EP0542070B1 - Fil hybride de fibres en polyamide et de fibres de renforcement - Google Patents

Fil hybride de fibres en polyamide et de fibres de renforcement 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)
English (en)
Other versions
EP0542070A1 (fr
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cytec Technology Corp filed Critical Cytec Technology Corp
Publication of EP0542070A1 publication Critical patent/EP0542070A1/fr
Application granted granted Critical
Publication of EP0542070B1 publication Critical patent/EP0542070B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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)

Claims (11)

  1. Fil hybride enveloppé constitué par des fibres de polyamide A et des fibres de renfort B et dans lequel les filaments individuels des deux types de fibres sont mélangés, l'enveloppement étant constitué par un fil de polyamide A', caractérisé en ce que le polyamide A possède une viscosité à l'état fondu inférieure à 220 Pa.s (mesurée selon DIN 54 811 pour une vitesse de cisaillement de 100 s-1 et à une température qui est supérieure de 30°c au point de fusion ou à la température de transition vitreuse du polyamide).
  2. Fil hybride selon la revendication 1, caractérisé en ce que le polyamide A est un polyamide-6 possédant une viscosité à l'état fondu inférieure à 180 Pa.s.
  3. Fil hybride selon la revendication 1, caractérisé en ce que le polyamide A est un polyamide-6,6 possédant une viscosité à l'état fondu inférieure à 180 Pa.s.
  4. Fil hybride selon la revendication 1, caractérisé en ce que le polyamide A et le polyamide A' sont des polymères identiques.
  5. Fil hybride selon la revendication 1, caractérisé en ce que les fibres de renfort B sont des fibres de carbone.
  6. Fil hybride selon la revendication 1, caractérisé en ce que les fibres de renfort B sont des fibres de verre.
  7. Fil hybride selon l'une des revendications 1 à 6, caractérisé en ce qu'il contient 26 à 80 % en poids de fibres de polyamide A, 20 à 75 % en poids de fibres de renfort B et 0,2 à 3 % en poids d'un fil d'enveloppement A'.
  8. Etoffe, bobine, tissu, tricot ou tresse réalisé avec un fil hybride selon la revendication 1.
  9. Etoffe, bobine, tissu, tricot ou tresse selon la revendication 8, caractérisé par une colle d'encollage appliquée après sa fabrication à partir d'un fil hybride.
  10. Matériau composite, formé d'une étoffe, d'une bobine, d'un tissu, d'un tricot ou d'une tresse selon la revendication 8, par consolidation.
  11. Matériau composite selon la revendication 10 sous la forme d'un article de sport, notamment d'un cadre de raquette de tennis.
EP92118673A 1991-11-14 1992-10-31 Fil hybride de fibres en polyamide et de fibres de renforcement Expired - Lifetime EP0542070B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914137406 DE4137406A1 (de) 1991-11-14 1991-11-14 Hybridgarn aus polyamidfasern und verstaerkungsfasern
DE4137406 1991-11-14
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

Publications (2)

Publication Number Publication Date
EP0542070A1 EP0542070A1 (fr) 1993-05-19
EP0542070B1 true EP0542070B1 (fr) 1996-07-10

Family

ID=25909115

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92118673A Expired - Lifetime EP0542070B1 (fr) 1991-11-14 1992-10-31 Fil hybride de fibres en polyamide et de fibres de renforcement

Country Status (4)

Country Link
US (1) US5464684A (fr)
EP (1) EP0542070B1 (fr)
JP (1) JPH05247761A (fr)
DE (1) DE4137406A1 (fr)

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DE4412376C3 (de) * 1994-04-13 1999-09-09 Buck Halbzeug
US5756206A (en) * 1995-03-15 1998-05-26 Custom Composite Materials, Inc. Flexible low bulk pre-impregnated tow
EP0758693B1 (fr) 1995-08-11 2001-10-24 BUCK, Alfred Demi-produit pour matériau composite
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DE19613965A1 (de) * 1996-04-09 1997-10-16 Hoechst Trevira Gmbh & Co Kg Schrumpfarme Hybridgarne, Verfahren zu deren Herstellung und deren Verwendung
US6531218B2 (en) 1996-09-16 2003-03-11 Basf Corporation Dyed sheath/core fibers and methods of making same
US20010007706A1 (en) * 1996-09-16 2001-07-12 Matthew B. Hoyt Colored fibers having resistance to ozone fading
EP1085968B1 (fr) * 1998-06-08 2003-05-14 Complastik Corporation Articles composites comprenant des preimpregnes, des preformes, des lamines et des produits moules sandwich, et leur procede de fabrication
US6117548A (en) * 1998-12-18 2000-09-12 Glen Raven Mills, Inc. Self-coating composite stabilizing yarn
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AU2002241584A1 (en) 2000-12-06 2002-06-18 Complastik Corporation Hybrid composite articles and methods for their production
JP2003055850A (ja) * 2001-08-10 2003-02-26 Fukushima Prefecture 複合糸および繊維強化プラスチック
EP1594341B1 (fr) * 2004-05-06 2008-01-23 Harman/Becker Automotive Systems GmbH Membrane de haut-parleur
US7185481B2 (en) * 2005-02-15 2007-03-06 Banom, Inc. Cut resistant yarns for glove and sleeves, gloves and sleeves made with such yarns and methods of making such cut resistant yarns
DE502005006007D1 (de) * 2005-07-15 2009-01-02 Teijin Aramid Bv Cord
DE102007028373B4 (de) * 2007-06-11 2012-12-20 Technische Universität Dresden Faserverbundwerkstoff und Verfahren zur Herstellung von Faserverbundwerkstoffen
CN101707929B (zh) * 2007-06-20 2017-01-18 罗地亚管理公司 复合聚酰胺制品
GB2477531B (en) * 2010-02-05 2015-02-18 Univ Leeds Carbon fibre yarn and method for the production thereof
DE102010028433A1 (de) * 2010-04-30 2011-11-03 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Hybridgarn zur Herstellung von Formteilen
JP2014173196A (ja) * 2013-03-06 2014-09-22 Gifu Univ 混繊糸、織物および編み物、複合材料、並びに、複合材料の製造方法
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US20150137409A1 (en) * 2013-11-21 2015-05-21 Hsien-Hsiao Hsieh Method For Forming Textile Article
EP3332055A2 (fr) 2015-08-03 2018-06-13 Kordsa Teknik Tekstil Anonim Sirketi Procédé de fabrication de préimprégné thermoplastique
TR201809192T1 (tr) 2015-12-31 2018-07-23 Kordsa Teknik Tekstil As Termoplasti̇k prepreg üreti̇m yöntemi̇
DE102020105167A1 (de) 2020-02-27 2021-09-02 Thüringisches Institut für Textil- und Kunststoff-Forschung e. V. Rudolstadt Verfahren zur Herstellung eines Hybridgarnes
JP7354037B2 (ja) 2020-03-23 2023-10-02 株式会社日立ハイテクサイエンス 集束イオンビーム加工装置
DE102021120429A1 (de) * 2021-08-05 2023-02-09 Universität Stuttgart, Körperschaft Des Öffentlichen Rechts Transparente Faser-Matrix-Komposite und Verfahren zur deren Herstellung
BE1030711B1 (nl) * 2022-07-12 2024-02-12 Sioen Ind Composietprofiel en gemengd garen voor het vervaardigen van composietprofielen

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Also Published As

Publication number Publication date
DE4137406A1 (de) 1993-05-19
US5464684A (en) 1995-11-07
JPH05247761A (ja) 1993-09-24
EP0542070A1 (fr) 1993-05-19

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