the nip.
  • the test duration is 4 hours, i.e. 3600 cycles.
  • the quality of the felt is judged by the percentage air permeability (L) of the felt (L 1 ) after this treatment based on the air permeability of the felt (L 0 ) before the treatment.
  • L percentage air permeability
  • comparison variant 1 due to total compacting at high Temperatures are unusable, results in comparison variant 3, a very bad Abrasion resistance.
  • comparison variant 2 the compacting significantly reduced, but the level is not acceptable and the Abrasion resistance decreases significantly.
  • comparison variant 4 too Compacting still too strong.

Description

Die vorliegende Erfindung bezieht sich auf das Gebiet der Kunstfasern wie sie üblicherweise zur Herstellung von Papiermaschinenfilzen, insbesondere von Papiermaschinenfilzen zur Verwendung im Pressenbereich von Papiermaschinen verwendet werden. Sie betrifft eine Kern-Mantel-Bikomponentenfaser welche zu wesentlichen Teilen aus Polyamid besteht. Ausserdem betrifft sie die Verwendung einer solchen Faser zur Herstellung von Papiermaschinenfilzen. The present invention relates to the field of synthetic fibers as they are usually for the production of paper machine felts, especially of Paper machine felts for use in the press area of paper machines be used. It concerns a core-sheath bicomponent fiber which too essential parts made of polyamide. It also affects use of such a fiber for the production of paper machine felts.

STAND DER TECHNIKSTATE OF THE ART

Pressfilze dienen dazu, in Papiermaschinen die Papiermasse zu unterstützen und während des Pressvorgangs Wasser aus der Papiermasse aufzunehmen. Dies geschieht im Papierherstellungsprozess üblicherweise unmittelbar nach dem Stoffauflauf und der Langsiebpartie, und bevor die Papierbahn in der Trockenpartie vollständig getrocknet wird.Press felts serve to support the paper mass in paper machines and absorb water from the paper pulp during the pressing process. This usually happens in the paper making process immediately after Headbox and the Fourdrinier section, and before the paper web in the dryer section is completely dried.

Zur Erhöhung der Entwässerungsleistung im Pressvorgang wurden in den letzten Jahren die Temperaturen im Pressenbereich von Papiermaschinen immer weiter erhöht (B. Wahlstrom, "Pressing-the state of the art and future possibilities", Paper technology, February 1991, S. 18-27). Neue Entwicklungen wie "Hot Pressing" oder "Impulse Pressing" (siehe z.B. D. Orloff et al. TAPPI Journal Vol. 81 (07/1998), S. 113 - 116 und H. Larsson et al. TAPPI Journal Vol. 81 (07/1998), S. 117 - 122) arbeiten teilweise mit sehr hohen Temperaturen. Die hohen Temperaturen (beim Impulse Pressing teilweise über 200°C) führen einerseits zu einer vorteilhaften Erniedrigung der Viskosität des Wassers, beanspruchen aber andererseits die in den Pressfilzen verarbeiteten Fasern enorm. So werden infolge der hohen Temperaturen insbesondere Kunstfasern zumindest in der Mantelregion weich, was zu einer Zunahme der Kompaktierung und der Abrasion der Filze führen kann. Bei zunehmender Kompaktierung verkleben die Fasern, die Zwischenräume im Filz werden geringer und damit nimmt auch das Vermögen des Filzes ab, Wasser aus dem Papier aufzunehmen und abzutransportieren.To increase the drainage capacity in the pressing process, the last Years, the temperatures in the press area of paper machines continue to rise increased (B. Wahlstrom, "Pressing-the state of the art and future possibilities", Paper technology, February 1991, pp. 18-27). New developments such as "hot pressing" or "Impulse Pressing" (see e.g. D. Orloff et al. TAPPI Journal Vol. 81 (07/1998), p. 113-116 and H. Larsson et al. TAPPI Journal Vol. 81 (07/1998), pp. 117 - 122) sometimes work at very high temperatures. The high temperatures (at On the one hand, impulse pressing (sometimes above 200 ° C) leads to an advantageous one Lowering the viscosity of the water, but on the other hand, claiming that in the Press felts processed fibers enormously. So are due to the high temperatures especially synthetic fibers, at least in the sheath region, which leads to a Increase in compaction and abrasion of the felts. at increasing compaction, the fibers stick together, the spaces in the felt become smaller and with it the ability of the felt to decrease water pick up and remove the paper.

Um hohe Filzlaufzeiten und damit möglichst geringe Stillstandzeiten der Maschinen zu haben, ist ein sehr wesentliches Kriterium für die Einsetzbarkeit von Fasern für Pressfilze eine hohe Abrasionsbeständigkeit und eine geringe Kompaktierung. Aus diesem Grund bestehen heute Pressfilze fast ausschliesslich aus Polyamid 6 (PA 6) oder PA 66 Fasern und Monofilen, in der Literatur werden aber auch Filze aus PA 11 Fasern (EP 0 372 769), und PA 12 Fasern (EP 0 287 297) etc. beschrieben. For long felt runtimes and therefore the shortest possible downtimes of the machines Having is a very important criterion for the applicability of fibers for Press felts have high abrasion resistance and low compaction. Out For this reason, press felts are made almost exclusively of polyamide 6 (PA 6) or PA 66 fibers and monofilaments, but felts made from PA 11 are also used in the literature Fibers (EP 0 372 769), and PA 12 fibers (EP 0 287 297) etc.

Ebenso wurden beispielsweise PEEK(Polyetheretherketon)-Fasern (EP 0 473 430) oder PTFE(Polytetrafluoroethylen)-Fasern (WO 92/10607) für den Einsatz in Papiermaschinenfilzen getestet. Sie erweisen sich zwar hinsichtlich Temperaturbeständigkeit als geeignet, aufgrund Ihrer geringen Abrasionsbeständigkeit ermöglichen sie aber keine akzeptablen Filzlaufzeiten.PEEK (polyether ether ketone) fibers were also used, for example (EP 0 473 430) or PTFE (polytetrafluoroethylene) fibers (WO 92/10607) for use in Paper machine felts tested. They prove to be true Temperature resistance as suitable, due to your low Abrasion resistance, however, does not allow acceptable felt runtimes.

Die Verwendung von Fasern aus teilaromatischen Polyamiden, sowie ein Aufbau der Fasern als Bikomponentenfasern aus zwei Seite an Seite angeordneten Komponenten wurde vorgeschlagen (EP 529 506), es werden jedoch auch mit derartigen Fasern noch keine ausreichenden Abriebbeständigkeiten erreicht.The use of fibers from partially aromatic polyamides, as well as a structure of the Fibers arranged as bicomponent fibers from two side by side Components have been proposed (EP 529 506), but they are also used such fibers have not yet achieved sufficient abrasion resistance.

Kompaktierung sollte verhindert werden durch Beschichtung von Fasern mit Schichtsilikaten, bzw. durch Herstellung von Schichtsilikate enthaltenden Fasern und Monofilen (WO 97/27356; EP 0 070 709). Das Einarbeiten der Schichtsilikate ins Faser-Polymer hat jedoch den Nachteil, dass die Festigkeit der Fasern stark abnimmt.Compacting should be prevented by coating fibers with it Layered silicates, or by producing fibers containing layered silicates and Monofilaments (WO 97/27356; EP 0 070 709). Incorporation of the layered silicates into the However, fiber polymer has the disadvantage that the strength of the fibers is strong decreases.

In der EP 0 741 204 wird die Verwendung von Kern-Mantel-Bikomponenten-Klebefasern für Pressfilze beschrieben, welche hauptsächlich darauf ausgelegt sind, die Oberflächenqualität, die Laufeigenschaften des Filzes, die Wiedererholung und die Entwässerung zu verbessern. Dies geschieht durch Verklebungen, welche durch Aufschmelzen der Mantelkomponente erzeugt werden.EP 0 741 204 describes the use of core-jacket bicomponent adhesive fibers described for press felts, which are mainly designed to the surface quality, the running properties of the felt, the recovery and improve drainage. This happens through sticking, which by Melting the jacket component are generated.

DARSTELLUNG DER ERFINDUNGPRESENTATION OF THE INVENTION

Der Erfindung liegt demnach die Aufgabe zugrunde, eine Faser bereitzustellen, die, beispielsweise zu einem Papiermaschinenfilz verarbeitet, eine ausreichende Abrasionsbeständigkeit besitzt und gleichzeitig hohen Temperaturen, insbesondere unter den beim Impulse Pressing auftretenden Bedingungen, standhält ohne wesentlich kompaktiert und verklebt zu werden.The invention is therefore based on the object of providing a fiber which, processed into a paper machine felt, for example Has abrasion resistance and at the same time high temperatures, in particular under the conditions that occur with Impulse Pressing, withstands without to be compacted and glued.

Diese Aufgabe wird bei einer Faser der eingangs genannten Art gelöst, indem die Faser als Kern-Mantel-Bikomponentenfaser ausgebildet ist, welche einen Kern und einen den Kern wenigstens teilweise umschliessenden Mantel aufweist, und dadurch, dass der Mantel zu 45 - 98 Gew.% aus einem ersten Polyamid besteht, welches einen Schmelzpunkt von mehr als 280°C aufweist, und 2 - 20 Gew.% eines Schichtsilikates enthält. Weiter besteht der Kern aus einem zweiten Polyamid. Ausserdem enthält der Mantel auch noch bis zu 35 Gew.% dieses zweiten Polyamids. Der Kern der Erfindung besteht somit darin, die Faser als Kem-Mantel-Bikomponentenfaser aufzubauen, und durch einen Schichtsilikate enthaltenden und hochschmelzenden Mantel sowohl die Kompaktierung zu verhindern als auch eine hohe Abrasionsbeständigkeit zu erreichen, die durch die Einlagerung der Silikate bewirkte Reduktion der Festigkeit der Faser aber dadurch zu verhindern, dass ein fester Kern vorhanden ist. Dadaurch, dass der Kern aus einem zweiten Polyamid besteht und der Mantel auch noch bis zu 35 Gew.% dieses zweiten Polyamids enthält, wird eine innige Verbindung zwischen dem Kernmaterial und dem Mantelmaterial sichergestellt.This object is achieved with a fiber of the type mentioned by the Fiber is designed as a core-jacket bicomponent fiber, which has a core and has a jacket at least partially enclosing the core, and in that the sheath consists of 45-98% by weight of a first polyamide, which has a melting point of more than 280 ° C, and 2 - 20% by weight of one Contains layered silicates. The core also consists of a second polyamide. In addition, the coat also contains up to 35% by weight of this second Polyamide. The essence of the invention is therefore the fiber as a core-jacket bicomponent fiber build up, and by a layered silicate containing and refractory mantle both to prevent the compaction as well as a Achieve high abrasion resistance by storing the silicates caused reduction in the strength of the fiber but by preventing a solid core is present. Because the core is made of a second polyamide and the sheath also contains up to 35% by weight of this second polyamide contains an intimate connection between the core material and the Jacket material ensured.

Eine bevorzugte Ausführungsform weist das Merkmal auf, dass wenigstens der Kern oder der Mantel oder beide Teile bis zu 1 Gew.% Hitzestabilisatoren enthält, und dass insbesondere diese Hitzestabilisatoren sterisch gehinderte Phenole, Phosphonsäurederivate, Phosphite bzw. Kombinationen dieser Stabilisatoren sind. Dies ist eine weitere, effektive Massnahme zur Erhöhung der Wärmestabilität und damit zur Verhinderung des Kompaktierens der Zweikomponentenfaser.A preferred embodiment has the feature that at least the core or the jacket or both parts contains up to 1% by weight of heat stabilizers, and that especially these heat stabilizers hindered phenols, Phosphonic acid derivatives, phosphites or combinations of these stabilizers are. This is another effective measure to increase heat stability and thus to prevent the two-component fiber from compacting.

Zusätzlich beansprucht die Erfindung die Verwendung einer solchen erfindungsgemässen Faser zur Herstellung eines Papiermaschinenfilzes, insbesondere eines genadelten Papiermaschinenfilzes, welcher weiterhin bevorzugt auf die Anwendung im Pressenbereich, insbesondere beim Impulse Pressing oder beim Hot Pressing ausgelegt ist.In addition, the invention claims the use of such fiber according to the invention for producing a paper machine felt, especially a needled paper machine felt, which is still preferred for use in the press area, especially for impulse pressing or is designed for hot pressing.

Weitere Ausführungsformen der Kern-Mantel-Bikomponentenfaser und der Verwendung derselben ergeben sich aus den abhängigen Ansprüchen. Other embodiments of the core-sheath bicomponent fiber and the Use of the same results from the dependent claims.

WEGE ZUR AUSFÜHRUNG DER ERFINDUNGWAYS OF CARRYING OUT THE INVENTION

Bei der Beschreibung der Herstellung einer erfindungsgemässen Faser aus zwei als Kern und Mantel ausgebildeten Komponenten soll zunächst die Zusammensetzung des Kerns, anschliessend diejenige des Mantels diskutiert werden.In the description of the production of a fiber according to the invention from two as The core and sheath-formed components should initially be the composition of the core, then that of the cladding are discussed.

Der Kern wird bevorzugt aus PA 6 oder PA 66 mit einer relativen Lösungsviskosität von 2.4 - 5.0 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C) oder aus Mischungen entsprechender PA 6 und PA 66 Qualitäten im Verhältnis 1:99 bis 99:1 hergestellt. Ebenfalls können für den Kern Polyamide der Arten PA 11, PA 12, PA 69, PA 610, PA 612 oder PA 1212 mit einer relativen Lösungsviskosität von 1.6 - 2.8 (0.5 g Polymer pro 100 ml m-Kresol bei 25°C) Verwendung finden. Des weiteren sollte der Kern bevorzugt 0 - 1 Gew.% Hitzestabilisatoren enthalten, z.B. auf Basis sterisch gehinderter Phenole, Phosphonsäurederivate oder Phosphite bzw. Kombinationen dieser Stabilisatoren. Der Kern sorgt damit für die nötige Festigkeit der Fasern, wenn sie beispielsweise zu Filzen verarbeitet werden.The core is preferably made of PA 6 or PA 66 with a relative solution viscosity from 2.4 - 5.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) or from Mixtures of appropriate PA 6 and PA 66 qualities in a ratio of 1:99 to 99: 1 manufactured. Polyamides of the types PA 11, PA 12, PA 69, PA 610, PA 612 or PA 1212 with a relative solution viscosity of 1.6 - 2.8 (0.5 g polymer per 100 ml m-cresol at 25 ° C) are used. Furthermore the core should preferably contain 0-1% by weight of heat stabilizers, e.g. based sterically hindered phenols, phosphonic acid derivatives or phosphites or Combinations of these stabilizers. The core thus provides the necessary strength the fibers, for example when they are processed into felts.

Der Mantel sollte aus einem Polyamid mit einem Schmelzpunkt von mindestens 280°C bestehen, und er sollte zusätzlich 2-20 Gew.% Schichtsilikate (z.B. MICROMICA® MK 100 der Firma CO-OP Chemical CO., LTD. Japan) und 0 - 35 Gew.% des Polyamid-Typs, aus dem der Kern aufgebaut ist, enthalten. Geeignete Polyamide mit einem Schmelzpunkt von mindestens 280°C sind z.B. PA 46, PA 46/4T, PA 66/6T, PA6T/6I, PA 9T, PA 10T, PA 12T und 2-Methyl-1,5 Pentandiamin T/61 (MPMD T/61), wobei diese Polyamide bis zu 20 Gew.% an weiteren Monomeren wie z.B. Caprolactam oder Laurinlactam enthalten können. Der Mantel enthält ausserdem jeweils 0 - 1 Gew.% Hitzestabilisatoren, z.B. auf Basis sterisch gehinderter Phenole, Phosphonsäurederivate oder Phosphite bzw. Kombinationen dieser Stabilisatoren. Die Schichtsilikate können entweder durch Eincompoundieren mittels eines Zweischneckenextruders in das Polymer eingearbeitet werden oder aber bei der Polymerisation einer der PA-Komponenten schon zu Beginn der Polymerisation zugesetzt werden, was eine bessere Verteilung ermöglicht. Zur Verbesserung der Haftung zwischen Polyamid und Schichtsilikat-Teilchen können selbstverständlich zusätzlich Haftvermittler wie z.B. Amino-Silane eingesetzt werden.The jacket should be made of a polyamide with a melting point of at least 280 ° C, and it should also contain 2-20% by weight of layered silicates (e.g. MICROMICA® MK 100 from CO-OP Chemical CO., LTD. Japan) and 0-35 % By weight of the type of polyamide from which the core is constructed. suitable Polyamides with a melting point of at least 280 ° C are e.g. PA 46, PA 46 / 4T, PA 66 / 6T, PA6T / 6I, PA 9T, PA 10T, PA 12T and 2-methyl-1,5 pentanediamine T / 61 (MPMD T / 61), these polyamides up to 20% by weight of other monomers such as. Caprolactam or Laurinlactam can contain. The coat contains each also 0-1% by weight of heat stabilizers, e.g. sterically based hindered phenols, phosphonic acid derivatives or phosphites or combinations of these stabilizers. The layered silicates can either be compounded can be incorporated into the polymer by means of a twin-screw extruder or but in the polymerization of one of the PA components right from the start Polymerization can be added, which enables better distribution. to Can improve the adhesion between polyamide and layered silicate particles of course additional adhesion promoters such as Amino silanes are used.

Der Kern kann konzentrisch oder nicht konzentrisch vom Mantel umgeben sein: Bei einer nicht konzentrischen Kern-Mantel Verteilung kann durch geeignete Spinn- und Streckbedingungen eine helikale Kräuselung erzeugt werden.The core can be surrounded concentrically or non-concentrically by the jacket: at A non-concentric core-shell distribution can be achieved by suitable spinning and Stretching conditions a helical crimp can be generated.

Das Massenverhältnis von Kern zu Mantel liegt sinnvollerweise zwischen 30:70 und 70:30, aber auch andere Komponentenverhältnisse sind möglich.The mass ratio of core to cladding is between 30:70 and 70:30, but other component ratios are also possible.

Der Titerbereich, d.h. der Feinheitsgrad der Bikomponenten-Fasern, ausgedrückt als längenbezogene Masse, erstreckt sich von 6.7 bis 100 dtex (1dtex = 0.1 tex = 0.1 g/km), es sind aber prinzipiell auch Fasern ausserhalb dieses Bereichs herstellbar.The titer range, i.e. the fineness of the bicomponent fibers, expressed as length-related mass, extends from 6.7 to 100 dtex (1dtex = 0.1 tex = 0.1 g / km), but in principle there are also fibers outside this range produced.

Im Gegensatz zur oben beschriebenen Kern-Mantel-Bikomponenten-Klebefaser (EP 0 741 204) bewirkt die erfindungsgemässe Kern-Mantel-Bikomponentenfaser ein Verhindern des Verklebens bzw. Kompaktierens des Faservlieses bei hohen Temperaturen. Dies ist sehr wichtig, da die erfindungsgemässen Kem-Mantel-Bikomponentenfasern nicht nur in kleinen Anteilen im Filz eingesetzt werden, sondern zumindest in der Deckschicht die Hauptfaserkomponente darstellen.In contrast to the core-sheath bicomponent adhesive fiber described above (EP 0 741 204) brings about the core-jacket bicomponent fiber according to the invention Prevention of sticking or compacting of the nonwoven fabric at high Temperatures. This is very important since the core-jacket bicomponent fibers according to the invention not only used in small amounts in the felt, but represent the main fiber component at least in the top layer.

Die Herstellung mehrerer Vergleichsbeispiele sowie der Ausführungsbeispiele wird im Detail folgendermassen vorgeschlagen:The production of several comparative examples as well as the exemplary embodiments will proposed in detail as follows:

Beispiel 1: (Vergleichsbeispiel) Aus 17 dtex PA 6 Fasern des Typs TM 4000 der EMS Chemie AG wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.Example 1: (Comparative example) A fleece with a basis weight of 200 g / m 2 was produced from 17 dtex PA 6 fibers of the type TM 4000 from EMS Chemie AG. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

Beispiel 2: (Vergleichsbeispiel) 17 dtex Fasern wurden folgendermassen hergestellt: 89.5 Gew.% PA 6 mit relativer Viskosität 3.4 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C), 10 Gew.% Schichtsilikat Typ MICROMICA® MK 100, 0.5 Gew.% Hitzestabilisator Irganox® 1098 (Clariant, vorm. Ciba-Geigy), wurden mit einem Zweiwellenextruder bei 280°C compoundiert, nachdem alle Komponenten vorgetrocknet worden waren. Das compoundierte Material wurde getrocknet und auf einer Spinnanlage zu Fasern versponnen, verstreckt, gekräuselt und geschnitten.Example 2: (Comparative example) 17 dtex fibers were produced as follows: 89.5% by weight PA 6 with relative viscosity 3.4 (1 g polymer per 100 ml 96% Sulfuric acid at 25 ° C), 10% by weight layered silicate type MICROMICA® MK 100, 0.5 % By weight heat stabilizer Irganox® 1098 (Clariant, formerly Ciba-Geigy) was also used a twin screw extruder compounded at 280 ° C after all components had been pre-dried. The compounded material was dried and opened spun into fibers in a spinning system, stretched, crimped and cut.

Einstellungen der Maschine: Schmelzetemperatur am Extruderkopf: 300°C; Temperatur Spinnbalken und Düsenpaket: 300°C Spinndüse 279 Loch Lochdurchmesser 0.6 mm Durchsatz 1066 g/min Spinngeschwindigkeit 1000 m/min Präparationsauflage (Phosphorsäureester) 0.3% Verstreckverhältnis 2.4 Temperatur Streckgaletten
Air-Jet-Texturierung 170°C Trockner-Temperatur 170°C Schnittlänge 80 mm Machine settings: melt temperature at the extruder head: 300 ° C; Temperature spinning beam and nozzle pack: 300 ° C spinneret 279 holes Hole diameter 0.6 mm throughput 1066 g / min spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets
Air-jet texturing 170 ° C Dryer temperature 170 ° C cutting length 80 mm

Aus den resultierenden Fasern wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.A fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

Beispiel 3: (Vergleichsbeispiel) 17 dtex Fasern wurden folgendermassen hergestellt: 89.5 Gew.% PA 6T/66 Typ Arlen® C2300 (PA 66/6T, von MITSUI, Schmelzpunkt 290-295°C), 10 Gew.% Schichtsilikat Typ MICROMICA® MK 100 und 0.5 Gew.% Hitzestabilisator Irganox® 1098 wurden mit einem Zweiwellenextruder bei 315°C compoundiert, nachdem alle Komponenten vorgetrocknet worden waren. Das compoundierte Material wurde getrocknet und auf der erwähnten Spinnanlage zu Fasern versponnen.Example 3: (Comparative example) 17 dtex fibers were produced as follows: 89.5% by weight of PA 6T / 66 type Arlen® C2300 (PA 66 / 6T, from MITSUI, melting point 290-295 ° C), 10% by weight layered silicate type MICROMICA® MK 100 and 0.5% by weight Heat stabilizers Irganox® 1098 were used with a twin-screw extruder at 315 ° C compounded after all components had been pre-dried. The Compounded material was dried and added to the spinning system mentioned Spun fibers.

Einstellungen der Maschine: Schmelzetemperatur am Extruderkopf: 315°C; Temperatur Spinnbalken und Düsenpaket: 315°C Spinndüse 279 Loch Lochdurchmesser 0.6 mm Durchsatz 1066 g/min Spinngeschwindigkeit 1000 m/min Präparationsauflage (Phosphorsäureester) 0.3% Verstreckverhältnis 2.4 Temperatur Streckgaletten Air-Jet-Texturierung 190°C Trockner-Temperatur 190°C Schnittlänge 80 mm Machine settings: melt temperature at the extruder head: 315 ° C; Temperature spinning beam and nozzle pack: 315 ° C spinneret 279 holes Hole diameter 0.6 mm throughput 1066 g / min spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets air jet texturing 190 ° C Dryer temperature 190 ° C cutting length 80 mm

Aus den resultierenden Fasern wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.A fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

Beispiel 4: (Vergleichsbeispiel) 17 dtex Kern-Mantel-Bikomponentenfasern mit einem Kern-Mantel-Verhältnis 50/50 wurden folgendermassen hergestellt:

  • Kernkomponente: PA 6 mit relativer Viskosität 4.0 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C) und 0.5 Gew.% Hitzestabilisator Irganox® 1098.
  • Mantelkomponente: 99.5 Gew.% PA 6T/66 (Arlen® C 2300), 0.5 Gew.% Hitzestabilisator Irganox® 1098, wobei der Hitzestabilisator in Form eines 5%igen Masterbatch in PA 6T/66 (Arlen® C 2300) zudosiert wurde. Beide Komponenten wurden getrocknet und auf der erwähnten Anlage mit einer Bikomponenten-Spinndüse zu Kern-Mantel-Fasern versponnen.
    • Example 4: (Comparative example) 17 dtex core-sheath bicomponent fibers with a core / sheath ratio of 50/50 were produced as follows:
  • Core component: PA 6 with relative viscosity 4.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098.
  • Jacket component: 99.5% by weight PA 6T / 66 (Arlen® C 2300), 0.5% by weight heat stabilizer Irganox® 1098, the heat stabilizer being added in the form of a 5% masterbatch in PA 6T / 66 (Arlen® C 2300). Both components were dried and spun on the system mentioned with a bicomponent spinneret to form core-sheath fibers.

    • Einstellungen der Maschine: Schmelzetemperatur der Kernkomponente am Extruderkopf: 300°C; Schmelzetemperatur der Mantelkomponente am Extruderkopf: 315°C; Temperatur Spinnbalken und Düsenpaket: 315°C Spinndüse 210 Loch Lochdurchmesser 0.7 mm Durchsatz pro Komponente 401 g/min Spinngeschwindigkeit 1000 m/min Präparationsauflage (Phosphorsäureester) 0.3% Verstreckverhältnis 2.4 Temperatur Streckgaletten
    Air-Jet-Texturierung     180°C     Trockner-Temperatur 190°C Schnittlänge 80 mm     Machine settings: melt temperature of the core component at the extruder head: 300 ° C; Melt temperature of the jacket component at the extruder head: 315 ° C; Temperature spinning beam and nozzle pack: 315 ° C spinneret 210 holes Hole diameter 0.7 mm Throughput per component 401 g / min spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets
    Air-jet texturing     180 ° C     Dryer temperature 190 ° C cutting length 80 mm

    Aus den resultierenden Fasern wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.A fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

    Beispiel 5: 17 dtex Kern-Mantel-Bikomponentenfasern mit einem Kern-Mantel-Verhältnis 50/50 wurden folgendermassen hergestellt: Kemkomponente: PA 6 mit relativer Viskosität 4.0 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C) und 0.5 Gew.% Hitzestabilisator Irganox® 1098. Mantelkomponente: 25 Gew.% PA 6 mit relativer Viskosität 2.8 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C), 10 Gew.% Schichtsilikat Typ MICROMICA® MK 100, 64.5 Gew.% PA 6T/66 (Arlen® C 2300) und 0.5 Gew.% Hitzestabilisator Irganox® 1098 wurden mit einem Zweiwellenextruder bei 315°C compoundiert nachdem alle Komponenten vorgetrocknet worden waren. Beide Komponenten wurden getrocknet und auf der Bikomponenten-Spinnanlage zu Kern-Mantel-Fasern versponnen.Example 5: 17 dtex core-sheath bicomponent fibers with a core-sheath ratio 50/50 were manufactured as follows: Core component: PA 6 with relative viscosity 4.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098. Sheath component: 25% by weight PA 6 with relative viscosity 2.8 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C), 10% by weight layered silicate type MICROMICA® MK 100, 64.5% by weight PA 6T / 66 (Arlen® C 2300) and 0.5% by weight heat stabilizer Irganox® 1098 were mixed with a Twin-shaft extruder at 315 ° C compounded after all components had been pre-dried. Both components were dried and on the Bicomponent spinning system spun into core-sheath fibers.

    Einstellungen der Maschine: Schmelzetemperatur der Kemkomponente am Extruderkopf: 300°C; Schmelzetemperatur der Mantelkomponente am Extruderkopf: 315°C; Temperatur Spinnbalken und Düsenpaket: 315°C. Spinndüse 210 Loch Lochdurchmesser 0.7 mm Durchsatz pro Komponente 401 g/min. Spinngeschwindigkeit 1000 m/min Präparationsauflage (Phosphorsäureester) 0.3% Verstreckverhältnis 2.4 Temperatur Streckgaletten Air-Jet-Texturierung 180°C Trockner-Temperatur 190°C Schnittlänge 80 mm Machine settings: melt temperature of the core component at the extruder head: 300 ° C; Melt temperature of the jacket component at the extruder head: 315 ° C; Temperature spinning beam and nozzle pack: 315 ° C. spinneret 210 holes Hole diameter 0.7 mm Throughput per component 401 g / min. spin speed 1000 m / min Preparation pad (phosphoric acid ester) 0.3% draw ratio 2.4 Temperature stretch godets air jet texturing 180 ° C Dryer temperature 190 ° C cutting length 80 mm

    Aus den resultierenden Fasern wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.A fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

    Beispiel 6: 17 dtex Kern-Mantel-Bikomponentenfasern mit einem Kern-Mantel-Verhältnis 50/50 wurden folgendermassen hergestellt: Kernkomponente: PA 66 mit relativer Viskosität 3.4 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C) und 0.5 Gew.% Hitzestabilisator Irganox® 1098. Mantelkomponente: 25 Gew.% PA 66 mit relativer Viskosität 2.8 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C), 10 Gew.% Schichtsilikat Typ MICROMICA® MK 100, 64.5 Gew.% PA 6T/66 (Arlen® C 2300) und 0.5 Gew.% Hitzestabilisator Irganox® 1098 wurden mit einem Zweiwellenextruder bei 315°C compoundiert nachdem alle Komponenten vorgetrocknet worden waren. Beide Komponenten wurden getrocknet und auf der Bikomponenten-Spinnanlage mit den gleichen Einstellungen wie bei Beispiel 4 zu Kern-Mantel-Fasern versponnen.Example 6: 17 dtex core-sheath bicomponent fibers with a core-sheath ratio 50/50 were manufactured as follows: Core component: PA 66 with relative viscosity 3.4 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098. Sheath component: 25% by weight PA 66 with relative viscosity 2.8 (1 g polymer per 100 ml 96% sulfuric acid 25 ° C), 10% by weight layered silicate type MICROMICA® MK 100, 64.5% by weight PA 6T / 66 (Arlen® C 2300) and 0.5% by weight heat stabilizer Irganox® 1098 were mixed with a Twin-shaft extruder at 315 ° C compounded after all components had been pre-dried. Both components were dried and on the Bicomponent spinning system with the same settings as in example 4 Core-sheath fibers spun.

    Aus den resultierenden Fasern wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.A fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

    Beispiel 7: 17 dtex Kern-Mantel-Bikomponentenfasern mit einem Kern-Mantel-Verhältnis 50/50 wurden folgendermassen hergestellt: Kernkomponente: PA 6 mit relativer Viskosität 4.0 (1 g Polymer pro 100 ml 96%iger Schwefelsäure bei 25°C) und 0.5 Gew.% Hitzestabilisator Irganox® 1098. Mantelkomponente: 10 Gew.% Schichtsilikat Typ MICROMICA® MK 100, 89.5 Gew.% PA 6T/66 (Arlen® C 2300) und 0.5 Gew.% Hitzestabilisator Irganox® 1098 wurden mit einem Zweiwellenextruder bei 315°C compoundiert nachdem alle Komponenten vorgetrocknet worden waren. Beide Komponenten wurden getrocknet und auf der Bikomponenten-Spinnanlage mit den gleichen Einstellungen wie bei Beispiel 4 zu Kern-Mantel-Fasern versponnen.Example 7: 17 dtex core-sheath bicomponent fibers with a core-sheath ratio 50/50 were manufactured as follows: Core component: PA 6 with relative viscosity 4.0 (1 g polymer per 100 ml 96% sulfuric acid at 25 ° C) and 0.5% by weight heat stabilizer Irganox® 1098. Sheath component: 10% by weight Layered silicate type MICROMICA® MK 100, 89.5% by weight PA 6T / 66 (Arlen® C 2300) and 0.5 wt.% Irganox® 1098 heat stabilizer was used with a twin-screw extruder 315 ° C compounded after all components had been pre-dried. Both components were dried and on the bicomponent spinning system spun the same settings as in Example 4 to core-sheath fibers.

    Aus den resultierenden Fasern wurde ein Vlies mit einem Flächengewicht von 200 g/m2 hergestellt. Von diesem Vlies wurden je drei Lagen auf die Papierseite und zwei Lagen auf die Maschinenseite eines PA 6 Monofilamentgewebes aufgenadelt. Dieser Testfilz wurde anschliessend bei 165°C 10 Minuten fixiert.A fleece with a basis weight of 200 g / m 2 was produced from the resulting fibers. Three layers of this fleece were needled onto the paper side and two layers onto the machine side of a PA 6 monofilament fabric. This test felt was then fixed at 165 ° C for 10 minutes.

    Die obigen zu Filzen verarbeiteten Beispielfasern wurden folgenden Tests unterzogen, die Resultate sind in Tabelle 1 zusammengestellt.The above example fibers processed into felts were the following tests subjected, the results are summarized in Table 1.

    1. Abrasionstest:1. Abrasion test:

    Ein Teil des Filzes wurde auf einer Filztestpresse (FTP) behandelt (gemäss DE 44 34 898 C2, Seite 5 Zeilen 27 bis 56 und Figuren). Die Wassertemperatur wurde auf 50°C eingestellt.Part of the felt was treated on a felt test press (FTP) (according to DE 44 34 898 C2, page 5 lines 27 to 56 and figures). The water temperature was up 50 ° C set.

    Zur Beurteilung der Abrasion wird der Faserverlust angegeben. Je geringer der Faserverlust ist, desto besser ist die Abriebbeständigkeit.The fiber loss is given to assess the abrasion. The lower the Fiber loss is the better the abrasion resistance.

    2. Temperaturbeständigkeit (Beständigkeit gegen Kompaktierung bei hohen Temperaturen):2. Temperature resistance (resistance to compaction at high Temperatures):

    Ein weiterer Teil des Filzes wurde zunächst 24 Stunden in demineralisiertem Wasser bei Raumtemperatur gelagert und anschliessend folgendermassen behandelt:Another part of the felt was initially in demineralized water for 24 hours stored at room temperature and then treated as follows:

    In einer Spannapparatur wird der feuchte Filz mit einem Kalander behandelt (untere Walze T = 205°C, obere Walze kalt, Liniendruck: 70 kN/m). Der Filz durchläuft bei einer Filzlänge von 2 m und einer Geschwindigkeit von 30 m/min den Kalander alle 4 Sekunden. Bei einer angenommenen Nip-Breite von 20 mm beträgt die Verweilzeit im Nip ca. 40 Millisekunden. Die Testdauer liegt bei 4 Stunden also 3600 Zyklen. The moist felt is treated with a calender in a tensioning device (bottom Roller T = 205 ° C, upper roller cold, line pressure: 70 kN / m). The felt runs through a felt length of 2 m and a speed of 30 m / min the calender every 4 Seconds. With an assumed nip width of 20 mm, the dwell time is approx. 40 milliseconds in the nip. The test duration is 4 hours, i.e. 3600 cycles.

    Beurteilt wird die Qualität des Filzes an der prozentualen Luftdurchlässigkeit (L) des Filzes (L1) nach dieser Behandlung bezogen auf die Luftdurchlässigkeit des Filzes (L0) vor der Behandlung. Je grösser dieser Wert ist, desto besser sind der Filz bzw. die entsprechenden Fasern geeignet. Bei einer Kalandertemperatur von 50°C liegt dieser Wert für Vergleichsbeispiel 1 bei L = 71 %. Variante 1 2 3 4 5 6 7 Faserverlust [g/m2] 16 93 163 43 30 38 45 Luftdurchlässigkeit L [%] 3 35 65 45 63 67 65 The quality of the felt is judged by the percentage air permeability (L) of the felt (L 1 ) after this treatment based on the air permeability of the felt (L 0 ) before the treatment. The larger this value, the better the felt or the corresponding fibers are suitable. At a calender temperature of 50 ° C, this value for Comparative Example 1 is L = 71%. variant 1 2 3 4 5 6 7 Fiber loss [g / m 2 ] 16 93 163 43 30 38 45 Air permeability L [%] 3 35 65 45 63 67 65

    Während Vergleichsvariante 1 wegen totaler Kompaktierung bei hohen Temperaturen unbrauchbar ist, resultiert bei Vergleichsvariante 3 eine sehr schlechte Abrasionsbeständigkeit. Bei Vergleichsvariante 2 wird zwar die Kompaktierung signifikant verringert, das Niveau ist aber nicht akzeptabel und die Abrasionsbeständigkeit nimmt wesentlich ab. Auch bei Vergleichsvariante 4 ist die Kompaktierung immer noch zu stark.During comparison variant 1 due to total compacting at high Temperatures are unusable, results in comparison variant 3, a very bad Abrasion resistance. In comparison variant 2, the compacting significantly reduced, but the level is not acceptable and the Abrasion resistance decreases significantly. In comparison variant 4, too Compacting still too strong.

    Bei den erfindungsgemässen Beispielen 5 bis 7 nimmt die Abrasionsbeständigkeit zwar ebenfalls ab, die Resultate liegen aber immer noch in einem Bereich, der in der Papierindustrie Stand der Technik und akzeptiert ist.In examples 5 to 7 according to the invention, the abrasion resistance decreases Although also from, the results are still in a range that in the Paper industry state of the art and accepted.

    Die Kompaktierung bei hohen Temperaturen ist deutlich geringer als bei den Vergleichsvarianten 1 und 2.Compacting at high temperatures is significantly less than that of the Comparative variants 1 and 2.

    Claims (10)

    1. A core/sheath bicomponent fibre which exhibits a core and a sheath at least partly enclosing the core, characterised in that the sheath consists to an amount of 45-98 % by wt. of a first polyamide which has a melting point of more than 280 °C, and contains 2-20 % by wt. of a layer silicate, that the core consists essentially of a second polyamide and that the sheath also contains 0-35 % by wt. of this second polyamide.
    2. The core/sheath bicomponent fibre according to claim 1 characterised in that the second polyamide consists of PA 6 or PA 66 with a relative solution viscosity of 2.4-5.0, measured in sulphuric acid, 1g polymer being taken per 100 ml of 96 % sulphuric acid at 25 °C, or a mixture of corresponding PA 6 and PA 66 grades.
    3. The sheath/core bicomponent fibre according to claim 1 characterised in that the second polyamide consists of PA 11, PA 12, PA 69, PA 610, PA 612 or PA 1212 with a relative solution viscosity of 1.6-2.8, measured in m-cresol, 0.5 g polymer being taken per 100 ml m-cresol at 25 °C, or a mixture of the above-named substances.
    4. The core/sheath bicomponent fibre according to one of claims 1 to 3 characterised in that the first polyamide consists of PA 46, PA 46/4T, PA 66/6T, PA6T/61, PA 9T, PA 10T, PA 12T or MPMDT/61 or a mixture of the above-named substances and that it contains up to 20 % by wt. of further copolymers, such as caprolactam or laurolactam.
    5. The sheath/core bicomponent fibre according to one of claims 1 to 4 characterised in that the core or sheath or both components contain up to 1 % by wt. of heat stabilisers.
    6. The sheath/core bicomponent fibre according to claim 5 characterised in that the heat stabilisers are sterically hindered phenols, phosphonic acid derivatives, phosphites or combinations of these stabilisers.
    7. The sheath/core bicomponent fibre according to one of claims 1 to 6 characterised in that the fibre has a linear density in the region of 5 to 200 dtex, particularly preferably in the region 6.7 to 100 dtex.
    8. The sheath/core bicomponent fibre according to one of claims 1 to 7 characterised in that the density ratio of core to sheath is in a region of 7:3 to 3:7.
    9. A use of a sheath/core bicomponent fibre according to one of claims 1 to 8 for producing a paper maker's felt, in particular a needled paper marker's felt.
    10. The use of a core/sheath bicomponent fibre according to claim 9 characterised in that the paper maker's felt is designed for use in the pressing sector, in particular for impulse pressing or for hot pressing.
    EP19990810970 1998-11-26 1999-10-26 Core-sheath bicomponent fibres for papermaking clothing Expired - Lifetime EP1004691B1 (en)

    Applications Claiming Priority (2)

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    DE19854732 1998-11-26
    DE1998154732 DE19854732C1 (en) 1998-11-26 1998-11-26 Core-jacket bicomponent fiber and its use

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    EP1004691A1 EP1004691A1 (en) 2000-05-31
    EP1004691B1 true EP1004691B1 (en) 2003-12-17

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    EP (1) EP1004691B1 (en)
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    DE (2) DE19854732C1 (en)

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1985752A1 (en) 2006-02-14 2008-10-29 Ichikawa Co., Ltd. Press felt for papermaking
    EP2213788A1 (en) 2007-11-20 2010-08-04 Ichikawa Co., Ltd. Carrier belt for wet paper web

    Families Citing this family (21)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    ATE298016T1 (en) * 1998-09-14 2005-07-15 Cerex Advanced Fabrics Inc NON-WOVEN FABRICS
    US20060252332A9 (en) * 1998-09-14 2006-11-09 Ortega Albert E Nonwoven fabrics with two or more filament cross sections
    US6465389B1 (en) * 1999-07-29 2002-10-15 Sumitomo Chemical Company, Limited Heat resistant catalyst sheet and process for producing same
    US20040216828A1 (en) * 2001-08-17 2004-11-04 Ortega Albert E. Nonwoven fabrics with two or more filament cross sections
    US6670034B2 (en) 2001-10-18 2003-12-30 Shakespeare Company, Llc Single ingredient, multi-structural filaments
    US7175902B2 (en) * 2001-10-18 2007-02-13 Cerex Advanced Fabrics, Inc. Nonwoven fabrics containing yarns with varying filament characteristics
    DE60329921D1 (en) * 2002-09-13 2009-12-17 Cerex Advanced Fabrics Inc METHOD FOR REDUCING STATIC CHARGES IN A SPUNBOND PROCESS
    JP2007039823A (en) * 2005-08-01 2007-02-15 Ichikawa Co Ltd Felt for producing paper
    US7799708B2 (en) * 2006-02-10 2010-09-21 Cerex Advanced Fabrics, Inc. Coated fabrics with increased abrasion resistance
    JP4891826B2 (en) 2007-03-30 2012-03-07 イチカワ株式会社 Press felt for papermaking
    JP5148973B2 (en) 2007-11-20 2013-02-20 イチカワ株式会社 Felt for papermaking
    CA2708804C (en) * 2007-12-14 2016-01-12 3M Innovative Properties Company Fiber aggregate
    MX2010006456A (en) * 2007-12-14 2010-09-28 Schlumberger Technology Bv Proppants and uses thereof.
    WO2009079231A2 (en) * 2007-12-14 2009-06-25 Schlumberger Canada Limited Methods of contacting and/or treating a subterranean formation
    MX2010006455A (en) * 2007-12-14 2010-09-28 Schlumberger Technology Bv Methods of treating subterranean wells using changeable additives.
    US10058808B2 (en) 2012-10-22 2018-08-28 Cummins Filtration Ip, Inc. Composite filter media utilizing bicomponent fibers
    US20140179189A1 (en) * 2012-12-20 2014-06-26 Taiwan Textile Research Institute Nylon Composite Fiber and Fabric Thereof
    EP3004437B1 (en) 2013-05-29 2019-03-06 Invista Technologies S.à r.l. Fusible bicomponent spandex
    TW201600538A (en) * 2014-05-14 2016-01-01 英威達技術有限公司 Amorphous high performance polyamide
    CN111139583B (en) * 2019-12-27 2021-10-26 福建省锋源盛纺织科技有限公司 Waterproof mesh cloth and preparation method thereof
    CN111155232B (en) * 2019-12-27 2021-08-10 福建省锋源盛纺织科技有限公司 Mesh cloth with good thermal insulation performance and preparation method thereof

    Family Cites Families (14)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    SE446994B (en) * 1977-11-21 1986-10-20 Nordiskafilt Ab dewatering
    CA1235249A (en) * 1981-07-17 1988-04-12 William B. Bond Aluminum silicate filled abrasion-resistant polyamide monofilament
    JPS5818497A (en) * 1981-07-17 1983-02-03 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− Papermaking belt
    GB8709067D0 (en) * 1987-04-15 1987-05-20 Albany Int Corp Monofilaments
    GB8827789D0 (en) 1988-11-28 1988-12-29 Albany Research Uk Paper machine felts
    GB9018987D0 (en) 1990-08-31 1990-10-17 Albany Research Uk Peek hot press felts and fabrics
    GB9026475D0 (en) * 1990-12-05 1991-01-23 Albany Research Uk Improvements in and relating to paper machine clothing
    DE4226592A1 (en) * 1991-08-23 1993-03-04 Inventa Ag PAPER MACHINE FELTS AND METHOD FOR PRODUCING THE SAME
    JP3348260B2 (en) * 1994-06-02 2002-11-20 日本フエルト株式会社 Felt for papermaking
    JPH08158160A (en) * 1994-12-05 1996-06-18 Unitika Ltd Conjugated fiber for air bag
    US5549967A (en) * 1995-05-04 1996-08-27 Huyck Licensco, Inc. Papermakers' press fabric with increased contact area
    GB9601525D0 (en) * 1996-01-25 1996-03-27 Scapa Group Plc Industrial fabrics
    US5617903A (en) * 1996-03-04 1997-04-08 Bowen, Jr.; David Papermaker's fabric containing multipolymeric filaments
    US5888915A (en) * 1996-09-17 1999-03-30 Albany International Corp. Paper machine clothings constructed of interconnected bicomponent fibers

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1985752A1 (en) 2006-02-14 2008-10-29 Ichikawa Co., Ltd. Press felt for papermaking
    EP2213788A1 (en) 2007-11-20 2010-08-04 Ichikawa Co., Ltd. Carrier belt for wet paper web

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    US6207276B1 (en) 2001-03-27
    JP2000273722A (en) 2000-10-03
    DE59908100D1 (en) 2004-01-29
    DE19854732C1 (en) 2000-09-14
    EP1004691A1 (en) 2000-05-31

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