EP0801159B1 - Fils hybrides à faible retrait, méthode pour sa fabrication et son utilisation - Google Patents

Fils hybrides à faible retrait, méthode pour sa fabrication et son utilisation Download PDF

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Publication number
EP0801159B1
EP0801159B1 EP97105367A EP97105367A EP0801159B1 EP 0801159 B1 EP0801159 B1 EP 0801159B1 EP 97105367 A EP97105367 A EP 97105367A EP 97105367 A EP97105367 A EP 97105367A EP 0801159 B1 EP0801159 B1 EP 0801159B1
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EP
European Patent Office
Prior art keywords
hybrid
yarns
filaments
matrix
shrinkage
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
EP97105367A
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German (de)
English (en)
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EP0801159A3 (fr
EP0801159A2 (fr
Inventor
Josef Geirhos
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INVISTA TECHNOLOGIES Sarl
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Arteva Technologies SARL
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Publication of EP0801159A2 publication Critical patent/EP0801159A2/fr
Publication of EP0801159A3 publication Critical patent/EP0801159A3/fr
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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
    • 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
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/16—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics using jets or streams of turbulent gases, e.g. air, steam
    • 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
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/447—Yarns or threads for specific use in general industrial applications, e.g. as filters or reinforcement
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
    • D02J13/001—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass in a tube or vessel
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/06—Glass
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/08—Ceramic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/14—Carbides; Nitrides; Silicides; Borides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/14—Carbides; Nitrides; Silicides; Borides
    • D10B2101/16—Silicon carbide
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/20—Metallic fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/06—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyethers
    • D10B2331/061—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyethers polyetherketones, polyetheretherketones, e.g. PEEK
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/14—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S57/00—Textiles: spinning, twisting, and twining
    • Y10S57/908—Jet interlaced or intermingled
    • 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.]
    • 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
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2925—Helical or coiled
    • 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
    • Y10T428/2973—Particular cross section
    • Y10T428/2976—Longitudinally varying

Definitions

  • the present invention relates to new hybrid yarns, which are characterized by a special low thermal shrinkage.
  • Such yarns can be advantageously to composite materials or to textile fabrics, such as Process occasionally.
  • Hybrid games i.e. yarns made of reinforcement and matrix filaments, are in themselves known. Such yarns are used, for example, as preliminary products for production of composite materials. This is usually done with a textile Fabric made from the hybrid game; the matrix filaments of this Hybrid games are then created by melting or melting into a matrix transferred, which embeds or flows around the reinforcing filaments and builds the network together with them.
  • the matrix filaments are generally not subject to high requirements in terms of strength and other mechanical properties, as these are melted anyway in later processing steps. It is therefore no longer necessary an elaborate aftertreatment in the production of such filaments spinning, like stretching or fixing. Show matrix filaments therefore inherently a significant thermal shrinkage, which is in the later processing steps can adversely affect the product.
  • Such yarns are so-called two-component loop yarns with high strength and low shrinkage.
  • Such yarns were especially for the Developed for use as sewing thread and for example in EP-B-363,798 described.
  • such yarns usually do not have any Matrix filaments from deep-melting filaments, but are made Filaments of one type but different strengths, in a core-sheath structure are arranged, built.
  • the yarns according to the invention are characterized by a relatively large size Temperature interval from very low thermal shrinkage.
  • the present invention relates to containing low-shrinkage hybrid yarns Reinforcing filaments and matrix filaments made of thermoplastic polymers, the a lower melting point than the melting or decomposition point of the Have reinforcing filaments, and are characterized in that the thermal shrink, at a load of 0.0004 cN / dtex and an air temperature of 160 ° C of less than 2% and at an air temperature of 200 ° C of less than or equal to 5%, in particular less than or equal to Is 3%, and that the static shrinkage force at Temperatures of up to 200 ° C up to 0.01cN / dtex.
  • the mechanical properties of the hybrid yarns according to the invention are shown in Dependence of the composition, such as type and proportion of the reinforcing filaments or the matrix filaments depending on the physical structure of the yarn, such as. Degree of turbulence, can be varied within wide limits. Usually is the proportion of the matrix filaments 5 to 60% by weight, preferably 10 to 50% by weight, based on the weight of the hybrid yarn.
  • hybrid yarn is at its broadest within the scope of this description Understand meaning. Every combination is therefore included Reinforcement filaments and to understand the matrix filaments defined above.
  • Hybrid yarn types are filament yarns made of different Types of filaments that are intermingled or by another Technology, such as twisting, are combined. All these Hybrid games are characterized by the presence of two or more types of Filaments characterized, with at least one filament type Reinforcing filament and at least one filament type is a matrix filament in the sense of the definitions given above.
  • Intermingling or commingling techniques are particularly preferred manufactured hybrid yarns; it can be a loop game act, but preferably smooth yarns.
  • the flat yarns according to the invention are distinguished by a particularly good one Processability with area-forming technologies and good fabric samples out.
  • the subject shrinkage is a burden of 0.0004 CN / dtex and a temperature of 160 ° C less than or equal to 2%, in particular less than or equal to 1%.
  • the number of swirling points in the hybrid games according to the invention leaves can be set in a wide range by the choice of the swirling conditions.
  • Preferred hybrid yarns have a intermingling distance of less than 60 mm, preferably less than 30 mm; this value refers to a Measurement with the Rothschild Entanglement Tester 2050 needle tester.
  • the matrix filaments of the hybrid yarns according to the invention consist of thermoplastic polymers. These preferably have a melting point, which is at least 30 ° C below the melting or destruction point of each reinforcement filament used.
  • Reinforcing filaments can be a variety of filaments Trade materials. In addition to organic polymers, inorganic Materials are used. Reinforcement filaments in the sense of this Description mean filaments which are in the desired textile Flat structures or composite material take on a reinforcing function. In a first preferred embodiment, the reinforcement filaments are made of Single filaments built that have an initial module of more than 50 GPa exhibit.
  • Preferred reinforcing filaments of this type are made of glass; Carbon; Metals or metal alloys, such as steel, aluminum or tungsten; Non-metals, like boron; Metal, semi-metal or non-metal oxides, carbides or nitrides, such as Aluminum oxide, zirconium oxide, boron nitride, boron carbide, silicon carbide, silicon dioxide (Quartz); Ceramics, or high-performance polymers (i.e.
  • Fibers that have no or only low stretch a very high initial modulus and a very high one Tensile strength such as liquid crystalline polyester (LCP), poly (bisbenzimidazo-benzophenanthrolines (BBB), poly (amide imides) (PAI), Polybenzimidazoles (PBI), poly (p-phenylene benzobisoxazoles (PBO), poly (p-phenylene benzobistiazoles) (PBT), polyether ketones (PEK, PEEK, PEEKK), Polyetherimides (PEI), polyether sulfones (PESU), polyimides (PI), poly- (p-phenylenes) (PPP), polyarylene sulfides (PPS), polysulfones (PSU), polyolefins, such as polyethylene (PE) or polypropylene (PP), and aramids (HMA), such as poly- (m-phenylene-isophthalamide), Poly (m-phenylene terephthalamide), poly (p-phen
  • reinforcement and Matrix filaments used which are made of polymeric materials from a Polymer class, for example from polyolefins, from polyamides or preferably consist of polyesters.
  • the single filaments of the reinforcing filaments have an initial modulus of more than 10 GPa.
  • Reinforcement filaments for this Embodiments are preferably high-strength and low-shrinkage Polyester filament yarns, in particular with a yarn count of less than or equal to 1100 dtex, a tenacity greater than or equal to 55 cN / tex, one Maximum tensile strength expansion of greater than or equal to 12% and a hot air shrinkage (measured at 200 ° C) of less than or equal to 9%.
  • the measurement of the maximum tensile force and the maximum tensile force elongation used upcoming polyester game is based on DIN 53 830, part 1.
  • Matrix filaments in the hybrid games according to the invention consist of or contain thermoplastic polymers. It can be any melt-spinnable thermoplastics act as long as the manufactured therefrom Melt filaments at a temperature that is lower than the melting or Decomposition temperature of the reinforcing filaments used in the respective case.
  • Matrix filaments made from polybutylene terephthalate and / or from are preferred Polyethylene terephthalate and / or from chemically modified Polyethylene terephthalate.
  • Matrix filaments made from a thermoplastic are very particularly preferred modified polyester, especially a modified polyethylene terephthalate used; the modification lowers the melting point in the Comparison with the filament made of unmodified polyester.
  • modified polyesters of this type contain the recurring structural units of the formulas I and II -O-OC-Ar 1 -CO-OR 1 - -O-OC-R 2 -CO-OR 3 - wherein Ar 1 represents a divalent mononuclear or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position with respect to one another, preferably 1,4-phenylene and / or 2,6-naphthylene , R 1 and R 3 independently of one another represent divalent aliphatic or cycloaliphatic radicals, in particular radicals of the formula -C n H 2n -, in which n is an integer between 2 and 10, in particular ethylene, or a radical derived from cyclohexanedimethanol, and R 2 represents a divalent aliphatic, cycloaliphatic or mononuclear or polynuclear aromatic radical, the free valences of which are in the meta position
  • Very particularly preferred modified polyesters of this type contain 40 to 95 mol% of the repeating structural units of the formula I and 60 to 5 mol% of the repeating structural units of the formula II, in which Ar 1 is 1,4-phenylene and / or 2,6-naphthylene, R 1 and R 3 are ethylene and R 2 is 1,3-phenylene.
  • matrix filaments are used Use that consist of a thermoplastic and elastomeric polymer or contain this. It can also be any melt-spinnable and elastomeric thermoplastics act as long as the filaments made from them melt at a temperature that is lower than the melting or Decomposition temperature of the reinforcing filaments used in the respective case.
  • a "elastomeric polymer” means a polymer understand whose glass transition temperature is less than 0 ° C, preferably is less than 23 ° C.
  • thermoplastic and elastomeric polymers are elastomeric polyamides, polyolefins, polyesters and polyurethanes. Such polymers are known per se.
  • any radicals mean divalent aliphatic radicals, including branched and in particular straight-chain
  • alkylene for example alkylene with two to twenty, preferably with two to ten carbon atoms.
  • examples of such radicals are ethane-1,2-diyl, Propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl or octane-1,8-diyl.
  • radicals in the structural formulas defined above mean divalent cycloaliphatic radicals, they are to be understood as meaning groups which contain carbocyclic radicals having five to eight, preferably six, ring carbon atoms. Examples of such radicals are cyclohexane-1,4-diyl or the group -CH 2 -C 6 H 10 -CH 2 -.
  • any radicals mean divalent aromatic residues, these are single- or multi-core aromatic Hydrocarbon radicals or heterocyclic-aromatic radicals, the one or can be multi-core. Show in the case of heterocyclic aromatic radicals these in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic core.
  • Polynuclear aromatic radicals can be condensed with one another or via C-C bonds or via bridge groups, such as -O-, -S-, -CO- or -CO-NH- groups be connected.
  • the valence bonds of the divalent aromatic radicals can be in para or are in a comparable coaxial or parallel position to each other, or also in a meta or comparable angular position to each other.
  • valence bonds that are in coaxial or parallel position stand are directed in opposite directions.
  • An example of coaxial, opposite directional bonds are the biphen-4,4'-diyl bonds.
  • An example of parallel, oppositely directed bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene-1,8 bonds are rectified in parallel.
  • Examples of preferred divalent aromatic radicals, their valence bonds in a para- or comparable coaxial or parallel position to each other are mononuclear aromatic radicals with free para to each other Valences, especially 1,4-phenylene or dinuclear fused aromatic Residues with parallel, oppositely directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear linked via a C-C bond aromatic residues with coaxial, oppositely directed bonds, especially 4,4'-biphenylene.
  • Examples of preferred divalent aromatic radicals are in a meta or comparable angular position to each other mononuclear aromatic residues with meta-constant free valences, in particular 1,3-phenylene or dinuclear condensed aromatic radicals bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a C-C bond with angled bonds, in particular 3,4'-biphenyls.
  • substituents are alkyl, alkoxy or halogen.
  • Alkyl radicals include branched and in particular straight-chain alkyl understand, for example alkyl with one to six carbon atoms, in particular Methyl.
  • Alkoxy radicals include branched and in particular straight-chain alkoxy understand, for example alkoxy with one to six carbon atoms, especially methoxy.
  • radicals are halogen, these are, for example Fluorine, bromine or especially chlorine.
  • the matrix filaments used in the hybrid yarn according to the invention can be made from thermoplastic polymers, which are usually intrinsic Have viscosity of at least 0.5 dl / g, preferably 0.6 to 1.5 dl / g.
  • the intrinsic viscosity is measured in a solution of the thermoplastic Polymers in dichloroacetic acid at 25 ° C.
  • these polyesters usually have an intrinsic Viscosity of at least 0.5 dl / g, preferably 0.6 to 1.5 dl / g.
  • the measurement the intrinsic viscosity is as described above.
  • the hybrid yarns according to the invention usually have a yarn count of 6000 to 150 dtex, preferably from 4500 to 150 dtex.
  • the single fiber titer of the reinforcing filaments and the matrix filaments moves usually in the range of 2 to 10 dtex, preferably 4 to 8 dtex.
  • the cross sections of the reinforcing filaments and the matrix filaments can be arbitrary; for example elliptical, bi- or multilobal, ribbon-shaped or preferably round.
  • thermoplastic polymers are produced according to known methods Process by polycondensation of the corresponding bifunctional Monomer components.
  • polyesters usually come Dicarboxylic acids or dicarboxylic acid esters and the corresponding Diol components for use.
  • Such thermoplastic and optionally elastomeric polyesters, polyurethanes, polyamides and polyolefins are already known.
  • the blowing is carried out by means of a fluid in a swirl nozzle, e.g. Water or in particular by a gas which is inert to the roving strands, in particular by air that may be humidified.
  • a fluid in a swirl nozzle e.g. Water or in particular by a gas which is inert to the roving strands, in particular by air that may be humidified.
  • the filament material of the blowing nozzle is also involved in the blowing fed at greater speed than withdrawn from it.
  • the Excess speed of the feed compared to the deduction, expressed in Percentages based on the take-off speed are called the Overfeed.
  • the blow-blowing process known per se is used modified in such a way that before shrinking the shrinkable Matrix filaments in the intermingling nozzle partially or completely shrink is triggered by heating.
  • the advance of this roving component before The heating step must therefore be chosen larger in the process than without one such heating step.
  • the selected advance when entering the Swirl nozzle and the selected swirl conditions can be Loop hybrid yarns or, in particular, hybrid plain yarns are obtained.
  • Conventional swirl nozzles can be used for swirling.
  • the intermingling distance or the intermingling density is primarily determined by the pressure of the swirling medium and the selected nozzle type certainly.
  • a suitable swirl pressure can be selected for a specific nozzle type.
  • the working pressure is expediently in the range from 1 to 8 bar, preferably from 1.5 to 6 bar, in particular from 1.5 to 3 bar.
  • the triggering of the shrinkage of the matrix roving before entering the Swirling nozzle can be done according to methods known per se. For example by heating with godets, by contact with a heating rail or a heating pin, without contact by passing through a heating device, for example by a device as described in EP-A-579,092 or through a steam stuffer box process.
  • High-strength multifilament yarns can either already be used as reinforcement can be presented to the interlacing device or the multifilament yarns can stretched immediately before entering the swirl nozzle and if necessary be fixed.
  • Reinforcement rovings are preferably used which have a maximum tensile force, based on the final titer, of at least 60 cN / tex.
  • Further preferred reinforcement programs have a maximum tensile strength extension of 0.5 to 25%.
  • the mechanical properties of the matrix examples are not very high Requirements. These at least have the swirling step survive.
  • the primary hybrid yarn After leaving the intermingling nozzle, the primary hybrid yarn subtracted, whereby usually only a low voltage may occur.
  • the primary hybrid yarn train a small or high proportion of loops.
  • the primary yarn can have a low or high proportion of loops are heated with shrinkage approval. The loops pull together and the yarn structure is largely smoothed.
  • already in the Swirl nozzles created smooth games are usually pulled off directly and spooled.
  • the swirling of the hybrid game from reinforcement and matrix filaments of the above described first embodiment is preferably carried out by means of a special warm swirling process, which is described in EP-B-0,455,193.
  • the heating can be by godets and / or Heating tube done while the low melting thermoplastic Single filaments of polyester are also preheated to shrink trigger, and are fed to the higher swirl nozzle.
  • the resulting smooth, high thread closure hybrid games are easy to use on the web.
  • the hybrid games according to the invention can be according to methods known per se textile fabrics are processed. Examples include tissues, Knitted fabrics, knitted fabrics and, in particular, scrims. Such textile fabrics can by melting the matrix component in composite materials be transferred or stabilized.
  • the invention also relates to the use of the hybrid yarns for these purposes.
  • the reinforcement roving was made by a delivery plant consisting of three godets fed directly to a swirl nozzle. In some trials, between the Delivery gods interposed a heater. It was a device for the contactless heating of running threads, as they in EP-A-569,082.
  • the matrix program was made up of a delivery plant consisting of two godets and an intermediate heating device also the texturing nozzle fed. Instead of or in addition to the intermediate heating device the delivery godets were heated.
  • the heater was one Device for the contactless heating of running threads, as in the EP-A-579,092.
  • the temperatures of the godets of the delivery plants were between 80 and 130 ° C.
  • the primary hybrid yarn was subtracted another godet, the surface speed of the Galette was adjusted so that the yarn structure on the textile Performance characteristics has been optimized. Details on how to run the Procedures can be found in the table below.
  • the properties of the hybrid yarns obtained are shown in a further Table 2. Manufacturing conditions of the hybrid yarns Example No. Reinforcement roving (type; titer dtex) Matrix roving (type; titer dtex) tradition Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Reinforced.
  • Example 1 Analogously to Example 1, hybrid games were produced by swirling. High-strength PET multifilament yarns with a titre of 1100 dtex were used as reinforcement and filament yarns with a titre of 280 dtex based on isophthalic acid-modified PET as matrix rovings. Details of the manufacturing conditions are listed in Table 3. The properties of the yarns obtained are shown in Table 4. Manufacturing conditions of the hybrid yarns Example No. tradition Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Reinforced.
  • Example 1 Analogously to Example 1, hybrid games were produced by swirling. Glass multifilament yarns of 3000 dtex titre were used as reinforcement rovings and filament yarns of 750 dtex titre based on isophthalic acid-modified PET were used as matrix roving yarns. Details of the manufacturing conditions are listed in Table 5. The properties of the yarns obtained are shown in Table 6. Manufacturing conditions of the hybrid yarns Example No. tradition Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Reinforced.
  • a low-shrinkage hybrid yarn with reinforcing yarn made of PET and with matrix yarn made of isophthalic acid-modified PET was produced.
  • the yarn titer was 1380 dtex.
  • This game was loaded with different preload weights and treated for 15 minutes in a forced air oven at an air temperature of 100 ° C or 160 ° C.
  • the following thermal shrinkage values were measured: Preload weight (cN) 0.16 0.5 0.8 1.5 3 Thermal shrink at 100 ° C 33.5 2.3 1 0.5 0.5 Thermal shrink at 160 ° C 0.4 0.3 0.3 0.2 0.1
  • low-shrinkage hybrid yarns were made from reinforcing pregam from PET and from matrix roving from different isophthalic acid-modified PET types.
  • the manufacturing conditions were the same in each case.
  • the matrix programs differed in the melting range of the PET type.
  • the proportion of the matrix component in the hybrid games was 15 to 20% by volume.
  • the delivery of the matrix roving was between 50 and 100%.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)
  • Artificial Filaments (AREA)

Claims (16)

  1. Fils hybrides contenant des filaments de renfort et des filaments de matrice constitués de polymères thermoplastiques présentant un point de fusion inférieur à celui des filaments de renfort, caractérisés en ce que le retrait thermique sous une contrainte de 0,0004 cN/dtex est inférieur ou égal à 2 % à une température de l'air de 160° C, et inférieur ou égal à 5 %, en particulier inférieure ou égale à 3 %, à une température de l'air de 200° C, et en ce que la force de retrait statique à des températures jusqu'à 200° C atteint 0,01 cN/dtex.
  2. Fils hybrides selon la revendication 1, caractérisés en ce que le retrait thermique sous une contrainte de 0,0004 cN/dtex et à une température de 160° C est inférieur ou égal à 1 %.
  3. Fils hybrides selon la revendication 1, caractérisés en ce qu'ils présentent une distance d'enchevêtrement inférieure à 60 mm, de préférence inférieure à 30 mm, cette valeur se rapportant à une mesure effectuée avec un instrument d'essai à aiguille Rothschild Entanglement 2050.
  4. Fils hybrides selon la revendication 1, caractérisés en ce qu'il s'agit de fils lisses.
  5. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de matrice constitués de polymères thermoplastiques présentent un point de fusion qui se situe au moins 30° C au-dessous du point de fusion ou du point de décomposition des filaments de renfort.
  6. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de renfort présentent un module initial supérieur à 50 GPa, et sont de préférence constitués de verre, de carbone ou de polyamide aromatique.
  7. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de renfort présentent un module initial supérieur à 10 GPa, et sont constitués de polyester, en particulier de polyéthylène téréphtalate.
  8. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de matrice sont constitués de polybutylène téréphtalate et/ou de polyéthylène téréphtalate et/ou de polyéthylène téréphtalate modifié chimiquement.
  9. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de renfort et les filaments de matrice sont constitués d'une classe de polymères, de préférence d'une combinaison polyamide/polyamide, polyoléfine/polyoléfine, ou en particulier polyester/polyester.
  10. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de matrice sont en polyéthylène téréphtalate modifié chimiquement contenant les unités structurales récurrentes des formules I et II O-OC-Ar1-CO-O-R1- O-OC-R2-CO-O-R3    dans lesquelles Ar1 représente un résidu aromatique bivalent à un ou plusieurs noyaux, dont les valences libres se trouvent l'une par rapport à l'autre en position para ou dans une position coaxiale ou parallèle comparable à cette position, et représente de préférence du 1,4-phénylène et/ou du 2,6-naphthylène, R1 et R3 représentent indépendamment l'un de l'autre des résidus aliphatiques ou cycloaliphatiques bivalents, en particulier résidus de la formule -CnH2n-, dans laquelle n est un nombre entier entre 2 et 10, et représentent en particulier de l'éthylène ou un résidu dérivé du cyclohexanediméthanol, et R2 représente un résidu aromatique bivalent aliphatique, cycloaliphatique ou à un ou plusieurs noyaux, dont les valences libres se trouvent l'un par rapport à l'autre en position meta ou dans une position coudée comparable à cette position, et représente du préférence du 1,3-phénylène.
  11. Fils hybrides selon la revendication 10, caractérisés en ce les filaments de matrice sont constitués d'un polyéthylène téréphtalate modifié chimiquement, qui contient 40 à 95 % en poids moléculaire des unités structurales récurrentes de la formule I et 60 à 5 % en poids moléculaire des unités structurales récurrentes de la formule II, dans lesquelles Ar1 est 1,4-phénylène et/ou 2,6-naphtalène, R1 et R3 correspondent à éthylène, et R2 est 1,3-phénylène.
  12. Fils hybrides selon la revendication 1, caractérisés en ce que les filaments de matrice sont constitués d'un polymère thermoplastique et élastomère, en particulier d'un polyuréthane, d'un polyamide ou de préférence d'un polyester.
  13. Procédé de fabrication des fils hybrides à faible retrait selon la revendication 1, comprenant les mesures qui consistent à
    a) Amener deux ou plus de deux écheveaux de mèche se déplaçant à des vitesses différentes à une buse d'enchevêtrement, au moins une partie des écheveaux de mèche (mèche de renfort) étant constituée de filaments de renfort, et une autre partie des écheveaux de mèche (mèche de matrice) étant constituée de filaments de matrice à bas point de fusion constitués de polymères thermoplastiques, qui présentent un retrait thermique à 200° C supérieur à 20 %,
    b) chauffer la mèche de matrice pendant le passage dans la buse d'enchevêtrement à une température telle qu'au moins une partie du retrait est déclenché,
    c) enchevêtrer les écheveaux de mèche dans la buse d'enchevêtrement dans des conditions telles que se forme un fil hybride primaire, et
    d) étirer le fils hybride primaire obtenu, le cas échéant avec retrait et/ou chauffage supplémentaire.
  14. Procédé selon la revendication 13, caractérisé en ce que les différences d'avance des mèches passant dans la buse d'enchevêtrement sont choisies de façon à ce qu'un fil hybride lisse se forme lors de l'enchevêtrement.
  15. Procédé selon la revendication 13, caractérisé en ce que les différences d'avance des mèches passant dans la buse d'enchevêtrement sont choisies de façon à ce que se forme lors de l'enchevêtrement un fil hybride bouclé dont les boucles sont à nouveau sensiblement lissées par le déclenchement du retrait en une ou plusieurs étapes successives de chauffage.
  16. Utilisation des fils hybrides à faible retrait thermique selon la revendication 1 pour la fabrication de matières composites ou de produits textiles plats, en particulier pour la fabrication de non-tissés.
EP97105367A 1996-04-09 1997-04-01 Fils hybrides à faible retrait, méthode pour sa fabrication et son utilisation Expired - Lifetime EP0801159B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19613965A DE19613965A1 (de) 1996-04-09 1996-04-09 Schrumpfarme Hybridgarne, Verfahren zu deren Herstellung und deren Verwendung
DE19613965 1996-04-09

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EP0801159A2 EP0801159A2 (fr) 1997-10-15
EP0801159A3 EP0801159A3 (fr) 1998-09-16
EP0801159B1 true EP0801159B1 (fr) 2003-09-03

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US (2) US5879800A (fr)
EP (1) EP0801159B1 (fr)
JP (1) JPH1096133A (fr)
KR (1) KR970070267A (fr)
CN (1) CN1165211A (fr)
DE (2) DE19613965A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001293379A1 (en) * 2000-04-14 2001-10-30 Ihc Rehabilitation Products Method of forming a composite part with complex carbon fiber architecture by resistive heating
US7119036B2 (en) * 2001-02-09 2006-10-10 E. I. Du Pont De Nemours And Company Protective apparel fabric and garment
US6365556B1 (en) * 2001-02-22 2002-04-02 New Hampshire Ball Bearings, Inc. Self-lubricating liner using poly (p-phenylene-2,6-benzobisoxazole) fiber
CN100422410C (zh) * 2001-05-05 2008-10-01 苏拉有限及两合公司 用于生产低收缩直丝纱的方法和设备
US6715191B2 (en) * 2001-06-28 2004-04-06 Owens Corning Fiberglass Technology, Inc. Co-texturization of glass fibers and thermoplastic fibers
US7413214B2 (en) * 2002-01-08 2008-08-19 Milliken & Company Airbag made from low tenacity yarns
WO2005090662A2 (fr) * 2004-03-18 2005-09-29 Diolen Industrial Fibers B.V. Procede de melange de fils continus
DE102005034394A1 (de) * 2005-07-22 2007-02-01 Airbus Deutschland Gmbh Fixierfaden zum Heften von Verstärkungsfasern
FR2928154B1 (fr) * 2008-03-03 2011-05-06 E Bourgeois Ets Bande transporteuse en fils de polysulfure de phenylene
US8474115B2 (en) 2009-08-28 2013-07-02 Ocv Intellectual Capital, Llc Apparatus and method for making low tangle texturized roving
JP5780968B2 (ja) * 2009-11-17 2015-09-16 倉敷紡績株式会社 繊維強化樹脂用紡績糸と中間体及びこれを用いた繊維強化樹脂成形体
JP6297311B2 (ja) * 2013-11-20 2018-03-20 旭化成株式会社 布帛
US10145040B2 (en) * 2014-12-12 2018-12-04 E I Du Pont De Nemours And Company Knit reinforcing fabric
KR101694611B1 (ko) * 2015-03-31 2017-01-09 주식회사 라지 텍스처링노즐을 구비한 섬유합사장치
CN107130329B (zh) * 2017-04-28 2019-03-29 东华大学 基于热熔丝粘接制备稳定结构拉胀复合纱的装置及方法
CN107227525A (zh) * 2017-08-14 2017-10-03 太仓市天茂化纤有限公司 一种高强度高模量舒适混纺纤维

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB153927A (en) * 1919-05-19 1920-11-19 Llewellyn Wynn Williams Improvements in or relating to railway signalling apparatus
US3423809A (en) * 1967-11-15 1969-01-28 Du Pont Process for forming differential shrinkage bulked yarn
IT1108000B (it) * 1977-11-08 1985-12-02 Barmag Barmer Maschf Procedimento per la produzione di un filato increspato da fibre aperte(open end)a multifilamenti
GB8310072D0 (en) * 1983-04-14 1983-05-18 Coats Ltd J & P Synthetic yarn
EP0327600A1 (fr) * 1987-08-26 1989-08-16 Heltra Incorporated Fil hybride
CA1323488C (fr) * 1988-07-13 1993-10-26 Edwina Ying Fil hybride irretrecissable
DE3834139A1 (de) * 1988-10-07 1990-04-19 Hoechst Ag Zweikomponenten-schlingennaehgarn und verfahren zu seiner herstellung
JPH03130427A (ja) * 1989-10-11 1991-06-04 Teijin Kakoshi Kk 改善されたドレープ風合を呈するポリエステル系混繊糸
DE4013946A1 (de) * 1990-04-30 1991-10-31 Hoechst Ag Verwirbeltes multifilamentgarn aus hochmodul-einzelfilamenten und verfahren zum herstellen eines solchen garnes
US5434123A (en) * 1990-09-13 1995-07-18 Ishihara Sangyo Kaisha, Ltd. Herbicidal composition comprising glyphosate and 1-(4,6-dimethoxypyrimidin-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl)urea
JPH05329172A (ja) * 1991-07-03 1993-12-14 Smith & Nephew Inc エラストマー物品
JP2652918B2 (ja) * 1991-09-26 1997-09-10 東レ株式会社 複合捲縮糸及び織物
DE4137406A1 (de) * 1991-11-14 1993-05-19 Basf Ag Hybridgarn aus polyamidfasern und verstaerkungsfasern
DE59309821D1 (de) * 1992-08-26 1999-11-11 Hoechst Ag Feintitrige Zweikomponenten-Schlingengarne hoher Festigkeit, Verfahren zu deren Herstellung und deren Verwendung als Nähgarne und Stickgarne
DE59505342D1 (de) * 1994-01-20 1999-04-22 Hoechst Ag Zweikomponenten-Schlingengarne, Verfahren zu deren Herstellung und deren Verwendung als Nähgarne und Stickgarne
ATE199946T1 (de) * 1994-12-16 2001-04-15 Hoechst Trevira Gmbh & Co Kg Hybridgarn und daraus hergestelltes schrumpffähiges und geschrumpftes, permanent verformbares textilmaterial, seine herstellung und verwendung
DE19506038A1 (de) * 1995-02-22 1996-08-29 Hoechst Trevira Gmbh & Co Kg Verformbare, hitzestabilisierbare textile Schlingenpolware
DE19513506A1 (de) * 1995-04-10 1996-10-17 Hoechst Ag Hybridgarn und daraus hergestelltes permanent verformbares Textilmaterial, seine Herstellung und Verwendung
DE19537702A1 (de) * 1995-10-11 1997-04-17 Hoechst Trevira Gmbh & Co Kg Gewebe und Gelege mit einstellbarer Gas- und/oder Flüssigkeitsdichtigkeit enthaltend Hybridgarne, Verfahren zu deren Weiterverarbeitung, textile Flächengebilde mit vorbestimmter Gas- und/durch Flüssigkeitsdurchlässigkeit und deren Verwendung

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EP0801159A3 (fr) 1998-09-16
DE59710673D1 (de) 2003-10-09
CN1165211A (zh) 1997-11-19
US6109016A (en) 2000-08-29
JPH1096133A (ja) 1998-04-14
EP0801159A2 (fr) 1997-10-15
KR970070267A (ko) 1997-11-07
US5879800A (en) 1999-03-09
DE19613965A1 (de) 1997-10-16

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