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EP0542070B1 - Hybrid yarn made of polyamide fibres and reinforcing fibres - Google Patents

Hybrid yarn made of polyamide fibres and reinforcing fibres Download PDF

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Publication number
EP0542070B1
EP0542070B1 EP92118673A EP92118673A EP0542070B1 EP 0542070 B1 EP0542070 B1 EP 0542070B1 EP 92118673 A EP92118673 A EP 92118673A EP 92118673 A EP92118673 A EP 92118673A EP 0542070 B1 EP0542070 B1 EP 0542070B1
Authority
EP
European Patent Office
Prior art keywords
polyamide
hybrid yarn
fibres
fabric
yarn
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.)
Expired - Lifetime
Application number
EP92118673A
Other languages
German (de)
French (fr)
Other versions
EP0542070A1 (en
Inventor
Joerg Dr. Vogelsang
Giorgio Dr. Greening
Regina Laws
Peter Dr. Ittemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cytec Technology Corp
Original Assignee
Cytec Technology Corp
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Publication date
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Publication of EP0542070A1 publication Critical patent/EP0542070A1/en
Application granted granted Critical
Publication of EP0542070B1 publication Critical patent/EP0542070B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/402—Yarns in which fibres are united by adhesives; Impregnated yarns or threads the adhesive being one component of the yarn, i.e. thermoplastic yarn
    • 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
    • Y10T428/2936—Wound or wrapped core or coating [i.e., spiral or helical]
    • 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.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065—Including strand which is of specific structural definition
    • Y10T442/313—Strand material formed of individual filaments having different chemical compositions
    • Y10T442/3138—Including inorganic filament
    • 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]
    • Y10T442/425—Including strand which is of specific structural definition
    • Y10T442/438—Strand material formed of individual filaments having different chemical compositions

Definitions

  • the invention relates to a wrapped hybrid yarn made of polyamide fibers and reinforcing fibers according to the preamble of claim 1.
  • a hybrid yarn is known for example from document EP-A-0 156 599.
  • Hybrid yarns in which thermoplastic fibers and reinforcing fibers are intimately mixed, have been increasingly used in the past few years for the production of high-performance composite materials.
  • the hybrid yarns and the fabrics made from them are very flexible and can therefore be deformed as required. If they are consolidated by pressing at temperatures above the softening point of the thermoplastic, it melts and forms a matrix in which the reinforcing fibers are embedded in the preferred direction.
  • EP-B 156 599 describes a process for the production of hybrid yarn from carbon fibers and thermoplastic fibers, in which the two types of fiber are spread apart, mixed with one another by being brought together via rollers or rods, and the mixed yarn is then optionally wrapped with another thermoplastic yarn. Such wrapping brings about a good thread closure, so that the yarn can be easily woven without the addition of a size.
  • Hybrid yarn based on the thermoplastics mentioned in the examples of EP-B 156 599 is not suitable for the production of inexpensive and easily processable high-performance composite materials. In principle, however, this is possible with polyamides, which, in addition to many others, are also mentioned in the description of EP-B 156 599. Attempting to produce hybrid yarns from the usual high and medium viscosity polyamide fibers shows that the time required for consolidation to the composite material is relatively long and that some mechanical properties of the composite materials, in particular the transverse tensile strength, are too low.
  • the object of the invention was therefore to provide a hybrid yarn which does not have these disadvantages.
  • This object is achieved in that an extremely low-viscosity polyamide is used in the production of hybrid yarn from polyamide fibers and reinforcing fibers.
  • the invention accordingly relates to a hybrid yarn composed of polyamide fibers A and reinforcing fibers B, in which the individual filaments of the two types of fibers are mixed, and which is wrapped with a polyamide yarn A ', the polyamide A having a melt viscosity of less than 220 Pa ⁇ s (measured according to DIN 54 811 at a shear rate of 100 s -1 and at a temperature that is 30 ° C above the melting point or the glass transition temperature of the polyamide).
  • GB-A 2 105 247 describes fiber composite materials which are produced by wrapping a fiber core made of reinforcing fibers with a thermoplastic wrapping yarn.
  • the core consists of a carbon fiber yarn and two ends of a nylon multifilament yarn, and a nylon multifilament yarn is also used as the wrapping yarn.
  • the three multifilament yarns are arranged side by side in the fiber core; the individual filaments have not been mixed, the fiber composite material therefore has a low level of mechanical properties.
  • Preferred reinforcing fibers B are carbon fibers and glass fibers.
  • fibers made of ceramic materials, silicon carbide and boron nitride are also suitable, as well as those made of polymers with a softening point which is more than 70 ° C. above the softening point of polyamide A, for example from polyether ketone or fully aromatic polyamides.
  • polyamide fibers A preferably polyamide-6 and polyamide-6.6.
  • polyamide-6,6 T, polyamide-6,10, polyamide-10, and a polyamide made of adipic acid and 1,3-xylylenediamine and copolyamides based on the corresponding monomers are also suitable.
  • the polyamides A have a melt viscosity of less than 220, preferably less than 180, measured according to DIN 54 811 at a shear rate of 100 s -1 and at a temperature 30 ° C. above the melting point (in the case of partially crystalline) Polyamides) or above the glass transition temperature (in the case of amorphous polyamides) of the polymer.
  • the hybrid yarns are preferably produced in accordance with EP-B 156 599 by spreading the two types of fibers separately from one another by blowing with air and then mixing them by bringing them together over rolls or rods.
  • the spreading can in principle also be carried out by a liquid jet, by electrostatic charging or by separating the individual filaments by means of combs.
  • intimate mixing of the individual filaments is obtained, so that thermoplastic and reinforcing fibers are evenly and statistically distributed in the mixed yarn.
  • Such intimate mixing is not necessary for all purposes; one can also dispense with spreading the starting fibers and mix them using simple methods, e.g. by pulling them together over rollers or rods or swirling them together in an air stream.
  • a polyamide yarn A ' is used for this, preferably the same polyamide as that used for the polyamide fiber A.
  • a different type of polyamide can also be used; in principle also a polyamide, whose melt viscosity is over 220 Pa ⁇ s.
  • the wrapping yarn should preferably have a titer of 40 to 100 dtex.
  • the proportions should preferably be selected so that in the finished hybrid yarn contains 26 to 80% by weight of polyamide fibers A, 20 to 75% by weight of reinforcing fibers B and 0.2 to 3% by weight of wrapping yarn A '.
  • the hybrid yarn according to the invention can be processed into woven, knitted or braided fabrics without the additional application of a size.
  • a plurality of yarns can be laid down in parallel to scrims or ribbons, a plurality of such scrims being stacked parallel or at predetermined angles to one another can be. You can also wind the yarns over tubes to tubes.
  • These semi-finished products can then be consolidated into composites by pressing at temperatures above the softening point of the polyamide and, if necessary, deformed. It is advisable to apply a size to the semi-finished product beforehand, which can reduce the consolidation time.
  • This is preferably an aqueous dispersion of a thermoplastic which is compatible with polyamide A.
  • the composite materials based on the hybrid yarn according to the invention can be used to manufacture heavy-duty articles, e.g. Tennis racket frames, baseball and hockey sticks, frames for badminton and squash rackets, and bicycle frames.
  • heavy-duty articles e.g. Tennis racket frames, baseball and hockey sticks, frames for badminton and squash rackets, and bicycle frames.
  • Ultramid® B a polyamide 6 from BASF AG with different melt viscosity
  • a multifilament yarn made of 184 filaments with a total of 217 tex Two of these yarns were intimately mixed together with a Celion® G30-500 carbon fiber yarn from Celion Carbon Fibers, consisting of 12,000 individual carbon filaments, as described in EP 156 599, by spreading the individual multifilament yarns with air and then together over and were brought together under two bars. Then they are wound with a 6 tex strong auxiliary yarn (consisting of 12 single filaments) made of Ultramid® B (melt viscosity 260 Pa ⁇ s). The winding rate of the auxiliary yarn was 150 turns / m of the resulting hybrid yarn. The product had an even distribution of thermoplastic and carbon fibers, it contained 64.1% carbon fibers 34.8% polyamide fibers A 1.1% thread A '.
  • a consolidated test specimen was then produced from the hybridized and wound yarn thus produced.
  • the hybridized yarn was wound on a metal reel that had a free area of 220 mm x 270 mm on the inside.
  • a total of six layers (three on each side) were wound and then the reel was placed between two steel tools designed for this purpose, which were to transmit pressure and heat to the wound hybrid yarn.
  • the hybrid yarn was consolidated in a hot press.
  • the tool was placed in the press preheated to the temperature T and kept at a pressure of 5.5 bar for 15 minutes so that the hybridized yarn was heated to T. The pressure was then increased to 14 bar within one minute and this pressure was held for Z minutes. The tool was then cooled in the same press for 10 minutes by inserting cooling cassettes between the hybrid yarn tool and the press jaws. A 2 mm thick, consolidated plate with a smooth, non-porous surface was found when the tool was opened.
  • the material was subjected to a 90 ° tensile test according to SAC-MA 4-88.
  • the 2 mm thick plate was cut into 25 mm x 210 mm specimens with a diamond saw, taking care to ensure that the reinforcing fibers were aligned exactly parallel to the 25 mm long side of the specimens was respected.
  • the tensile strength is shown in the table.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Artificial Filaments (AREA)
  • Woven Fabrics (AREA)

Description

Die Erfindung betrifft ein umwicheltes Hybridgarn aus Polyamidfasern und Verstärkungsfasern gemäß Oberbegriff des Anspruches 1. Ein derartiges Hybridgarn ist beispielsweise aus dem Dokument EP-A-0 156 599 bekannt. Hybridgarne, in denen Thermoplastfasern und Verstärkungsfasern innig vermischt sind, werden in den letzten Jahren in zunehmendem Maße zur Herstellung von Hochleistungsverbundwerkstoffen verwendet. Die Hybridgarne sowie daraus hergestellte Flächengebilde sind sehr flexibel und deshalb beliebig verformbar. Wenn man sie durch Verpressen bei Temperaturen oberhalb des Erweichungspunktes des Thermoplasten konsolidiert, schmilzt dieser und bildet eine Matrix, in der die Verstärkungsfasern in Vorzugsrichtung orientiert eingelagert sind.The invention relates to a wrapped hybrid yarn made of polyamide fibers and reinforcing fibers according to the preamble of claim 1. Such a hybrid yarn is known for example from document EP-A-0 156 599. Hybrid yarns, in which thermoplastic fibers and reinforcing fibers are intimately mixed, have been increasingly used in the past few years for the production of high-performance composite materials. The hybrid yarns and the fabrics made from them are very flexible and can therefore be deformed as required. If they are consolidated by pressing at temperatures above the softening point of the thermoplastic, it melts and forms a matrix in which the reinforcing fibers are embedded in the preferred direction.

In der EP-B 156 599 ist ein Verfahren zur Herstellung von Hybridgarn aus Kohlenstoffasern und Thermoplastfasern beschrieben, bei dem die beiden Faserarten gespreizt, durch Zusammenführen über Rollen oder Stäben miteinander vermischt und das Mischgarn anschließend gegebenenfalls durch ein weiteres Thermoplastgarn umwickelt wird. Ein solches Umwickeln bewirkt einen guten Fadenschluß, so daß das Garn auch ohne zusätzliches Aufbringen einer Schlichte problemlos gewoben werden kann. Hybridgarn auf Basis der in den Beispielen von EP-B 156 599 genannten Thermoplasten ist nicht zur Herstellung von kostengünstigen und leicht verarbeitbaren Hochleistungsverbundwerkstoffen geeignet. Dies ist jedoch grundsätzlich mit Polyamiden möglich, die in der Beschreibung der EP-B 156 599 neben vielen anderen ebenfalls genannt sind. Versucht man, aus den üblichen hoch- und mittelviskosen Polyamidfasern Hybridgarne herzustellen, so zeigt sich, daß die für die Konsolidierung zum Verbundwerkstoff benötigte Zeit verhältnismäßig lang ist, und daß einige mechanische Eigenschaften der Verbundwerkstoffe, insbesondere die Querzugfestigkeit, ein zu niedriges Niveau haben.EP-B 156 599 describes a process for the production of hybrid yarn from carbon fibers and thermoplastic fibers, in which the two types of fiber are spread apart, mixed with one another by being brought together via rollers or rods, and the mixed yarn is then optionally wrapped with another thermoplastic yarn. Such wrapping brings about a good thread closure, so that the yarn can be easily woven without the addition of a size. Hybrid yarn based on the thermoplastics mentioned in the examples of EP-B 156 599 is not suitable for the production of inexpensive and easily processable high-performance composite materials. In principle, however, this is possible with polyamides, which, in addition to many others, are also mentioned in the description of EP-B 156 599. Attempting to produce hybrid yarns from the usual high and medium viscosity polyamide fibers shows that the time required for consolidation to the composite material is relatively long and that some mechanical properties of the composite materials, in particular the transverse tensile strength, are too low.

Der Erfindung lag also die Aufgabe zugrunde, ein Hybridgarn bereitzustellen, welches diese Nachteile nicht aufweist.The object of the invention was therefore to provide a hybrid yarn which does not have these disadvantages.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man bei der Herstellung von Hybridgarn aus Polyamidfasern und Verstärkungsfasern ein extrem niedrigviskoses Polyamid einsetzt.This object is achieved in that an extremely low-viscosity polyamide is used in the production of hybrid yarn from polyamide fibers and reinforcing fibers.

Gegenstand der Erfindung ist demzufolge ein Hybridgarn aus Polyamidfasern A und Verstärkungsfasern B, in dem die Einzelfilamente der beiden Faserarten vermischt sind, und welches von einem Polyamidgarn A' umwickelt ist, wobei das Polyamid A eine Schmelzviskosität von weniger als 220 Pa·s aufweist (gemessen nach DIN 54 811 bei einer Schergeschwindigkeit von 100 s-1 und bei einer Temperatur, die 30°C über dem Schmelzpunkt bzw. der Glastemperatur des Polyamids liegt).The invention accordingly relates to a hybrid yarn composed of polyamide fibers A and reinforcing fibers B, in which the individual filaments of the two types of fibers are mixed, and which is wrapped with a polyamide yarn A ', the polyamide A having a melt viscosity of less than 220 Pa · s (measured according to DIN 54 811 at a shear rate of 100 s -1 and at a temperature that is 30 ° C above the melting point or the glass transition temperature of the polyamide).

In der GB-A 2 105 247 sind Faserverbundwerkstoffe beschrieben, die hergestellt werden durch Umwickeln eines Faserkerns aus Verstärkungsfasern mit einem thermoplastischen Umwindegarn. Im Beispiel 2 besteht der Kern aus einem Kohlenstoffasergarn und zwei Enden eines Nylon-Multifilamentgarns, als Umwindegarn wird ebenfalls ein Nylon-Multifilamentgarn eingesetzt. Im Faserkern liegen die drei Multifilamentgarne nebeneinander angeordnet vor; eine Vermischung der Einzelfilamente hat nicht stattgefunden, der Faserverbundwerkstoff weist deshalb ein niedriges mechanisches Eigenschaftsniveau auf.GB-A 2 105 247 describes fiber composite materials which are produced by wrapping a fiber core made of reinforcing fibers with a thermoplastic wrapping yarn. In example 2, the core consists of a carbon fiber yarn and two ends of a nylon multifilament yarn, and a nylon multifilament yarn is also used as the wrapping yarn. The three multifilament yarns are arranged side by side in the fiber core; the individual filaments have not been mixed, the fiber composite material therefore has a low level of mechanical properties.

Bevorzugte Verstärkungsfasern B sind Kohlenstoffasern und Glasfasern. Daneben sind auch Fasern aus keramischen Materialien, Siliciumcarbid und Bornitrid geeignet, sowie solche aus Polymeren mit einem Erweichungspunkt, der mehr als 70°C über dem Erweichungspunkt des Polyamids A liegt, zum Beispiel aus Polyetherketon oder vollaromatischen Polyamiden.Preferred reinforcing fibers B are carbon fibers and glass fibers. In addition, fibers made of ceramic materials, silicon carbide and boron nitride are also suitable, as well as those made of polymers with a softening point which is more than 70 ° C. above the softening point of polyamide A, for example from polyether ketone or fully aromatic polyamides.

Für die Polyamidfasern A können die üblichen aliphatischen oder teilaromatischen Homo- und Copolyamide eingesetzt werden, bevorzugt Polyamid-6 und Polyamid-6.6. Daneben sind auch Polyamid-6,6 T, Polyamid-6,10, Polyamid-10, und ein Polyamid aus Adipinsäure und 1,3-Xylylendiamin sowie Copolyamide auf Basis der entsprechenden Monomeren geeignet.The usual aliphatic or partially aromatic homo- and copolyamides can be used for the polyamide fibers A, preferably polyamide-6 and polyamide-6.6. In addition, polyamide-6,6 T, polyamide-6,10, polyamide-10, and a polyamide made of adipic acid and 1,3-xylylenediamine and copolyamides based on the corresponding monomers are also suitable.

Die Polyamide A weisen erfindungsgemäß eine Schmelzeviskosität von weniger als 220, vorzugsweise von weniger als 180 Pa·s auf, gemessen nach DIN 54 811 bei einer Schergeschwindigkeit von 100 s-1 und bei einer Temperatur, die 30°C über dem Schmelzpunkt (bei teilkristallinen Polyamiden) bzw. über der Glastemperatur (bei amorphen Polyamiden) des Polymeren liegt.According to the invention, the polyamides A have a melt viscosity of less than 220, preferably less than 180, measured according to DIN 54 811 at a shear rate of 100 s -1 and at a temperature 30 ° C. above the melting point (in the case of partially crystalline) Polyamides) or above the glass transition temperature (in the case of amorphous polyamides) of the polymer.

Die Hybridgarne werden vorzugsweise nach EP-B 156 599 hergestellt, indem man die beiden Faserarten getrennt voneinander durch Anblasen mit Luft spreizt und dann durch Zusammenführen über Rollen oder Stäbe vermischt. Das Spreizen kann grundsätzlich auch durch einen Flüssigkeitsstrahl, durch elektrostatische Aufladung oder durch Separieren der Einzelfilamente durch Kämme erfolgen. Bei den bisher genannten Arbeitsweisen erhält man eine innige Vermischung der Einzelfilamente, so daß im Mischgarn Thermoplast- und Verstärkungsfasern gleichmäßig statistisch verteilt sind. Eine solche innige Vermischung ist aber nicht für alle Anwendungszwecke notwendig; man kann auch auf das Spreizen der Ausgangsfasern verzichten und diese nach einfachen Methoden vermischen, z.B. indem man sie zusammen über Rollen oder Stäbe zieht oder gemeinsam in einem Luftstrom verwirbelt.The hybrid yarns are preferably produced in accordance with EP-B 156 599 by spreading the two types of fibers separately from one another by blowing with air and then mixing them by bringing them together over rolls or rods. The spreading can in principle also be carried out by a liquid jet, by electrostatic charging or by separating the individual filaments by means of combs. In the previously mentioned working methods, intimate mixing of the individual filaments is obtained, so that thermoplastic and reinforcing fibers are evenly and statistically distributed in the mixed yarn. Such intimate mixing is not necessary for all purposes; one can also dispense with spreading the starting fibers and mix them using simple methods, e.g. by pulling them together over rollers or rods or swirling them together in an air stream.

Wesentlich ist, daß das Hybridgarn nach dem Vermischen der Polyamid- und Verstärkungsfasern umwickelt wird. Dafür wird ein Polyamidgarn A' verwendet, wobei vorzugsweise das gleiche Polyamid wie bei der Polyamidfaser A eingesetzt wird. Es kann aber auch ein andersartiges Polyamid verwendet werden; grundsätzlich auch ein Polyamid, dessen Schmelzviskosität über 220 Pa·s liegt. Das Umwindegarn soll vorzugsweise einen Titer von 40 bis 100 dtex aufweisen.It is essential that the hybrid yarn is wrapped after the polyamide and reinforcing fibers have been mixed. A polyamide yarn A 'is used for this, preferably the same polyamide as that used for the polyamide fiber A. However, a different type of polyamide can also be used; in principle also a polyamide, whose melt viscosity is over 220 Pa · s. The wrapping yarn should preferably have a titer of 40 to 100 dtex.

Die Mengenverhältnisse sollen vorzugsweise so gewählt werden, daß im fertigen Hybridgarn 26 bis 80 Gew. -% Polyamidfasern A, 20 bis 75 Gew.-% Verstärkungsfasern B und 0,2 bis 3 Gew.-% Umwindegarn A' enthält.The proportions should preferably be selected so that in the finished hybrid yarn contains 26 to 80% by weight of polyamide fibers A, 20 to 75% by weight of reinforcing fibers B and 0.2 to 3% by weight of wrapping yarn A '.

Das erfindungsgemäße Hybridgarn kann ohne zusätzliches Aufbringen einer Schlichte zu Geweben, Gewirken oder Geflechten verarbeitet werden. Mehrere Garne können parallel zu Gelegen oder Bändern abgelegt werden, wobei mehrere solcher Gelege parallel oder in vorbestimmten Winkeln zueinander gestapelt werden können. Ferner kann man die Garne über Kerne zu Rohren wickeln. Diese Halbzeuge können dann durch Verpressen bei Temperaturen oberhalb des Erweichungspunktes des Polyamids zu Verbundwerkstoffen konsolidiert und gegebenenfalls verformt werden. Dabei ist es zweckmäßig, vorher auf das Halbzeug eine Schlichte aufzubringen, wodurch die Konsolidierungszeit verkürzt werden kann. Diese ist vorzugsweise eine wäßrige Dispersion eines Thermoplasten, der mit dem Polyamid A verträglich ist.The hybrid yarn according to the invention can be processed into woven, knitted or braided fabrics without the additional application of a size. A plurality of yarns can be laid down in parallel to scrims or ribbons, a plurality of such scrims being stacked parallel or at predetermined angles to one another can be. You can also wind the yarns over tubes to tubes. These semi-finished products can then be consolidated into composites by pressing at temperatures above the softening point of the polyamide and, if necessary, deformed. It is advisable to apply a size to the semi-finished product beforehand, which can reduce the consolidation time. This is preferably an aqueous dispersion of a thermoplastic which is compatible with polyamide A.

Aus den Verbundwerkstoffen auf Basis des erfindungsgemäßen Hybridgarn können hochbelastbare Gebrauchsartikel hergestellt werden, die z.B. Tennisschlägerrahmen, Baseball- und Hockeyschläger, Rahmen für Badminton- und Squash-Schläger, sowie Farradrahmen.The composite materials based on the hybrid yarn according to the invention can be used to manufacture heavy-duty articles, e.g. Tennis racket frames, baseball and hockey sticks, frames for badminton and squash rackets, and bicycle frames.

Die in den Beispielen genannten Teile und Prozente beziehen sich auf das Gewicht.The parts and percentages given in the examples relate to the weight.

BeispieleExamples Allgemeine Versuchsdurchführung:General experimentation:

Ultramid® B, ein Polyamid 6 der BASF AG, mit unterschiedlicher Schmelzeviskosität, wurde durch ein einstufiges Spinnstreckverfahren zu einem Multifilamentgarn aus 184 Filamenten mit insgesamt 217 tex versponnen. Zwei dieser Garne wurden zusammen mit einem Celion® G30-500 Kohlenstoffasergarn der Firma Celion Carbon Fibers, bestehend aus 12000 einzelnen Kohlenstoffilamenten, wie in EP 156 599 beschrieben, miteinander innig vermischt, indem die einzelnen Multifilamentgarne durch Anblasen mit Luft gespreizt und dann gemeinsam über und unter zwei Stäben zusammengeführt wurden. Anschließend werden sie mit einem 6 tex starken Hilfsgarn (bestehend aus 12 Einzelfilamenten) aus Ultramid® B (Schmelzeviskosität 260 Pa·s) umwunden. Die Umwindungsrate des Hilfsgarns betrug 150 Umdrehungen/m des entstehenden Hybridgarnes. Das Produkt wies eine gleichmäßige Verteilung von Thermoplast- und Kohlenstoffasern auf, es enthielt
64,1 % Kohlenstoffasern
34,8 % Polyamidfasern A
1,1 % Umwindegarn A'.Ultramid® B, a polyamide 6 from BASF AG with different melt viscosity, was spun using a one-step spin-stretching process to a multifilament yarn made of 184 filaments with a total of 217 tex. Two of these yarns were intimately mixed together with a Celion® G30-500 carbon fiber yarn from Celion Carbon Fibers, consisting of 12,000 individual carbon filaments, as described in EP 156 599, by spreading the individual multifilament yarns with air and then together over and were brought together under two bars. Then they are wound with a 6 tex strong auxiliary yarn (consisting of 12 single filaments) made of Ultramid® B (melt viscosity 260 Pa · s). The winding rate of the auxiliary yarn was 150 turns / m of the resulting hybrid yarn. The product had an even distribution of thermoplastic and carbon fibers, it contained
64.1% carbon fibers
34.8% polyamide fibers A
1.1% thread A '.

Einige Proben des Hybridgarns wurden dann durch eine wäßrige Schlichtedispersion geführt, die aus einer alkoholischen Lösung eines Terpolyamids (ELVAMID 8063 von DuPont) hergestellt wurden. Dabei wurden 0,6 % Schlichte aufgetragen. In der folgenden Tabelle sind diese Versuche mit (S) gekennzeichnet.Some samples of the hybrid yarn were then passed through an aqueous size dispersion made from an alcoholic solution of a terpolyamide (ELVAMID 8063 from DuPont). 0.6% size was applied. These tests are marked with (S) in the following table.

Anschließend wurde aus dem so hergestellten hybridisierten und umwundenen Garn ein konsolidierter Probekörper hergestellt. Um eine möglichst unidirektionale Ausrichtung der Verstärkungsfasern zu erhalten, wurde das hybridisierte Garn auf eine Metall-Haspel gewickelt, die innen eine freie Fläche von 220 mm x 270 mm hatte. Es wurden insgesamt sechs Lagen (drei auf jeder Seite) gewickelt und danach wurde die Haspel zwischen zwei dafür konstruierte Stahlwerkzeuge gelegt, die Druck und Wärme auf das gewickelte Hybridgarn übertragen sollten. Die Kcnsolidierung des Hybridgarns erfolgte in einer heißen Presse.A consolidated test specimen was then produced from the hybridized and wound yarn thus produced. In order to get the reinforcement fibers to be as unidirectional as possible, the hybridized yarn was wound on a metal reel that had a free area of 220 mm x 270 mm on the inside. A total of six layers (three on each side) were wound and then the reel was placed between two steel tools designed for this purpose, which were to transmit pressure and heat to the wound hybrid yarn. The hybrid yarn was consolidated in a hot press.

Zuerst wurde das Werkzeug in die auf die Temperatur T vorgeheizten Presse gelegt und bei einem Druck von 5.5 bar 15 Minuten lang belassen, damit das hybridisierte Garn auf T erhitzt wurde. Danach wurde der Druck auf 14 bar innerhalb einer Minute erhöht und dieser Druck für Z Minuten gehalten. Anschließend wurde das Werkzeug 10 Minuten lang in derselben Presse abgekühlt, indem Kühlkassetten zwischen dem Hybridgarnwerkzeug und den Preßbacken eingeschoben wurden. Eine 2 mm starke, konsolidierte Platte mit einer glatten porenfreien Oberfläche wurde beim Öffnen des Werkzeugs vorgefunden.First the tool was placed in the press preheated to the temperature T and kept at a pressure of 5.5 bar for 15 minutes so that the hybridized yarn was heated to T. The pressure was then increased to 14 bar within one minute and this pressure was held for Z minutes. The tool was then cooled in the same press for 10 minutes by inserting cooling cassettes between the hybrid yarn tool and the press jaws. A 2 mm thick, consolidated plate with a smooth, non-porous surface was found when the tool was opened.

Um die Anbindung der Polyamidmatrix an die Kohlenstoffasern zu prüfen, wurde das Material einer 90°-Zugprüfung nach SAC-MA 4-88 unterzogen. Hierfür wurde die 2 mm starke Platte zu 25 mm x 210 mm großen Probekörpern mit einer Diamantsäge zerschnitten, wobei auf die genaue parallele Ausrichtung der Verstärkungsfasern zur 25 mm langen Seite der Probekörpern geachtet wurde. Die Zugfestigkeit ist in der Tabelle wiedergegeben. Tabelle Beispiel Viskosität [Pa·s] T [°C] Z [min] Zugfestgkeit [MPa] 1 260 260 20 48.4 2 260 260 5 27.4 3 130 260 20 63.2 3S 130 260 20 64.0 4 130 260 5 44.2 4S 130 260 5 60.3 5 130 270 5 49.8 5S 130 270 5 63.8 6 130 240 20 44.8 In order to test the connection of the polyamide matrix to the carbon fibers, the material was subjected to a 90 ° tensile test according to SAC-MA 4-88. For this purpose, the 2 mm thick plate was cut into 25 mm x 210 mm specimens with a diamond saw, taking care to ensure that the reinforcing fibers were aligned exactly parallel to the 25 mm long side of the specimens was respected. The tensile strength is shown in the table. table example Viscosity [Pa · s] T [° C] Z [min] Tensile strength [MPa] 1 260 260 20th 48.4 2nd 260 260 5 April 27 3rd 130 260 20th 63.2 3S 130 260 20th 64.0 4th 130 260 5 44.2 4S 130 260 5 60.3 5 130 270 5 49.8 5S 130 270 5 63.8 6 130 240 20th 44.8

Die Beispiele 1 und 2 sind nicht erfindungsgemäß.Examples 1 and 2 are not according to the invention.

Claims (11)

  1. A covered hybrid yarn consisting of polyamide fibres A and reinforcement fibres B, in which the individual filaments of the two types of fibre are mixed, the covering consisting of a polyamide yarn A', characterised in that the polyamide A has a melting viscosity of less than 220 Pa·s (measured in accordance with DIN 54 811 at a shear rate of 100 s-1 and at a temperature which is 30°C above the melting point or the glass temperature of the polyamide).
  2. A hybrid yarn according to Claim 1, characterised in that the polyamide A is a polyamide-6 having a melt viscosity of less than 180 Pa·s.
  3. A hybrid yarn according to Claim 1, characterised in that the polyamide A is a polyamide-6,6 having a melt viscosity of less than 180 Pa·s.
  4. A hybrid yarn according to Claim 1, characterised in that polyamide A and polyamide A' are identical polymers.
  5. A hybrid yarn according to Claim 1, characterised in that the reinforcement fibres B are carbon fibres.
  6. A hybrid yarn according to Claim 1, characterised in that the reinforcement fibres B are glass fibres.
  7. A hybrid yarn according to one of Claims 1 to 6, characterised in that it contains 26 to 80% by weight polyamide fibres A, 20 to 75% by weight reinforcement fibres B and 0.2 to 3% by weight covering yarn A'.
  8. A laid fabric, package, woven fabric, knitted fabric or mesh fabric, produced from the hybrid yarn according to Claim 1.
  9. A laid fabric, package, woven fabric, knitted fabric or mesh fabric according to Claim 8, characterised by a size applied after the production thereof from the hybrid yarn.
  10. A composite material, produced from a laid fabric, package, woven fabric, knitted fabric or mesh fabric according to Claim 8 by consolidation.
  11. A composite material according to Claim 10 in the form of a sports article, in particular a tennis racquet frame.
EP92118673A 1991-11-14 1992-10-31 Hybrid yarn made of polyamide fibres and reinforcing fibres Expired - Lifetime EP0542070B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4137406 1991-11-14
DE19914137406 DE4137406A1 (en) 1991-11-14 1991-11-14 HYBRID YARN MADE OF POLYAMIDE FIBERS AND REINFORCING FIBERS
US07/970,455 US5464684A (en) 1991-11-14 1992-11-02 Hybrid yarn comprising a core of intermixed polyamide filaments and reinforcing rilaments wherein the core is wrapped by a polyamide fiber

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EP0542070A1 EP0542070A1 (en) 1993-05-19
EP0542070B1 true EP0542070B1 (en) 1996-07-10

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EP (1) EP0542070B1 (en)
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DE4137406A1 (en) 1993-05-19
EP0542070A1 (en) 1993-05-19
US5464684A (en) 1995-11-07

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