EP0801159A2 - Low-shrinking hybrid yarns, method for its production and its use - Google Patents

Low-shrinking hybrid yarns, method for its production and its use Download PDF

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Publication number
EP0801159A2
EP0801159A2 EP97105367A EP97105367A EP0801159A2 EP 0801159 A2 EP0801159 A2 EP 0801159A2 EP 97105367 A EP97105367 A EP 97105367A EP 97105367 A EP97105367 A EP 97105367A EP 0801159 A2 EP0801159 A2 EP 0801159A2
Authority
EP
European Patent Office
Prior art keywords
hybrid
filaments
matrix
hybrid yarns
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.)
Granted
Application number
EP97105367A
Other languages
German (de)
French (fr)
Other versions
EP0801159A3 (en
EP0801159B1 (en
Inventor
Josef Geirhos
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.)
INVISTA TECHNOLOGIES Sarl
Original Assignee
Hoechst Trevira GmbH and Co KG
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Publication date
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Publication of EP0801159A2 publication Critical patent/EP0801159A2/en
Publication of EP0801159A3 publication Critical patent/EP0801159A3/en
Application granted granted Critical
Publication of EP0801159B1 publication Critical patent/EP0801159B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 distinguished by a particularly low thermal shrinkage.
  • Such yarns can advantageously be processed into composite materials or textile fabrics, such as scrims.
  • Hybrid yarns i.e. yarns made from reinforcement and matrix filaments, are known per se. Such yarns are used, for example, as intermediate products for the production of composite materials.
  • a textile fabric is usually first produced from the hybrid yarn; The matrix filaments of these hybrid yarns are then converted by melting or melting into a matrix which embeds or flows around the reinforcement filaments and, together with them, builds up the composite.
  • the matrix filaments are generally not subject to high requirements with regard to strength and other mechanical properties, since these are melted anyway in later processing steps. This eliminates the need for costly post-spinning treatment such as stretching or fixing in the manufacture of such filaments. Matrix filaments therefore inherently show considerable thermal shrinkage, which can adversely affect the product in the later processing steps.
  • so-called two-component loop yarns with high strength and low shrinkage are known. Such yarns were developed in particular for use as sewing threads and are described, for example, in EP-B-363,798. However, such yarns usually do not have matrix filaments made from deep-melting filaments, but are made up of filaments of one type but of different strengths, which are arranged in a core-sheath structure.
  • the yarns according to the invention are distinguished by a very low thermal shrinkage over a relatively large temperature interval.
  • the present invention relates to low-shrinkage hybrid yarns containing reinforcing filaments and matrix filaments made of thermoplastic polymers which have a lower melting point than the melting or decomposition point of the reinforcing filaments.
  • the hybrid yarns according to the invention are characterized in that they have a thermal shrinkage, measured on a yarn sample under a load of 0.0004 cN / dtex at an air temperature of 160 ° C, of less than or equal to 2%, in particular of less than or equal to 1%, and at Air temperature of 200 ° C of less than or equal to 5%, in particular less than or equal to 3%.
  • loops are formed at the two ends of six yarn samples, each 60 cm long, and these yarn samples are hooked onto their loops on a shrink rod. These yarn samples are each subjected to a preload force of 0.0004 cN / dtex.
  • the shrink bar with the Yarn samples are suspended in a forced air oven and then treated with hot air at a defined temperature for 15 minutes. The change in length of the yarn sample before and after heating in% represents the thermal shrinkage.
  • the mechanical properties of the hybrid yarns according to the invention are dependent on the composition, such as the type and proportion of the reinforcing filaments or the matrix filaments, depending on the physical structure of the yarns, e.g. Degree of turbulence, can be varied within wide limits.
  • the proportion of the matrix filaments is usually 5 to 60% by weight, preferably 10 to 50% by weight, based on the weight of the hybrid yarn.
  • hybrid yarn is to be understood in its broadest meaning within the scope of this description. Accordingly, this includes any combination containing reinforcing filaments and the matrix filaments defined above.
  • hybrid yarn types are filament yarns from different types of filaments which are interwoven with one another or combined with one another by means of another technology, such as for example twisting. All of these hybrid yarns are characterized by the presence of two or more types of filaments, at least one type of filament being a reinforcing filament and at least one type of filament being a matrix filament as defined above.
  • Hybrid yarns produced by intermingling or commingling techniques are particularly preferably used; it can be loop yarns, but preferably plain yarns.
  • the smooth yarns according to the invention are notable for particularly good processability with area-forming technologies and good fabric samples.
  • the hybrid yarns according to the invention preferably have a static shrinkage force, measured according to DIN 53866, part 12, at temperatures of up to 200 ° C. of up to 0.01 cN / dtex.
  • the number of intermingling points in the hybrid yarns according to the invention can be set within wide ranges by the selection of the intermingling 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 the reinforcing filament elements used in each case.
  • the reinforcing filaments used in the hybrid yarns according to the invention can be filaments made from a large number of materials. In addition to organic polymers, inorganic materials can also be used. Reinforcement filaments in the sense of this description mean filaments which assume a reinforcing function in the desired textile fabric or composite material.
  • the reinforcement filaments are constructed from individual filaments which have an initial modulus of more than 50 GPa.
  • Preferred reinforcing filaments of this type are made of glass; Carbon; Metals or metal alloys, such as steel, aluminum or tungsten; Non-metals such as boron; Metal, semimetal 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 provide a very high initial modulus and a very high tensile strength with little or no stretching
  • LCP liquid-crystalline polyesters
  • BBB poly (bis-benzimidazo-benzophenanthrolines
  • PAI polybenzimidazoles
  • PBO poly (p-phenylene benzobisoxazoles
  • PBT poly (p-phenylene benzobisthiazoles)
  • PES polyether ketones
  • PEI polyether sulfones
  • PESU Polyether sulfones
  • PESU polyimides
  • PI poly (p-phenylenes)
  • PPS polyarylene sulfides
  • PSU polyolefins
  • PE polyethylene
  • PP polypropylene
  • HMA aramids
  • Reinforcement filaments made of glass, carbon or aromatic polyamide are particularly preferred.
  • reinforcement and matrix filaments are used which consist of polymeric materials from one polymer class, for example polyolefins, polyamides or preferably polyesters.
  • the individual filaments of the reinforcement filaments have an initial modulus of more than 10 GPa.
  • Reinforcing filaments for this embodiment are preferably high-strength and low-shrinkage polyester filament yarns, in particular with a yarn titer of less than or equal to 1100 dtex, a tenacity of greater than or equal to 55 cN / tex, a maximum tensile strength elongation of greater than or equal to 12% and a hot air shrinkage (measured at 200 ° C.) of less equal to 9%.
  • the maximum tensile force and the maximum tensile force elongation of the polyester yarns used are measured in accordance with DIN 53 830, Part 1.
  • Matrix filaments in the hybrid yarns according to the invention consist of or contain thermoplastic polymers. These can be any melt-spinnable thermoplastics, as long as the filaments produced therefrom melt at a temperature which is lower than the melting or decomposition temperature of the reinforcing filaments used in the respective case.
  • Matrix filaments of polybutylene terephthalate and / or of polyethylene terephthalate and / or of chemically modified polyethylene terephthalate are preferred.
  • Matrix filaments made of a thermoplastic modified polyester, in particular a modified polyethylene terephthalate, are very particularly preferably used; the modification lowers the melting point compared to 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 - (I), -O-OC-R 2 -CO-OR 3 - (II), in which Ar 1 represents a divalent mono- 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
  • 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 which consist of or contain a thermoplastic and elastomeric polymer. These can also be any melt-spinnable and elastomeric thermoplastics, as long as the filaments produced therefrom melt at a temperature which is lower than the melting or decomposition temperature of the reinforcing filaments used in the respective case.
  • elastomeric polymer is understood to mean a polymer whose glass transition temperature is less than 0 ° C., preferably less than 23 ° C.
  • thermoplastic and elastomeric polymers are elastomeric polyamides, polyolefins, polyesters and polyurethanes. Such polymers are known per se.
  • radicals in the structural formulas defined above mean divalent aliphatic radicals, this means 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 are 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 -.
  • radicals in the structural formulas defined above mean divalent aromatic radicals, these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear.
  • heterocyclic-aromatic radicals these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.
  • Polynuclear aromatic radicals can be condensed with one another or connected to one another via C-C bonds or via bridging groups such as -O-, -S-, -CO- or -CO-NH groups.
  • the valence bonds of the divalent aromatic radicals can be in a para- or in a comparable coaxial or parallel position to one another, or also in a meta or in a comparable angular position to one another.
  • valence bonds which are in a coaxial or parallel position, are directed in opposite directions.
  • An example of coaxial, oppositely directed bonds are the biphen-4,4'-diyl bonds.
  • An example of parallel, opposite bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene 1,8 bonds are parallel aligned.
  • Examples of preferred divalent aromatic radicals whose valence bonds are in para- or in a comparable coaxial or parallel position to one another are mononuclear aromatic radicals with mutually para-free valences, in particular 1,4-phenylene or dinuclear fused aromatic radicals with parallel directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear aromatic residues linked via a CC bond with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.
  • Examples of preferred divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another are mononuclear aromatic radicals with free valences which are meta to one another, in particular 1,3-phenylene or dinuclear condensed aromatic radicals with bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a CC bond with bonds oriented at an angle to one another, in particular 3,4'-biphenylene.
  • substituents are alkyl, alkoxy or halogen.
  • Alkyl radicals are to be understood as meaning branched and in particular straight-chain alkyl, for example alkyl having one to six carbon atoms, in particular methyl.
  • Alkoxy radicals are to be understood as meaning branched and in particular straight-chain alkoxy, for example alkoxy having one to six carbon atoms, in particular methoxy.
  • radicals are halogen, it is, for example, fluorine, bromine or, in particular, chlorine.
  • the matrix filaments used in the hybrid yarn according to the invention can be constructed from thermoplastic polymers which usually have an intrinsic 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 polymer 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 intrinsic viscosity is measured as described above.
  • the hybrid yarns according to the invention usually have yarn count from 6000 to 150 dtex, preferably from 4500 to 150 dtex.
  • the individual fiber titer of the reinforcing filaments and the matrix filaments usually ranges from 2 to 10 dtex, preferably 4 to 8 dtex.
  • the cross sections of the reinforcing filaments and the matrix filaments can be any; for example elliptical, bi- or multilobal, ribbon-shaped or preferably round.
  • thermoplastic polymers are prepared by processes known per se by polycondensation of the corresponding bifunctional monomer components.
  • dicarboxylic acids or dicarboxylic acid esters and the corresponding diol components are usually used.
  • Such thermoplastic and optionally elastomeric polyesters, polyurethanes, polyamides and polyolefins are already known.
  • hybrid yarns according to the invention can be produced by means of special blowing intermingling processes.
  • 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, which 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, which may be humidified.
  • the filament material is fed to the blowing nozzle at a higher speed than is drawn from it.
  • Blown-twisted loop or plain yarns can be produced by different ropes of roving strands.
  • blow-swirling process known per se is modified in such a way that before the highly shrinkable matrix filaments run into the swirling nozzle, their shrinkage is partially or completely triggered by heating.
  • the leading of this roving component before the heating step is therefore to be chosen larger in the method than without such a heating step.
  • loop hybrid yarns or in particular hybrid plain yarns can be obtained.
  • the intermingling distance or the intermingling density is primarily determined by the pressure of the intermingling medium and the nozzle type selected in each case.
  • a corresponding swirl pressure must 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 shrinkage of the matrix roving prior to entering the intermingling nozzle can be triggered by methods known per se. For example by heating by means of 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 by a steam stuffer box method.
  • either high-strength multifilament yarns can be placed in the interlacing device or the multifilament yarns can be stretched and, if necessary, fixed immediately before entering the interlacing nozzle.
  • 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 rovings have a thermal shrinkage at 200 ° C. of 2 to 8%.
  • the primary hybrid yarn After leaving the intermingling nozzle, the primary hybrid yarn is drawn off, with usually only a low tension being allowed to occur.
  • a primary hybrid yarn can be formed with no, little or a high proportion of loops. If a plain yarn is desired, the primary yarn can be heated with a low or high proportion of loops with shrinkage approval. The loops contract and the yarn structure is largely smoothed. Smooth yarns that have already formed in the intermingling nozzle are usually drawn off and wound up directly.
  • the interlacing of the hybrid yarns from reinforcement and matrix filaments of the first embodiment described above is preferably carried out by means of a special warm interlacing process, which is described in EP-B-0,455,193.
  • the reinforcement filaments are warmed up to near the softening point before swirling (approx. 600 ° C for glass).
  • the heating can be done by godets and / or heating tube, while the low-melting thermoplastic single filaments made of polyester are also preheated to trigger the shrinkage and fed to the higher-level swirl nozzle.
  • the resulting smooth, high-thread-lock hybrid yarns are easily weaved.
  • the hybrid yarns according to the invention can be processed into textile fabrics by methods known per se. Examples of this are woven fabrics, knitted fabrics, knitted fabrics and, in particular, scrims. Such textile fabrics can be converted or stabilized by melting the matrix component in composite materials.
  • the invention also relates to the use of the hybrid yarns for these purposes.
  • a bobbin with reinforcing roving and a bobbin with matrix roving were placed on a creel.
  • the nature of the rovings and the yarn titer used are listed in Table 1 below.
  • the reinforcing roving was fed directly to a intermingling nozzle via a delivery system consisting of three godets.
  • a heater was interposed between the delivery godets. This was a device for the contactless heating of running threads, as described in EP-A-569,082.
  • the matrix roving was also fed to the texturing nozzle via a delivery unit consisting of two godets and a heating device arranged between them. Instead of or in addition to the intermediate heating device, the delivery godets were heated.
  • the heating device was a device for the contactless heating of running threads, as described in EP-A-579,092.
  • the temperatures of the godets of the delivery plants were between 80 and 130 ° C.
  • the primary hybrid yarn was drawn off by means of a further godet, the surface speed of the godet being adjusted in such a way that the yarn structure was optimized for the textile properties. Details on the implementation of the procedure can be found in the table below.
  • the properties of the hybrid yarns obtained are shown in a further Table 2.
  • Table 1 Manufacturing conditions of the hybrid yarns Example No. Reinforcement roving (type; titer dtex) Matrix roving (type; titer dtex) Lore Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Ampl.
  • hybrid yarns were produced by intermingling.
  • High-strength PET multifilament yarns with a titre of 1100 dtex were used as reinforcing rovings 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. Table 3 Manufacturing conditions of the hybrid yarns Example No. Lore Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Ampl.
  • Example 1 Analogous to Example 1, hybrid yarns were produced by intermingling. 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 as matrix rovings. Details of the manufacturing conditions are listed in Table 5. The properties of the yarns obtained are shown in Table 6. Table 5 Manufacturing conditions of the hybrid yarns Example No. Lore Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Ampl.
  • a low-shrinkage hybrid yarn with reinforcing roving made of PET and with matrix roving made of isophthalic acid-modified PET was produced.
  • the yarn titer was 1380 dtex. This yarn was loaded with different pretension weights and each 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 3rd 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 produced from reinforcing roving made from PET and from matrix roving made from different types of PET modified with isophthalic acid.
  • the manufacturing conditions were the same in each case.
  • the matrix rovings differ in the melting range of the PET type.
  • the proportion of the matrix component in the hybrid yarns was 15 to 20% by volume.
  • the delivery of the matrix roving was between 50 and 100%.

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Abstract

Composite yarns comprising reinforcing filaments and matrix filaments consisting of a thermoplastic polymer with a lower m.pt. than the degradation temperature or m.pt. of the reinforcing filament material. The yarns have heat shrinkage values less than or equal to 2 (1) and 5 (3) % in air at 160 and 200 degrees C respectively, measured under a load of 0.0004 cN/tex. The preparation of these yarns is also claimed.

Description

Die vorliegende Erfindung betrifft neue Hybridgarne, die sich durch einen besonders niedrigen Thermoschrumpf auszeichnen. Derartige Garne lassen sich in vorteilhafter Weise zu Verbundwerkstoffen oder zu textilen Flächengebilden, wie Gelegen verarbeiten.The present invention relates to new hybrid yarns which are distinguished by a particularly low thermal shrinkage. Such yarns can advantageously be processed into composite materials or textile fabrics, such as scrims.

Hybridgarne, also Garne aus Verstärkungs- und Matrixfilamenten, sind an sich bekannt. Derartige Garne dienen beispielsweise als Vorprodukte zur Herstellung von Verbundwerkstoffen. Dazu wird üblicherweise zunächst ein textiles Flächengebilde aus dem Hybridgarn hergestellt; die Matrixfilamente dieser Hybridgarne werden anschließend durch Auf- oder Anschmelzen in eine Matrix übergeführt, welche die Verstärkungsfilamente einbettet oder umfließt und zusammen mit diesen den Verbund aufbaut.Hybrid yarns, i.e. yarns made from reinforcement and matrix filaments, are known per se. Such yarns are used, for example, as intermediate products for the production of composite materials. For this purpose, a textile fabric is usually first produced from the hybrid yarn; The matrix filaments of these hybrid yarns are then converted by melting or melting into a matrix which embeds or flows around the reinforcement filaments and, together with them, builds up the composite.

An die Matrixfilamente werden im allgemeinen keine hohen Anforderungen bezüglich der Festigkeit und anderer mechanischer Eigenschaften gestellt, da diese ohnehin in späteren Verarbeitungsschritten aufgeschmolzen werden. Somit entfällt bei der Herstellung derartiger Filamente eine aufwendige Nachbehandlung nach dem Verspinnen, wie das Verstrecken oder das Fixieren. Matrixfilamente weisen daher von Haus aus einen erheblichen Thermoschrumpf auf, der sich bei den späteren Verarbeitungsschritten nachteilig auf das Produkt auswirken kann.The matrix filaments are generally not subject to high requirements with regard to strength and other mechanical properties, since these are melted anyway in later processing steps. This eliminates the need for costly post-spinning treatment such as stretching or fixing in the manufacture of such filaments. Matrix filaments therefore inherently show considerable thermal shrinkage, which can adversely affect the product in the later processing steps.

Es besteht ein Bedarf an Hybridgarnen, die einen geringen Schrumpf aufweisen. Derartige Garne schrumpfen naturgemäß nicht oder nur in einem sehr geringen Ausmaße beim Erhitzen zwecks Ausbildung der Matrix. Folglich wird die Lage der Verstärkungsfilamente beim Erzeugen der Matrix nicht oder nur unwesentlich gestört. Auch wird mit diesen neuen Garnen die Herstellung von Gelegen wesentlich vereinfacht. Bislang mußten beim Fixieren der übereinandergelegten Garne bei der Gelegeherstellung aufwendige Maßnahmen getroffen werden, um den durch das Erhitzen ausgelösten Schrumpf der Garne abzufangen und das Primärgelege zu stabilisieren. Mit den neuen Hybridgarnen können diese Maßnahmen weitgehend entfallen.There is a need for hybrid yarns that have low shrinkage. Such yarns naturally do not shrink or only to a very small extent when heated to form the matrix. As a result, the position of the reinforcement filaments is not or only slightly disturbed when the matrix is produced. These new yarns also significantly simplify the production of scrims. So far, when fixing the superimposed Elaborate measures are taken during the production of the scrim to intercept the shrinkage of the yarn caused by the heating and to stabilize the primary scrim. With the new hybrid yarns, these measures can largely be dispensed with.

Es sind zwar sogenannte Zweikomponenten-Schlingengarne mit hoher Festigkeit und geringem Schrumpf bekannt. Derartige Garne wurden insbesondere für den Einsatz als Nähgarne entwickelt und beispielsweise in der EP-B-363,798 beschrieben. Derartige Garne weisen allerdings üblicherweise keine Matrixfilamente aus tieferschmelzenden Filamenten auf, sondern sind aus Filamenten eines Typs aber unterschiedlicher Festigkeiten, die in einer Kern-Mantel-Struktur angeordnet sind, aufgebaut.So-called two-component loop yarns with high strength and low shrinkage are known. Such yarns were developed in particular for use as sewing threads and are described, for example, in EP-B-363,798. However, such yarns usually do not have matrix filaments made from deep-melting filaments, but are made up of filaments of one type but of different strengths, which are arranged in a core-sheath structure.

Es wurde jetzt ein Verfahren zur Herstellung von schrumpfarmen Hybridgarnen gefunden, daß zu Produkten mit dem oben geschilderten Eigenschaftsprofil führt. Die erfindungsgemäßen Garne zeichnen sich durch einen über ein relativ großes Temperaturintervall sehr niedrigen Thermoschrumpf aus.A process has now been found for the production of low-shrinkage hybrid yarns which leads to products with the property profile described above. The yarns according to the invention are distinguished by a very low thermal shrinkage over a relatively large temperature interval.

Die vorliegende Erfindung betrifft schrumpfarme Hybridgarne enthaltend Verstärkungsfilamente und Matrixfilamente aus thermoplastischen Polymeren, die einen tieferen Schmelzpunkt als der Schmelz- oder Zersetzungspunkt der Verstärkungsfilamente aufweisen. Die erfindungsgemäßen Hybridgarne sind dadurch gekennzeichnet, daß diese einen Thermoschrumpf, gemessen an einer Garnprobe unter einer Belastung von 0,0004 cN/dtex bei einer Lufttemperatur von 160 °C, von kleiner gleich 2 %, insbesondere von kleiner gleich 1 %, und bei einer Lufttemperatur von 200 °C von kleiner gleich 5 %, insbesondere von kleiner gleich 3 %, aufweisen.The present invention relates to low-shrinkage hybrid yarns containing reinforcing filaments and matrix filaments made of thermoplastic polymers which have a lower melting point than the melting or decomposition point of the reinforcing filaments. The hybrid yarns according to the invention are characterized in that they have a thermal shrinkage, measured on a yarn sample under a load of 0.0004 cN / dtex at an air temperature of 160 ° C, of less than or equal to 2%, in particular of less than or equal to 1%, and at Air temperature of 200 ° C of less than or equal to 5%, in particular less than or equal to 3%.

Zur Ermittlung des Thermoschrumpfes der erfindungsgemäßen Hybridgarne werden an den beiden Enden von sechs Garnproben von jeweils 60 cm Länge Schlaufen gebildet und diese Garnproben an ihren Schlaufen an einer Schrumpfstange eingehängt. Diese Garnproben werden jeweils mit einem Gewicht einer Vorspannkraft von 0,0004 cN/dtex ausgesetzt. Die Schrumpfstange mit den Garnproben wird in einen Umluftofen eingehängt und sodann 15 Minuten lang mit Heißluft definierter Temperatur behandelt. Die Längenänderung der Garnprobe vor und nach dem Erhitzen in % stellt den Thermoschrumpf dar.In order to determine the thermal shrinkage of the hybrid yarns according to the invention, loops are formed at the two ends of six yarn samples, each 60 cm long, and these yarn samples are hooked onto their loops on a shrink rod. These yarn samples are each subjected to a preload force of 0.0004 cN / dtex. The shrink bar with the Yarn samples are suspended in a forced air oven and then treated with hot air at a defined temperature for 15 minutes. The change in length of the yarn sample before and after heating in% represents the thermal shrinkage.

Die mechanischen Eigenschaften der erfindungsgemäßen Hybridgarne sind in Abhängigkeit der Zusammensetzung, wie Art und Anteil der Verstärkungsfilamente oder der Matrixfilamente in Abhängigkeit des physikalischen Aufbaus der Garne, wie z.B. Grad der Verwirbelung, in weiten Grenzen variierbar. Üblicherweise beträgt der Anteil der Matrixfilamente 5 bis 60 Gew.%, vorzugsweise 10 bis 50 Gew. %, bezogen auf das Gewicht des Hybridgarns.The mechanical properties of the hybrid yarns according to the invention are dependent on the composition, such as the type and proportion of the reinforcing filaments or the matrix filaments, depending on the physical structure of the yarns, e.g. Degree of turbulence, can be varied within wide limits. The proportion of the matrix filaments is usually 5 to 60% by weight, preferably 10 to 50% by weight, based on the weight of the hybrid yarn.

Der Begriff "Hybridgarn" ist im Rahmen dieser Beschreibung in seiner breitesten Bedeutung zu verstehen. Darunter ist demnach jede Kombination enthaltend Verstärkungsfilamente und die oben definierten Matrixfilamente zu verstehen.The term "hybrid yarn" is to be understood in its broadest meaning within the scope of this description. Accordingly, this includes any combination containing reinforcing filaments and the matrix filaments defined above.

Beispiele für mögliche Hybridgarntypen sind Filamentgarne aus verschiedenen Typen von Filamenten, welche miteinander verwirbelt oder mittels einer anderen Technologie, wie beispielsweise Zwirnen, miteinander kombiniert sind. Alle diese Hybridgarne sind durch die Anwesenheit von zwei oder mehreren Typen von Filamenten gekennzeichnet, wobei mindestens eine Filamenttype ein Verstärkungsfilament und mindestens eine Filamenttype ein Matrixfilament im Sinne der oben gegebenen Definitionen darstellt.Examples of possible hybrid yarn types are filament yarns from different types of filaments which are interwoven with one another or combined with one another by means of another technology, such as for example twisting. All of these hybrid yarns are characterized by the presence of two or more types of filaments, at least one type of filament being a reinforcing filament and at least one type of filament being a matrix filament as defined above.

Besonders bevorzugt eingesetzt werden durch Intermingling- oder Commingling-Techniken hergestellte Hybridgarne; dabei kann es sich um Schlingengarne handeln, vorzugsweise jedoch um Glattgarne.Hybrid yarns produced by intermingling or commingling techniques are particularly preferably used; it can be loop yarns, but preferably plain yarns.

Die erfindungsgemäßen Glattgarne zeichnen sich durch eine besonders gute Verarbeitbarkeit mit flächenbildenden Technologien sowie durch gute Stoffmuster aus.The smooth yarns according to the invention are notable for particularly good processability with area-forming technologies and good fabric samples.

Die erfindungsgemäßen Hybridgarne weisen vorzugsweise eine statische Schrumpfkraft, gemessen nach DIN 53866, Teil 12, bei Temperaturen von bis zu 200 °C von bis zu 0,01 cN/dtex auf.The hybrid yarns according to the invention preferably have a static shrinkage force, measured according to DIN 53866, part 12, at temperatures of up to 200 ° C. of up to 0.01 cN / dtex.

Zur Messung der statischen Schrumpfkratt werden je fünf Garnproben von 60 cm Länge unter einer Vorspannung von 0,01 cN/dtex in zwei Klemmen eingespannt. Anschließend wird die eingespannte Garnprobe mit Luft der gewünschten Temperatur eine Minute lang behandelt. Die bei Erwärmung in Fadenlängsrichtung auftretende Kraft ist die statische Schrumpfkratt und erreicht nach einem kurzen Zeitintervall einen Sättigungswert.To measure the static shrinkage, five yarn samples each 60 cm long are clamped in two clamps under a preload of 0.01 cN / dtex. The clamped yarn sample is then treated with air of the desired temperature for one minute. The force that occurs when heating in the longitudinal direction of the thread is the static shrinkage and reaches a saturation value after a short time interval.

Die Anzahl der Verwirbelungspunkte in den erfindungsgemäßen Hybridgarnen läßt sich durch die Wahl der Verwirbelungsbedingungen in weiten Bereichen einstellen. Je höher der Anteil an der mechanisch relativ labilen Matrixkomponente ist, umso weniger intensiv läßt sich die Verwirbelung ausführen und demzufolge ist der Abstand der Verwirbelungspunkte bei derartigen Garnen normalerweise relativ groß.The number of intermingling points in the hybrid yarns according to the invention can be set within wide ranges by the selection of the intermingling conditions. The higher the proportion of the mechanically relatively unstable matrix component, the less intensely the intermingling can be carried out and consequently the distance between the intermingling points in such yarns is normally relatively large.

Bevorzugte Hybridgarne weisen einen Verwirbelungsabstand von weniger als 60 mm, vorzugsweise weniger als 30 mm auf; dieser Wert bezieht sich auf eine Messung mit dem Nadeltestgerät Rothschild Entanglement Tester 2050.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.

Die Matrixfilamente der erfindungsgemäßen Hybridgarne bestehen aus thermoplastischen Polymeren. Diese weisen vorzugsweise einen Schmelzpunkt auf, der mindestens 30 °C unter dem Schmelz- oder Zerstetzungspunkt der jeweils eingesetzten Verstärkungsfilamtente liegt.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 the reinforcing filament elements used in each case.

Bei den in den erfindungsgemäßen Hybridgarnen zum Einsatz kommenden Verstärkungsfilamenten kann es sich um Filamente aus einer Vielzahl von Materialien handeln. Neben organischen Polymeren können auch anorganische Materialien zum Einsatz kommen. Verstärkungsfilamente im Sinne dieser Beschreibung bedeuten Filamente, welche in dem angestrebten textilen Flächengebilde bzw. Verbundwerkstoff eine verstärkende Funktion übernehmen.The reinforcing filaments used in the hybrid yarns according to the invention can be filaments made from a large number of materials. In addition to organic polymers, inorganic materials can also be used. Reinforcement filaments in the sense of this description mean filaments which assume a reinforcing function in the desired textile fabric or composite material.

In einer ersten bevorzugten Ausführungsform sind die Verstärkungsfilamente aus Einzelfilamenten aufgebaut, die einen Anfangsmodul von mehr als 50 GPa aufweisen.In a first preferred embodiment, the reinforcement filaments are constructed from individual filaments which have an initial modulus of more than 50 GPa.

Bevorzugte Verstärkungsfilamente dieses Typs bestehen aus Glas; Kohlenstoff; Metallen bzw. Metallegierungen, wie Stahl, Aluminium oder Wolfram; Nichtmetallen, wie Bor; Metall-, Halbmetall- oder Nichtmetalloxiden, -carbiden oder nitriden, wie Aluminiumoxid, Zirkonoxid, Bornitrid, Borcarbid, Siliziumcarbid, Siliziumdioxid (Quarz); Keramik, oder Hochleistungspolymeren (d.h. Fasern, die ohne oder nur bei geringer Verstreckung einen sehr hohen Anfangsmodul und eine sehr hohe Reißfestigkeit liefern), wie flüssigkristallinen Polyestern (LCP), Poly-(bis-benzimidazo-benzophenanthrolinen (BBB), Poly-(amid-imiden) (PAI), Polybenzimidazolen (PBI), Poly-(p-phenylenbenzo-bisoxazolen (PBO), Poly-(p-phenylenbenzo-bisthiazolen) (PBT), Polyetherketonen (PEK, PEEK, PEEKK), Polyetherimiden (PEI), Polyethersulfonen (PESU), Polyimiden (PI), Poly-(p-phenylenen) (PPP), Polyarylensulfiden (PPS), Polysulfonen (PSU), Polyolefinen, wie Polyethylen (PE) oder Polypropylen (PP), und Aramiden (HMA), wie Poly-(m-phenylen-isophthalamid), Poly-(m-phenylen-terephthalamid), Poly-(p-phenylen-isophthalamid), Poly-(p-phenylen-terephthalamid), oder aus organischen Lösungsmitteln, wie N-Methylpyrrolidon, spinnbare Aramide abgeleitet von Terephthalsäuredichlorid und einer Mischung von zwei oder mehr aromatischen Diaminen, beispielsweise der Kombination p-Phenylendiamin, 1,4-Bis-(4-aminophenoxy)-benzol, 3,3'-Dimethylbenzidin, oder p-Phenylendiamin, 1,4-Bis-(4-aminophenoxy)-benzol, 3,4'-Diaminodiphenylether, oder p-Phenylendiamin, m-Phenylendiamin, 1,4-Bis-(4-aminophenoxy)-benzol.Preferred reinforcing filaments of this type are made of glass; Carbon; Metals or metal alloys, such as steel, aluminum or tungsten; Non-metals such as boron; Metal, semimetal 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 provide a very high initial modulus and a very high tensile strength with little or no stretching), such as liquid-crystalline polyesters (LCP), poly (bis-benzimidazo-benzophenanthrolines (BBB), poly (amide -imides) (PAI), polybenzimidazoles (PBI), poly (p-phenylene benzobisoxazoles (PBO), poly (p-phenylene benzobisthiazoles) (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-phenylene-isophthalamide), poly- (p-phenylene-terephthalamide), or from organic solvents such as N- Methyl pyrrolidone, spinnable aramids derived from terephthalic acid dichloride and a mixture of two or more aromatic diamines, for example the Kombina tion p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 3,3'-dimethylbenzidine, or p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 3,4'- Diaminodiphenyl ether, or p-phenylenediamine, m-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene.

Besonders bevorzugt werden Verstärkungsfilamente aus Glas, Kohlenstoff oder aromatischem Polyamid.Reinforcement filaments made of glass, carbon or aromatic polyamide are particularly preferred.

In einer zweiten besonders bevorzugten Ausführungsform kommen Verstärkungs- und Matrixfilamente zum Einsatz, die aus polymeren Materialien aus einer Polymerklasse, beispielsweise aus Polyolefinen, aus Polyamiden oder vorzugsweise aus Polyestern bestehen.In a second particularly preferred embodiment, reinforcement and matrix filaments are used which consist of polymeric materials from one polymer class, for example polyolefins, polyamides or preferably polyesters.

In dieser Ausführungsform weisen die Einzelfilamente der Verstärkungsfilamente einen Anfangsmodul von mehr als 10 GPa auf. Verstärkungsfilamente für diese Ausführungsform sind vorzugsweise hochfeste und schrumpfarme Polyesterfilamentgarne, insbesondere mit einem Garntiter von kleiner gleich 1100 dtex, einer Feinheitsfestigkeit von größer gleich 55 cN/tex, einer Höchstzugkraftdehnung von größer gleich 12 % und einem Heißluftschrumpf (gemessen bei 200 °C) von kleiner gleich 9 %.In this embodiment, the individual filaments of the reinforcement filaments have an initial modulus of more than 10 GPa. Reinforcing filaments for this embodiment are preferably high-strength and low-shrinkage polyester filament yarns, in particular with a yarn titer of less than or equal to 1100 dtex, a tenacity of greater than or equal to 55 cN / tex, a maximum tensile strength elongation of greater than or equal to 12% and a hot air shrinkage (measured at 200 ° C.) of less equal to 9%.

Die Messung der Höchstzugkraft und der Höchstzugkraftdehnung der zum Einsatz kommenden Polyestergarne erfolgt in Anlehnung an DIN 53 830, Teil 1.The maximum tensile force and the maximum tensile force elongation of the polyester yarns used are measured in accordance with DIN 53 830, Part 1.

Matrixfilamente in den erfindungsgemäßen Hybridgarnen bestehen aus oder enthalten thermoplastische Polymere. Dabei kann es sich um beliebige schmelzspinnbare Thermoplaste handeln, solange die daraus hergestellten Filamente bei einer Temperatur schmelzen, die niedriger ist als die Schmelz- oder Zersetzungstemperatur der im jeweiligen Fall eingesetzten Verstärkungsfilamente.Matrix filaments in the hybrid yarns according to the invention consist of or contain thermoplastic polymers. These can be any melt-spinnable thermoplastics, as long as the filaments produced therefrom melt at a temperature which is lower than the melting or decomposition temperature of the reinforcing filaments used in the respective case.

Bevorzugt werden Matrixfilamente aus Polybutylenterephthalat und/oder aus Polyethylenterephthalat und/oder aus chemisch modifiziertem Polyethylenterephthalat.Matrix filaments of polybutylene terephthalate and / or of polyethylene terephthalate and / or of chemically modified polyethylene terephthalate are preferred.

Ganz besonders bevorzugt werden Matrixfilamente aus einem thermoplastischen modifizierten Polyester, insbesondere einem modifizierten Polyethylenterephthalat eingesetzt; die Modifizierung bewirkt ein Absenken des Schmelzpunktes im Vergleich mit dem Filament aus unmodifiziertem Polyester.Matrix filaments made of a thermoplastic modified polyester, in particular a modified polyethylene terephthalate, are very particularly preferably used; the modification lowers the melting point compared to the filament made of unmodified polyester.

Besonders bevorzugte modifizierte Polyester dieses Typs enthalten die wiederkehrenden Struktureinheiten der Formeln I und II

        -O-OC-Ar1-CO-O-R1-     (I),



        -O-OC-R2-CO-O-R3-     (II),

worin Ar1 einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, vorzugsweise 1,4-Phenylen und/oder 2,6-Naphthylen darstellt, R1 und R3 unabhängig voneinander zweiwertige aliphatische oder cycloaliphatische Reste darstellen, insbesondere Reste der Formel -CnH2n-, worin n eine ganze Zahl zwischen 2 und 10 ist, insbesondere Ethylen, oder einen von Cyclohexandimethanol abgeleiteten Rest darstellen, und R2 einen zweiwertigen aliphatischen, cycloaliphatischen oder ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in meta-Stellung oder in einer zu dieser Stellung vergleichbaren gewinkelten Stellung zueinander befinden, vorzugsweise 1,3-Phenylen darstellt.Particularly preferred modified polyesters of this type contain the recurring structural units of the formulas I and II

-O-OC-Ar 1 -CO-OR 1 - (I),



-O-OC-R 2 -CO-OR 3 - (II),

in which Ar 1 represents a divalent mono- 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 or in an angular position comparable to this position, preferably 1,3-phenylene.

Ganz besonders bevorzugte modifizierte Polyester dieses Typs enthalten 40 bis 95 Mol % der wiederkehrenden Struktureinheiten der Formel I und 60 bis 5 Mol % der wiederkehrenden Struktureinheiten der Formel II, worin Ar1 1,4-Phenylen und/oder 2,6-Naphthylen ist, R1 und R3 Ethylen bedeuten und R2 1,3-Phenylen ist.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.

In einer weiteren bevorzugten Ausführungsform kommen Matrixfilamente zum Einsatz, die aus einem thermoplastischen und elastomeren Polymeren bestehen oder dieses enthalten. Dabei kann es sich ebenfalls um beliebige schmelzspinnbare und elastomere Thermoplaste handeln, solange die daraus hergestellten Filamente bei einer Temperatur schmelzen, die niedriger ist als die Schmelz- oder Zersetzungstemperatur der im jeweiligen Fall eingesetzten Verstärkungsfilamente.In a further preferred embodiment, matrix filaments are used which consist of or contain a thermoplastic and elastomeric polymer. These can also be any melt-spinnable and elastomeric thermoplastics, as long as the filaments produced therefrom melt at a temperature which is lower than the melting or decomposition temperature of the reinforcing filaments used in the respective case.

Unter "elastomerem Polymer" ist im Rahmen dieser Beschreibung ein Polymer zu verstehen, dessen Glasübergangstemperatur weniger als 0 °C, vorzugsweise weniger als 23 °C beträgt.In the context of this description, “elastomeric polymer” is understood to mean a polymer whose glass transition temperature is less than 0 ° C., preferably less than 23 ° C.

Bevorzugte Beispiele für thermoplastische und elastomere Polymere sind elastomere Polyamide, Polyolefine, Polyester und Polyurethane. Derartige Polymere sind an sich bekannt.Preferred examples of thermoplastic and elastomeric polymers are elastomeric polyamides, polyolefins, polyesters and polyurethanes. Such polymers are known per se.

Bedeuten in den oben definierten Strukturformeln irgendwelche Reste zweiwertige aliphatische Reste, so ist darunter verzweigtes und insbesondere geradkettiges Alkylen zu verstehen, beispielsweise Alkylen mit zwei bis zwanzig, vorzugsweise mit zwei bis zehn Kohlenstoffatomen. Beispiele für derartige Reste sind Ethan-1,2-diyl, Propan-1,3-diyl, Butan-1,4-diyl, Pentan-1,5-diyl, Hexan-1,6-diyl oder Octan-1,8-diyl.If any radicals in the structural formulas defined above mean divalent aliphatic radicals, this means 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.

Bedeuten in den oben definierten Strukturformeln irgendwelche Reste zweiwertige cycloaliphatische Reste, so sind darunter Gruppen zu verstehen, die carbocyclische Reste mit fünf bis acht, vorzugsweise sechs Ringkohlenstoffatomen enthalten. Beispiele für derartige Reste sind Cyclohexan-1,4-diyl oder die Gruppe -CH2-C6H10-CH2-.If any radicals in the structural formulas defined above are 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 -.

Bedeuten in den oben definierten Strukturformeln irgendwelche Reste zweiwertige aromatische Reste, so handelt es sich dabei um ein- oder mehrkernige aromatische Kohlenwasserstoffreste oder um heterocyclisch-aromatische Reste, die ein- oder mehrkernig sein können. Im Falle von heterocyclisch-aromatischen Resten weisen diese insbesondere ein oder zwei Sauerstoff-, Stickstoff- oder Schwefelatome im aromatischen Kern auf.If any radicals in the structural formulas defined above mean divalent aromatic radicals, these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear. In the case of heterocyclic-aromatic radicals, these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.

Mehrkernige aromatische Reste können miteinander kondensiert sein oder über C-C-Bindungen oder über Brückengruppen, wie -O-, -S-, -CO- oder -CO-NH- Gruppen miteinander verbunden sein.Polynuclear aromatic radicals can be condensed with one another or connected to one another via C-C bonds or via bridging groups such as -O-, -S-, -CO- or -CO-NH groups.

Die Valenzbindungen der zweiwertigen aromatischen Reste können sich in para- oder in vergleichbarer koaxialer oder paralleler Position zueinander befinden, oder auch in meta- oder in vergleichbarer gewinkelter Position zueinander.The valence bonds of the divalent aromatic radicals can be in a para- or in a comparable coaxial or parallel position to one another, or also in a meta or in a comparable angular position to one another.

Die Valenzbindungen, die in koaxialer oder parallel zueinander befindlicher Stellung stehen, sind entgegengesetzt gerichtet. Ein Beispiel für koaxiale, entgegengesetzt gerichtete Bindungen sind die Biphen-4,4'-diyl Bindungen. Ein Beispiel für parallel, entgegegesetzt gerichtete Bindungen sind die Naphthalin-1,5- oder -2,6-Bindungen, während die Naphthalin-1,8-Bindungen parallel gleichgerichtet sind.The valence bonds, which are in a coaxial or parallel position, are directed in opposite directions. An example of coaxial, oppositely directed bonds are the biphen-4,4'-diyl bonds. An example of parallel, opposite bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene 1,8 bonds are parallel aligned.

Beispiele für bevorzugte zweiwertige aromatische Reste, deren Valenzbindungen sich in para- oder in vergleichbarer koaxialer oder paralleler Position zueinander befinden, sind einkernige aromatische Reste mit zueinander para-ständigen freien Valenzen, insbesondere 1,4-Phenylen oder zweikernige kondensierte aromatische Reste mit parallelen, entgegengesetzt gerichteten Bindungen, insbesondere 1,4-, 1,5- und 2,6-Naphthylen, oder zweikernige über eine C-C Bindung verknüpfte aromatische Reste mit koaxialen, entgegengesetzt gerichteten Bindungen, insbesondere 4,4'-Biphenylen.Examples of preferred divalent aromatic radicals whose valence bonds are in para- or in a comparable coaxial or parallel position to one another are mononuclear aromatic radicals with mutually para-free valences, in particular 1,4-phenylene or dinuclear fused aromatic radicals with parallel directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear aromatic residues linked via a CC bond with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.

Beispiele für bevorzugte zweiwertige aromatische Reste, deren Valenzbindungen sich in meta- oder in vergleichbarer gewinkelter Position zueinander befinden, sind einkernige aromatische Reste mit zueinander meta-ständigen freien Valenzen, insbesondere 1,3-Phenylen oder zweikernige kondensierte aromatische Reste mit zueinander gewinkelt gerichteten Bindungen, insbesondere 1,6- und 2,7-Naphthylen, oder zweikernige über eine C-C Bindung verknüpfte aromatische Reste mit zueinander gewinkelt gerichteten Bindungen, insbesondere 3,4'-Biphenylen.Examples of preferred divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another are mononuclear aromatic radicals with free valences which are meta to one another, in particular 1,3-phenylene or dinuclear condensed aromatic radicals with bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a CC bond with bonds oriented at an angle to one another, in particular 3,4'-biphenylene.

Alle diese aliphatischen, cycloaliphatischen oder aromatischen Reste können mit inerten Gruppen substituiert sein. Darunter sind Substituenten zu verstehen, die die ins Auge gefaßte Anwendung nicht negativ beeinflussen.All of these aliphatic, cycloaliphatic or aromatic radicals can be substituted with inert groups. These are to be understood as substituents that do not negatively influence the envisaged application.

Beispiele für solche Substituenten sind Alkyl, Alkoxy oder Halogen.Examples of such substituents are alkyl, alkoxy or halogen.

Unter Alkylresten ist verzweigtes und insbesondere geradkettiges Alkyl zu verstehen, beispielsweise Alkyl mit ein bis sechs Kohlenstoffatomen, insbesondere Methyl.Alkyl radicals are to be understood as meaning branched and in particular straight-chain alkyl, for example alkyl having one to six carbon atoms, in particular methyl.

Unter Alkoxyresten ist verzweigtes und insbesondere geradkettiges Alkoxy zu verstehen, beispielsweise Alkoxy mit ein bis sechs Kohlenstoffatomen insbesondere Methoxy.Alkoxy radicals are to be understood as meaning branched and in particular straight-chain alkoxy, for example alkoxy having one to six carbon atoms, in particular methoxy.

Bedeuten irgendwelche Reste Halogen, so handelt es sich dabei beispielsweise um Fluor, Brom oder insbesondere um Chlor.If any radicals are halogen, it is, for example, fluorine, bromine or, in particular, chlorine.

Die im erfindungsgemäßen Hybridgarn verwendeten Matrixfilamente können aus thermoplastischen Polymeren aufgebaut sein, die üblicherweise eine intrinsische Viskosität von mindestens 0,5 dl/g, vorzugsweise 0,6 bis 1,5 dl/g aufweisen. Die Messung der intrinsischen Viskosität erfolgt in einer Lösung des thermoplastischen Polymeren in Dichloressigsäure bei 25 °C.The matrix filaments used in the hybrid yarn according to the invention can be constructed from thermoplastic polymers which usually have an intrinsic 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 polymer in dichloroacetic acid at 25 ° C.

Werden im erfindungsgemäß einzusetzenden Hybridgarn Verstärkungsfilamente aus Polyestern verwendet, weisen diese Polyester üblicherweise eine intrinsische Viskosität von mindestens 0,5 dl/g, vorzugsweise 0,6 bis 1,5 dl/g auf. Die Messung der intrinsischen Viskosität erfolgt wie voranstehend beschrieben.If reinforcing filaments made of polyester are used in the hybrid yarn to be used according to the invention, these polyesters usually have an intrinsic viscosity of at least 0.5 dl / g, preferably 0.6 to 1.5 dl / g. The intrinsic viscosity is measured as described above.

Die erfindungsgemäßen Hybridgarne weisen üblicherweise Garntiter von 6000 bis 150 dtex auf, vorzugsweise von 4500 bis 150 dtex.The hybrid yarns according to the invention usually have yarn count from 6000 to 150 dtex, preferably from 4500 to 150 dtex.

Der Einzelfasertiter der Verstärkungsfilamente und der Matrixfilamente bewegt sich üblicherweise im Bereich von 2 bis 10 dtex, vorzugsweise 4 bis 8 dtex.The individual fiber titer of the reinforcing filaments and the matrix filaments usually ranges from 2 to 10 dtex, preferably 4 to 8 dtex.

Die Querschnitte der Verstärkungsfilamente und der Matrixfilamente können beliebig sein; beispielsweise ellipsenförmig, bi- oder multilobal, bändchenförmig oder vorzugsweise rund.The cross sections of the reinforcing filaments and the matrix filaments can be any; for example elliptical, bi- or multilobal, ribbon-shaped or preferably round.

Die Herstellung der thermoplastischen Polymeren erfolgt nach an sich bekannten Verfahren durch Polykondensation der entsprechenden bifunktionellen Monomerkomponenten. Im Falle der Polyester kommen üblicherweise Dicarbonsäuren oder Dicarbonsäureester und die entsprechenden Diolkomponenten zum Einsatz. Derartige thermoplastische und gegebenenfalls elastomere Polyester, Polyurethane, Polyamide und Polyolefine sind bereits bekannt.The thermoplastic polymers are prepared by processes known per se by polycondensation of the corresponding bifunctional monomer components. In the case of polyesters, dicarboxylic acids or dicarboxylic acid esters and the corresponding diol components are usually used. Such thermoplastic and optionally elastomeric polyesters, polyurethanes, polyamides and polyolefins are already known.

Es wurde weiterhin gefunden, daß die Herstellung der erfindungsgemäßen Hybridgarne mittels spezieller Blasverwirbelungsverfahren möglich ist.It has furthermore been found that the hybrid yarns according to the invention can be produced by means of special blowing intermingling processes.

Die Blasverwirbelung erfolgt mittels eines Fluids in einer Verwirbelungsdüse, z.B. Wasser oder insbesondere durch ein gegenüber den Vorgarnsträngen inertes Gas, insbesondere durch Luft, das gegebenenfalls befeuchtet ist.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, which may be humidified.

Bei der Blasverwirbelung wird bekanntlich das Filamentmaterial der Blasdüse mit größerer Geschwindigkeit zugeführt als aus ihr abgezogen. Der Geschwindigkeitsüberschuß der Zuführung gegenüber dem Abzug, ausgedrückt in Prozenten bezogen auf die Abzugsgeschwindigkeit, bezeichnet man als die Voreilung.As is known, in the process of blowing the filament, the filament material is fed to the blowing nozzle at a higher speed than is drawn from it. The excess speed of the feed compared to the take-off, expressed as a percentage of the take-off speed, is referred to as the advance.

Durch unterschiedliche Voreilungen von Vorgarnsträngen lassen sich blasverwirbelte Schlingen- oder Glattgarne herstellen.Blown-twisted loop or plain yarns can be produced by different ropes of roving strands.

In diesen Verfahren wird das an sich bekannte Blasverwirbelungsverfahren dahingehend modifiziert, daß vor dem Einlaufen der hochschrumpffähigen Matrixfilamente in die Verwirbelungsdüse deren Schrumpf teilweise oder vollständig durch Erhitzen ausgelöst wird. Die Voreilung dieser Vorgarnkomponente vor dem Erhitzungsschritt ist bei dem Verfahren also größer zu wählen als ohne einen solchen Erhitzungsschritt. Je nach gewählter Voreilung beim Einlauf in die Verwirbelungsdüse und den gewählten Verwirbelungsbedingungen lassen sich Schlingenhybridgarne oder insbesondere Hybridglattgarne erhalten.In these processes, the blow-swirling process known per se is modified in such a way that before the highly shrinkable matrix filaments run into the swirling nozzle, their shrinkage is partially or completely triggered by heating. The leading of this roving component before the heating step is therefore to be chosen larger in the method than without such a heating step. Depending on the selected advance when entering the intermingling nozzle and the selected intermingling conditions, loop hybrid yarns or in particular hybrid plain yarns can be obtained.

Zur Verwirbelung können herkömmliche Verwirbelungsdüsen verwendet werden. Der Verwirbelungsabstand bzw. die Verwirbelungsdichte wird in erster Linie durch den Druck des Verwirbelungsmediums und den jeweils gewählten Düsentyp bestimmt. Um einen erwünschten Verwirbelungsabstand zu erzielen, muß für einen bestimmten Düsentyp ein entsprechender Verwirbelungsdruck gewählt werden. Zweckmäßigerweise liegt der Arbeitsdruck im Bereich von 1 bis 8 bar, vorzugsweise von 1,5 bis 6 bar, insbesondere von 1,5 bis 3 bar.Conventional swirl nozzles can be used for swirling. The intermingling distance or the intermingling density is primarily determined by the pressure of the intermingling medium and the nozzle type selected in each case. In order to achieve a desired swirl distance, a corresponding swirl pressure must 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.

Die Erfindung betrifft auch ein Verfahren zur Herstellung der oben definierten schrumpfarmen Hybridgarne umfassend die Maßnahmen

  • a) Zuführen von zwei oder mehreren sich mit unterschiedlichen Geschwindigkeiten bewegenden Vorgarnsträngen zu einer Verwirbelungsdüse, wobei zumindest eine Teil der Vorgarnstränge (Verstärkungsvorgarn) aus Verstärkungsfilamenten besteht und ein weiterer Teil der Vorgarnstränge (Matrixvorgarn) aus tieferschmelzenden Matrifilamenten aus thermoplastischen Polymeren besteht, die einen Thermoschrumpf bei 200 °C von mehr als 20 % aufweisen,
  • b) Erwärmen des Matrixvorgarnes während des Zuführens in die Verwirbelungsdüse auf eine derartige Temperatur, daß zumindest ein Teil des Schrumpfes ausgelöst wird,
  • c) Verwirbeln der Vorgarnstränge in der Verwirbelungsdüse unter derartigen Bedingungen, daß sich ein primäres Hybridgarn ausbildet,
  • d) Abziehen des erhaltenen primären Hybridgarnes gegebenenfalls unter Zulassung von Schrumpf und/oder zusätzliches, vorzugsweise berührungsloses Erhitzen.
The invention also relates to a method for producing the low-shrinkage hybrid yarns defined above, comprising the measures
  • a) Feeding two or more roving strands moving at different speeds to a intermingling nozzle, wherein at least some of the roving strands (reinforcing roving) consist of reinforcing filaments and another part of the roving strands (matrix roving) consists of low-melting matrifilaments made of thermoplastic polymers, which are heat shrinkable Have 200 ° C of more than 20%,
  • b) heating the matrix roving to a temperature such that at least part of the shrinkage is triggered, while being fed into the intermingling nozzle,
  • c) intermingling the roving strands in the intermingling nozzle under conditions such that a primary hybrid yarn is formed,
  • d) pulling off the primary hybrid yarn obtained, optionally with the approval of shrinkage and / or additional, preferably non-contact heating.

Das Auslösen des Schrumpfes des Matrixvorgarnes vor dem Einlaufen in die Verwirbelungsdüse kann nach an sich bekannten Methoden erfolgen. Beispielsweise durch Erhitzen mittels Galetten, durch Kontakt mit einer Heizschiene bzw. einem Heizstift, berührungslos durch Durchleiten durch eine Heizvorrichtung, beispielsweise durch eine Vorrichtung, wie in der EP-A-579,092 beschrieben oder durch ein Dampfstauchkammerverfahren.The shrinkage of the matrix roving prior to entering the intermingling nozzle can be triggered by methods known per se. For example by heating by means of 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 by a steam stuffer box method.

Als Verstärkungsvorgarne können entweder bereits hochfeste Multifilamentgarne der Verwirbelungsvorrichtung vorgelegt werden oder die Multifilamentgarne können unmittelbar vor dem Einlauf in die Verwirbelungsdüse verstreckt und gegebenenfalls fixiert werden.As reinforcing rovings, either high-strength multifilament yarns can be placed in the interlacing device or the multifilament yarns can be stretched and, if necessary, fixed immediately before entering the interlacing nozzle.

Vorzugsweise werden Verstärkungsvorgarne eingesetzt, die eine Höchstzugkraft, bezogen auf den Endtiter, von mindestens 60 cN/tex aufweisen.Reinforcement rovings are preferably used which have a maximum tensile force, based on the final titer, of at least 60 cN / tex.

Weitere bevorzugte Verstärkungsvorgarne weisen einen Thermoschrumpf bei 200°C von 2 bis 8 % auf.Further preferred reinforcement rovings have a thermal shrinkage at 200 ° C. of 2 to 8%.

Weitere bevorzugte Verstärkungsvorgarne weisen eine Höchstzugkraftdehnung von 0,5 bis 25 % auf.Other preferred reinforcement rovings have a maximum tensile strength stretch of 0.5 to 25%.

An die mechanischen Eigenschaften der Matrixvorgarne werden keine hohen Anforderungen gestellt. Diese müssen zumindest den Verwirbelungsschritt überstehen.No high demands are made on the mechanical properties of the matrix rovings. These must at least survive the swirling step.

Nach dem Verlassen der Verwirbelungsdüse wird das primäre Hybridgarn abgezogen, wobei üblicherweise höchstens eine geringe Spannung auftreten darf. Je nach den Differenzen in der Voreilung der Vorgarne und den Verwirbelungsbedingungen in der Düse kann sich ein Primärhybridgarn mit keinem, geringem oder hohem Anteil von Schlingen ausbilden. Wird ein Glattgarn gewünscht, so kann das Primärgarn mit geringem oder hohem Anteil von Schlingen unter Schrumpfzulassung erhitzt werden. Dabei ziehen sich die Schlingen zusammen und die Garnstruktur wird weitgehend geglättet. Bereits in der Verwirbelungsdüse entstandene Glattgarne werden üblicherweise direkt abgezogen und aufgespult.After leaving the intermingling nozzle, the primary hybrid yarn is drawn off, with usually only a low tension being allowed to occur. Depending on the differences in the advance of the rovings and the intermingling conditions in the nozzle, a primary hybrid yarn can be formed with no, little or a high proportion of loops. If a plain yarn is desired, the primary yarn can be heated with a low or high proportion of loops with shrinkage approval. The loops contract and the yarn structure is largely smoothed. Smooth yarns that have already formed in the intermingling nozzle are usually drawn off and wound up directly.

Die Verwirbelung der Hybridgarne aus Verstärkungs- und Matrixfilamenten der oben beschriebenen ersten Ausführungsform erfolgt vorzugsweise mittels eines speziellen Warm-Verwirbelungsverfahrens, das in EP-B-0,455,193 beschrieben ist. Hierbei werden zur Vermeidung von Filamentbrüchen beim Verwirbeln die Verstärkungsfilamente vor deren Verwirbeln bis nahe dem Erweichungspunkt erwärmt (bei Glas ca. 600 °C). Die Erwärmung kann durch Galetten und/oder Heizrohr erfolgen, während die niedrigschmelzenden thermoplastischen Einzelfilamente aus Polyester ebenfalls vorerwärmt werden, um den Schrumpf auszulösen, und der übergeordneten Verwirbelungsdüse zugeführt werden. Die resultierenden glatten, mit hohem Fadenschluß ausgestatteten Hybridgarne sind problemlos webtauglich.The interlacing of the hybrid yarns from reinforcement and matrix filaments of the first embodiment described above is preferably carried out by means of a special warm interlacing process, which is described in EP-B-0,455,193. In order to avoid filament breakage during swirling, the reinforcement filaments are warmed up to near the softening point before swirling (approx. 600 ° C for glass). The heating can be done by godets and / or heating tube, while the low-melting thermoplastic single filaments made of polyester are also preheated to trigger the shrinkage and fed to the higher-level swirl nozzle. The resulting smooth, high-thread-lock hybrid yarns are easily weaved.

Es wurde gefunden, daß die Herstellung der Hybridgarne aus Verstärkungs- und Matrixfilamenten der oben beschriebenen zweiten Ausführungsform überraschenderweise nach an sich üblichen Verwirbelungstechniken, beispielsweise durch Intermingling- oder Commingling-Techniken erfolgen kann, wie beispielsweise in Chemiefasern/Textilindustrie, (7/8) 1989, T 185-7 beschrieben; allerdings durch den oben beschrieben Erhitzungsschritt des Matrixvorgarnes modifziert.It has been found that the production of the hybrid yarns from reinforcement and matrix filaments of the second embodiment described above can surprisingly be carried out according to conventional intermingling techniques, for example by intermingling or commingling techniques, such as in chemical fibers / textile industry, (7/8) 1989 , M 185-7; however modified by the heating step of the matrix roving described above.

Die erfindungsgemäßen Hybridgarne können nach an sich bekannten Verfahren zu textilen Flächengebilden verarbeitet werden. Beispiele dafür sind Gewebe, Gestricke, Gewirke und insbesondere Gelege. Derartige textile Flächengebilde können durch Aufschmelzen der Matrixkomponente in Verbundwerkstoffe übergeführt oder stabilisiert werden.The hybrid yarns according to the invention can be processed into textile fabrics by methods known per se. Examples of this are woven fabrics, knitted fabrics, knitted fabrics and, in particular, scrims. Such textile fabrics can be converted or stabilized by melting the matrix component in composite materials.

Die Erfindung betrifft auch die Verwendung der Hybridgarne zu diesen Zwecken.The invention also relates to the use of the hybrid yarns for these purposes.

Die nachfolgenden Beispiele verdeutlichen die Erfindung ohne diese zu begrenzen.The following examples illustrate the invention without limiting it.

BeispieleExamples 1) Herstellung von schrumpfarmen Hybridgarnen1) Production of low-shrink hybrid yarns

Auf einem Spulengatter wurde eine Spule mit Verstärkungsvorgarn und eine Spule mit Matrixvorgarn vorgelegt. Die Natur der Vorgarne sowie die verwendeten Garntiter sind in der nachstehenden Tabelle 1 aufgeführt.A bobbin with reinforcing roving and a bobbin with matrix roving were placed on a creel. The nature of the rovings and the yarn titer used are listed in Table 1 below.

Das Verstärkungsvorgarn wurde über ein Lieferwerk bestehend aus drei Galetten direkt einer Verwirbelungsdüse zugeführt. In einigen Versuchen wurde zwischen die Liefergaletten eine Heizvorrichtung dazwischengeschaltet. Dabei handelte es sich um eine Vorrichtung zum berührungslosen Beheizen von laufenden Fäden, wie sie in der EP-A-569,082 beschrieben worden ist.The reinforcing roving was fed directly to a intermingling nozzle via a delivery system consisting of three godets. In some trials, a heater was interposed between the delivery godets. This was a device for the contactless heating of running threads, as described in EP-A-569,082.

Das Matrixvorgarn wurde über ein Lieferwerk bestehend aus zwei Galetten und einer dazwischen angeordneten Heizvorrichtung ebenfalls der Texturierdüse zugeführt. Anstelle oder zusätzlich zur dazwischengeschalteten Heizvorrichtung wurden die Liefergaletten erhitzt. Bei der Heizvorrichtung handelte es sich um eine Vorrichtung zum berührungslosen Beheizen von laufenden Fäden, wie sie in der EP-A-579,092 beschrieben worden ist.The matrix roving was also fed to the texturing nozzle via a delivery unit consisting of two godets and a heating device arranged between them. Instead of or in addition to the intermediate heating device, the delivery godets were heated. The heating device was a device for the contactless heating of running threads, as described in EP-A-579,092.

Das Verhältnis der Überlieferung vor der Verwirbelungsdüse und dem nachgeschalteten Abzugswerk bei den Verstärkungsvorgarnen und bei den Matrixvorgarnen werden ebenfalls in der unten aufgeführten Tabelle angegeben.The relationship between the delivery before the intermingling nozzle and the downstream take-off unit for the reinforcement roving and for the matrix roving is also given in the table below.

Die Temperaturen der Galetten der Lieferwerke betrugen wahlweise zwischen 80 und 130 °C.The temperatures of the godets of the delivery plants were between 80 and 130 ° C.

Nach dem Verlassen der Verwirbelungsdüse wurde das primäre Hybridgarn mittels einer weiteren Galette abgezogen, wobei die Oberflächengeschwindigkeit der Galette so eingeregelt wurde, daß die Garnstruktur auf die textilen Gebrauchseigenschaften optimiert wurde. Einzelheiten zur Durchführung des Verfahrens finden sich in der nachfolgenden Tabelle.After leaving the intermingling nozzle, the primary hybrid yarn was drawn off by means of a further godet, the surface speed of the godet being adjusted in such a way that the yarn structure was optimized for the textile properties. Details on the implementation of the procedure can be found in the table below.

In einer weiteren Tabelle 2 werden die Eigenschaften der erhaltenen Hybridgarne dargestellt. Tabelle 1 Herstellungsbedingungen der Hybridgarne Beispiel Nr. Verstärkungsvorgarn (Typ; Titer dtex) Matrixvorgarn (Typ; Titer dtex) Überlieferung Heizer-/Galettentemperatur Verst.vorgarn (°C) Heizer-/Galetten temperatur Matr.vorgarn (°C) Verst. vorgarn Matrix vorgarn (%) 1 PET 1100 mod.PET 280 - 60 - 110 (Gal) 2 PET 550 mod.PET 280 - 30 - 110 (Gal) 3 Glas 3000 mod.PET 840 - 30 500 110 (Gal) 4 Glas 3000 mod.PET 840 - 10 - 160 5 Glas 3000 mod.PET 830 - 30 500 110 (Gal) 6 Glas 3000 mod.PET 750 - 60 500 210 60 (Gal) 7 Aramid 1100 mod.PET 280 - 50 100 (Gal) 110 (Gal) 8 C-Faser 3000 mod.PET 840 - 50 110 (Gal) 110 (Gal) PET = Polyethylenterephthalat
mod.PET = isophthalsäure-modifiziertes PET Tabelle 2 Eigenschaften der Hybridgarne Beispiel Nr. eff. Titer (dtex) Festigkeit (cN/tex) Dehnung (%) Schrumpf bei 200°C Schrumpf bei 160 °C 1 1600 50,2 18,1 3,5 1,1 2 930 37,9 21,8 3,9 1,0 3 4067 45,9 0,7 0 0 4 3880 46,5 0,8 0 0 5 4180 36,7 0,8 0,5 0 6 4590 39,8 0,8 3,1 0,6 7 1583 124,6 3,6 0,3 0 8 3219 56,1 1,3 0,1 0 The properties of the hybrid yarns obtained are shown in a further Table 2. Table 1 Manufacturing conditions of the hybrid yarns Example No. Reinforcement roving (type; titer dtex) Matrix roving (type; titer dtex) Lore Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Ampl. roving Roving matrix (%) 1 PET 1100 mod.PET 280 - 60 - 110 (gal) 2nd PET 550 mod.PET 280 - 30th - 110 (gal) 3rd Glass 3000 mod.PET 840 - 30th 500 110 (gal) 4th Glass 3000 mod.PET 840 - 10th - 160 5 Glass 3000 mod.PET 830 - 30th 500 110 (gal) 6 Glass 3000 mod.PET 750 - 60 500 210 60 (gal) 7 Aramid 1100 mod.PET 280 - 50 100 (gal) 110 (gal) 8th C-fiber 3000 mod.PET 840 - 50 110 (gal) 110 (gal) PET = polyethylene terephthalate
mod.PET = isophthalic acid-modified PET Properties of the hybrid yarns Example No. eff. Titer (dtex) Strength (cN / tex) Strain (%) Shrinkage at 200 ° C Shrinkage at 160 ° C 1 1600 50.2 18.1 3.5 1.1 2nd 930 37.9 21.8 3.9 1.0 3rd 4067 45.9 0.7 0 0 4th 3880 46.5 0.8 0 0 5 4180 36.7 0.8 0.5 0 6 4590 39.8 0.8 3.1 0.6 7 1583 124.6 3.6 0.3 0 8th 3219 56.1 1.3 0.1 0

2) Herstellung von schrumpfarmen Hybridgarnen (Variation der Voreilung des Matrixvorgarnes)2) Production of low-shrinkage hybrid yarns (variation of the advance of the matrix roving)

Analog zu Beispiel 1 wurden Hybridgarne durch Verwirbeln hergestellt. Als Verstärkungsvorgarne wurden hochfeste PET-Multifilamentgarne des Titers 1100 dtex eingesetzt und als Matrixvorgarne Filamentgarne des Titers 280 dtex auf der Basis von isophthalsäure-modifiziertem PET. Einzelheiten zu den Herstellungsbedingungen sind in Tabelle 3 aufgelistet. Die Eigenschaften der erhaltenen Garne sind in Tabelle 4 dargestellt. Tabelle 3 Herstellungsbedingungen der Hybridgarne Beispiel Nr. Überlieferung Heizer-/Galettentemperatur Verst.vorgarn (°C) Heizer-/Galetten temperatur Matr.vorgarn (°C) Verst. vorgarn Matrix vorgarn 9 - - - - 10 - 10 % 100 (Gal) 110 (Gal) 11 - 20 % 100 (Gal) 110 (Gal) 12 - 30 % 100 (Gal) 110 (Gal) 13 - 40 % 100 (Gal) 110 (Gal) 14 - 50 % 100 (Gal) 110 (Gal) 15 - 60 % 100 (Gal) 110 (Gal) Tabelle 4 Eigenschaften der Hybridgarne Beispiel Nr. eff. Titer (dtex) Festigkeit (cN/tex) Dehnung (%) Schrumpf bei 200°C Schrumpf bei 160 °C 9 1430 56,4 18,9 8,9 7 10 1455 55,8 18,0 5,4 1,9 11 1483 55,3 18,1 4,4 1,5 12 1517 53,7 18,2 4,2 1,4 13 1537 53,5 18,6 3,9 0,6 14 1577 50,5 17,9 3,7 1,1 15 1600 50,2 18,1 3,5 1,1 Analogous to Example 1, hybrid yarns were produced by intermingling. High-strength PET multifilament yarns with a titre of 1100 dtex were used as reinforcing rovings 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. Table 3 Manufacturing conditions of the hybrid yarns Example No. Lore Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Ampl. roving Roving matrix 9 - - - - 10th - 10% 100 (gal) 110 (gal) 11 - 20% 100 (gal) 110 (gal) 12th - 30% 100 (gal) 110 (gal) 13 - 40% 100 (gal) 110 (gal) 14 - 50% 100 (gal) 110 (gal) 15 - 60% 100 (gal) 110 (gal) Properties of the hybrid yarns Example No. eff. Titer (dtex) Strength (cN / tex) Strain (%) Shrinkage at 200 ° C Shrinkage at 160 ° C 9 1430 56.4 18.9 8.9 7 10th 1455 55.8 18.0 5.4 1.9 11 1483 55.3 18.1 4.4 1.5 12th 1517 53.7 18.2 4.2 1.4 13 1537 53.5 18.6 3.9 0.6 14 1577 50.5 17.9 3.7 1.1 15 1600 50.2 18.1 3.5 1.1

Diese Beispiele zeigen, daß der Schrumpf des verwirbelten Garnes sich bei der Vergrößerung der Voreilung des Matrixvorgarnes verringert.These examples show that the shrinkage of the intermingled yarn decreases as the advance of the matrix roving increases.

3) Herstellung Von schrumpfarmen Hybridgarnen (Variation der Voreilung und der Erhitzung des Matrixvorgarnes)3) Production of low-shrinkage hybrid yarns (variation of the advance and the heating of the matrix roving)

Analog zu Beispiel 1 wurden Hybridgarne durch Verwirbeln hergestellt. Als Verstärkungsvorgarne wurden Glas-Multifilamentgarne des Titers 3000 dtex eingesetzt und als Matrixvorgarne Filamentgarne des Titers 750 dtex auf der Basis von isophthalsäure-modifiziertem PET. Einzelheiten zu den Herstellungsbedingungen sind in Tabelle 5 aufgelistet. Die Eigenschaften der erhaltenen Garne sind in Tabelle 6 dargestellt. Tabelle 5 Herstellungsbedingungen der Hybridgarne Beispiel Nr. Überlieferung Heizer-/Galettentemperatur Verst.vorgarn (°C) Heizer-/Galetten temperatur Matr.vorgarn (°C) Verst. vorgarn Matrix vorgarn 16 - - - 210 17 - 10 % - 210 18 - 20 % - 210 19 - 30 % - 210 20 - 40 % - 210 21 - 50 % - 210 + 60 (Gal) 22 - 60 % - 210 + 60 (Gal) Tabelle 6 Eigenschaften der Hybridgarne Beispiel Nr. eff. Titer (dtex) Festigkeit (cN/tex) Dehnung (%) Schrumpf bei 200°C Schrumpf bei 160 °C 16 4181 36,1 1,1 65,5 n.b. 17 4250 34,4 0,7 33,4 n.b. 18 4310 28,7 0,9 29,5 n.b. 19 4380 27,5 0,7 25,1 n.b. 20 4450 29,3 1,1 18,8 n.b. 21 4515 30,8 1,3 7,5 3,8 22 4590 39,8 0,8 3,1 0,9 n.b. = nicht bestimmt Analogous to Example 1, hybrid yarns were produced by intermingling. 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 as matrix rovings. Details of the manufacturing conditions are listed in Table 5. The properties of the yarns obtained are shown in Table 6. Table 5 Manufacturing conditions of the hybrid yarns Example No. Lore Heater / godet temperature reinforcing roving (° C) Heater / godet temperature Mat roving (° C) Ampl. roving Roving matrix 16 - - - 210 17th - 10% - 210 18th - 20% - 210 19th - 30% - 210 20th - 40% - 210 21 - 50% - 210 + 60 (gal) 22 - 60% - 210 + 60 (gal) Properties of the hybrid yarns Example No. eff. Titer (dtex) Strength (cN / tex) Strain (%) Shrinkage at 200 ° C Shrinkage at 160 ° C 16 4181 36.1 1.1 65.5 nb 17th 4250 34.4 0.7 33.4 nb 18th 4310 28.7 0.9 29.5 nb 19th 4380 27.5 0.7 25.1 nb 20th 4450 29.3 1.1 18.8 nb 21 4515 30.8 1.3 7.5 3.8 22 4590 39.8 0.8 3.1 0.9 nb = not determined

Diese Beispiele zeigen, daß der Schrumpf des verwirbelten Garnes sich bei der Vergrößerung der Voreilung sowie einer verstärkten Erhitzung des Matrixvorgarnes verringert.These examples show that the shrinkage of the intermingled yarn decreases as the lead increases and the matrix roving heats up more.

4) Bestimmung des Schrumpfes eines Hybridgarnes bei unterschiedlicher Vorspannkraft4) Determination of the shrinkage of a hybrid yarn with different pretensioning forces

In Analogie zu den oben beschriebenen Beispielen wurde ein schrumpfarmes Hybridgarn mit Verstärkungsvorgarn aus PET und mit Matrixvorgarn aus isophthalsäure-modifiziertem PET hergestellt. Der Garntiter betrug 1380 dtex. Dieses Garn wurde mit unterschiedlichen Vorspanngewichten belastet und jeweils für 15 Minuten im Umluftofen bei einer Lufttemperatur von 100 °C bzw. von 160 °C behandelt. Es wurden folgende Thermoschrumpfwerte gemessen: Vorspanngewicht (cN) 0,16 0,5 0,8 1,5 3 Thermoschrumpf bei 100°C 33,5 2,3 1 0,5 0,5 Thermoschrumpf bei 160°C 0,4 0,3 0,3 0,2 0,1 In analogy to the examples described above, a low-shrinkage hybrid yarn with reinforcing roving made of PET and with matrix roving made of isophthalic acid-modified PET was produced. The yarn titer was 1380 dtex. This yarn was loaded with different pretension weights and each 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 3rd 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

5) Bestimmung des Verwirbelungsabstandes von Hybridgarnes mit unterschiedlichem Anteil an Matrixkomponente5) Determination of the intermingling distance of hybrid yarns with different proportions of matrix components

In Analogie zu den oben beschriebenen Beispielen wurden verschiedene schrumpfarme Hybridgarne mit Verstärkungsvorgarn aus hochfestem PET und mit Matrixvorgarn aus isophthalsäure-modifiziertem PET hergestellt. Die Garne unterschieden sich durch den Mengenanteil der Matrixkomponente und durch einen unterschiedlichen Verwirbelungsgrad. Der Verwirbelungsabstand wurde mittels eines Rothschild Entanglement Testers ermittelt. Es wurden folgende Werte gemessen: Volumen % Matrix im Hybridgarn 90 90 80 80 70 70 60 60 50 50 intensiv verwirbelt + - + - + - + - + - flach verwirbelt - + - + - + - + - + Verwirbelungsabstand (mm) 57 101 41 87 32 70 28 59 19 51 In analogy to the examples described above, various low-shrinkage hybrid yarns with reinforcing roving made from high-strength PET and with matrix roving made from isophthalic acid-modified PET were produced. The yarns differed by the amount of the matrix component and by a different degree of intermingling. The swirl distance was determined using a Rothschild Entanglement Tester. The following values were measured: Volume% matrix in hybrid yarn 90 90 80 80 70 70 60 60 50 50 swirled intensely + - + - + - + - + - swirled flat - + - + - + - + - + Swirl distance (mm) 57 101 41 87 32 70 28 59 19th 51

6) Charakterisierung von Eigenschaften von Hybridgarnen mit einer Matrixkomponente mit unterschiedlichem Schmelzpunkt6) Characterization of properties of hybrid yarns with a matrix component with different melting points

In Analogie zu den oben beschriebenen Beispielen wurden schrumpfarme Hybridgarne aus Verstärkungsvorgarn aus PET und aus Matrixvorgarn aus unterschiedlichen isophthalsäure-modifizierten PET-Typen hergestellt. Die Herstellungsbedingungen waren jeweils gleich. Die Matrixvorgarne unterschieden sich im Schmelzbereich des PET-Typs. Der Anteil der Matrixkomponente in den Hybridgarnen betrug jeweils 15 bis 20 Vol %. Die Überlieferung des Matrixvorgarnes lag zwischen 50 und 100 %. Einige Eigenschaften der hergestellten Hybridgarne sind in der folgenden Tabelle aufgelistet. Hybridgarn Probe A B C Schmelzbereich mod.PET Komponente (°C) ca. 130 ca. 170 ca. 225 Garntiter (dtex) 1330 1313 1558 Thermoschrumpf bei 160°C 0,7 0,9 0,9 Thermoschrumpf bei 200°C 1,3 1,8 1,9 Höchstzugkraftdehnung (%) 16 16,5 15,8 Höchstzugkraft (cN/tex) 51 52,5 48,8 In analogy to the examples described above, low-shrinkage hybrid yarns were produced from reinforcing roving made from PET and from matrix roving made from different types of PET modified with isophthalic acid. The manufacturing conditions were the same in each case. The matrix rovings differ in the melting range of the PET type. The proportion of the matrix component in the hybrid yarns was 15 to 20% by volume. The delivery of the matrix roving was between 50 and 100%. Some properties of the hybrid yarns produced are listed in the following table. Hybrid yarn sample A B C. Melting range mod.PET component (° C) about 130 approx. 170 approx. 225 Yarn titer (dtex) 1330 1313 1558 Thermal shrink at 160 ° C 0.7 0.9 0.9 Thermal shrink at 200 ° C 1.3 1.8 1.9 Maximum tensile force elongation (%) 16 16.5 15.8 Maximum tensile force (cN / tex) 51 52.5 48.8

Es ist zu erkennen, daß sich Hybridgarne mit unterschiedlichen Schmelzbereichen der Matrixkomponente aber vergleichbaren mechanischen Eigenschaften herstellen lassen.It can be seen that hybrid yarns with different melting ranges of the matrix component but comparable mechanical properties can be produced.

Claims (16)

Hybridgarne enthaltend Verstärkungsfilamente und Matrixfilamente aus thermoplastischen Polymeren, die einen tieferen Schmelzpunkt als der Schmelz- oder Zersetzungspunkt der Verstärkungsfilamente aufweisen, dadurch gekennzeichnet, daß die Hybridgarne einen Thermoschrumpf, gemessen an einer Garnprobe unter einer Belastung von 0,0004 cN/dtex bei einer Lufttemperatur von 160 °C, von kleiner gleich 2 %, insbesondere von kleiner gleich 1 %, und bei einer Lufttemperatur von 200 °C von kleiner gleich 5 %, insbesondere von kleiner gleich 3 %, aufweisen.Hybrid yarns containing reinforcing filaments and matrix filaments made of thermoplastic polymers, which have a lower melting point than the melting or decomposition point of the reinforcing filaments, characterized in that the hybrid yarns undergo thermal shrinkage, measured on a yarn sample under a load of 0.0004 cN / dtex at an air temperature of 160 ° C, less than or equal to 2%, in particular less than or equal to 1%, and at an air temperature of 200 ° C of less than or equal to 5%, in particular less than or equal to 3%. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß diese eine statische Schrumpfkraft, gemessen nach DIN 53866, Teil 12, bei Temperaturen von bis zu 200 °C von bis zu 0,01 cN/dtex aufweisen.Hybrid yarns according to claim 1, characterized in that they have a static shrinkage force, measured according to DIN 53866, part 12, at temperatures of up to 200 ° C of up to 0.01 cN / dtex. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß diese einen Verwirbelungsabstand von weniger als 60 mm, vorzugsweise weniger als 30 mm aufweisen, wobei dieser Wert sich auf eine Messung mit dem Rothschild Entanglement Nadeltestgerät 2050 bezieht.Hybrid yarns according to claim 1, characterized in that they have a swirl distance of less than 60 mm, preferably less than 30 mm, this value relating to a measurement with the Rothschild Entanglement needle tester 2050. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß es sich um Glattgarne handelt.Hybrid yarn according to claim 1, characterized in that it is plain yarn. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß die Matrixfilamente aus thermoplastischen Polymeren einen Schmelzpunkt aufweisen, der mindestens 30 °C unter dem Schmelz- oder Zerstetzungspunkt der Verstärkungsfilamtente liegt.Hybrid yarns according to claim 1, characterized in that the matrix filaments made of thermoplastic polymers have a melting point which is at least 30 ° C below the melting or destruction point of the reinforcing filament. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß die Verstärkungsfilamente einen Anfangsmodul von größer als 50 Gpa aufweisen, und vorzugsweise aus Glas, Kohlenstoff oder aromatischem Polyamid bestehen.Hybrid yarns according to claim 1, characterized in that the reinforcing filaments have an initial modulus of greater than 50 Gpa and preferably consist of glass, carbon or aromatic polyamide. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß die Verstärkungsfilamente einen Anfangsmodul von größer als 10 GPa aufweisen und aus Polyester, insbesondere aus Polyethylenterephthalat, bestehen.Hybrid yarns according to claim 1, characterized in that the reinforcing filaments have an initial modulus of greater than 10 GPa and consist of polyester, in particular of polyethylene terephthalate. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß die Matrixfilamente auf Polybutylenterephthalat und/oder aus Polyethylenterephthalat und/oder aus chemisch modifiziertem Polyethylenterephthalat bestehen.Hybrid yarns according to claim 1, characterized in that the matrix filaments consist of polybutylene terephthalate and / or of polyethylene terephthalate and / or of chemically modified polyethylene terephthalate. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß Verstärkungsfilamente und Matrixfilamente aus einer Polymerklasse bestehen, vorzugsweise aus Kombinationen Polyamid/Polyamid, Polyolefin/Polyolefin oder insbesondere aus Polyester/Polyester.Hybrid yarns according to claim 1, characterized in that reinforcing filaments and matrix filaments consist of a polymer class, preferably of combinations of polyamide / polyamide, polyolefin / polyolefin or in particular of polyester / polyester. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß die Matrixfilamente aus einem chemisch modifizierten Polyethylenterephthalat enthaltend die wiederkehrenden Struktureinheiten der Formeln I und II bestehen

        -O-OC-Ar1-CO-O-R1-     (I),



        -O-OC-R2-CO-O-R3-     (II),

worin Ar1 einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, vorzugsweise 1,4-Phenylen und/oder 2,6-Naphthylen darstellt, R1 und R3 unabhängig voneinander zweiertige alipahtische oder cycloaliphatische Reste darstellen, insbesondere Reste der Formel -CnH2n-, worin n eine ganze Zahl zwischen 2 und 10 ist, insbesondere Ethylen, oder einen von Cyclohexandimethanol agbeleiteten Rest darstellen, und R2 einen zweiwertigen aliphatischen, cycloaliphatischen oder ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in meta-Stellung oder in einer zu dieser Stellung vergleichbaren gewinkelten Stellung zueinander befinden, vorzugsweise 1,3-Phenylen darstellt.Hybrid yarns according to claim 1, characterized in that the matrix filaments consist of a chemically modified polyethylene terephthalate containing the recurring structural units of the formulas I and II

-O-OC-Ar 1 -CO-OR 1 - (I),



-O-OC-R 2 -CO-OR 3 - (II),

in which Ar 1 represents a divalent mono- 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 represent two-part 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 a divalent aliphatic, cycloaliphatic or mono- or represents polynuclear aromatic radical, the free valences of which are in the meta position or in an angular position comparable to this position, preferably represents 1,3-phenylene. Hybridgarne nach Anspruch 10, dadurch gekennzeichnet, daß die Matrixfilamente aus einem chemisch modifizierten Polyethylenterephthalat bestehen, das 40 bis 95 Mol % der wiederkehrenden Struktureinheiten der Formel I und 60 bis 5 Mol % der wiederkehrenden Struktureinheiten der Formel II enthält, worin Ar1 1,4-Phenylen und/oder 2,6-Naphthylen ist, R1 und R3 Ethylen bedeuten und R2 1,3-Phenylen ist.Hybrid yarns according to Claim 10, characterized in that the matrix filaments consist of a chemically modified polyethylene terephthalate which contains 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 1.4 -Phenylene and / or 2,6-naphthylene, R 1 and R 3 are ethylene and R 2 is 1,3-phenylene. Hybridgarne nach Anspruch 1, dadurch gekennzeichnet, daß die Matrixfilamente aus einem thermoplastischen und elastomeren Polymeren bestehen, insbesondere aus einem Polyurethan, einem Polyamid oder vorzugsweise aus einem Polyester.Hybrid yarns according to claim 1, characterized in that the matrix filaments consist of a thermoplastic and elastomeric polymer, in particular a polyurethane, a polyamide or preferably a polyester. Verfahren zur Herstellung der schrumpfarmen Hybridgarne nach Anspruch 1 umfassend die Maßnahmen a) Zuführen von zwei oder mehreren sich mit unterschiedlichen Geschwindigkeiten bewegenden Vorgarnsträngen zu einer Verwirbelungsdüse, wobei zumindest eine Teil der Vorgarnstränge (Verstärkungsvorgarn) aus Verstärkungsfilamenten besteht und ein weiterer Teil der Vorgarnstränge (Matrixvorgarn) aus tieferschmelzenden Matrixfilamenten aus thermoplastischen Polymeren besteht, die einen Thermoschrumpf bei 200 °C von mehr als 20 % aufweisen, b) Erwärmen des Matrixvorgarnes während des Zuführens in die Verwirbelungsdüse auf eine derartige Temperatur, daß zumindest ein Teil des Schrumpfes ausgelöst wird, c) Verwirbeln der Vorgarnstränge in der Verwirbelungsdüse unter derartigen Bedingungen, daß sich ein primäres Hybridgarn ausbildet, und d) Abziehen des erhaltenen primären Hybridgarnes gegebenenfalls unter Schrumpf und/oder zusätzlichem Erhitzen. A method for producing the low shrinkage hybrid yarn according to claim 1 comprising the measures a) Feeding two or more roving strands moving at different speeds to a intermingling nozzle, wherein at least some of the roving strands (reinforcing roving) consist of reinforcing filaments and a further part of the roving strands (matrix roving) consist of melting melting matrix filaments made of thermoplastic polymers, which heat shrink Have 200 ° C of more than 20%, b) heating the matrix roving to a temperature such that at least part of the shrinkage is triggered, while being fed into the intermingling nozzle, c) intermingling the roving strands in the intermingling nozzle under conditions such that a primary hybrid yarn is formed, and d) drawing off the primary hybrid yarn obtained, optionally with shrinkage and / or additional heating. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß die Unterschiede in der Voreilung der in die Verwirbelungsdüse einlaufenden Vorgarne so gewählt werden, daß sich beim Verwirbeln ein Hybridglattgarn ausbildet.A method according to claim 13, characterized in that the differences in the advance of the rovings entering the intermingling nozzle are selected so that a hybrid smooth yarn is formed during intermingling. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß die Unterschiede in der Voreilung der in die Verwirbelungsdüse einlaufenden Vorgarne so gewählt werden, daß sich beim Verwirbeln ein Hybridschlingengarn ausbildet, dessen Schlingen durch Auslösen des Schrumpfes in einer oder mehreren darauffolgenden Erhitzungsstufen wieder weitgehend geglättet werden.A method according to claim 13, characterized in that the differences in the advance of the rovings entering the intermingling nozzle are selected such that a hybrid loop yarn is formed during intermingling, the loops of which are largely smoothed out again by triggering the shrinkage in one or more subsequent heating stages. Verwendung der schrumpfarmen Hybridgarne nach Anspruch 1 zur Herstellung von Verbundwerkstoffen oder von textilen Flächengebilden, insbesondere zur Herstellung von Gelegen.Use of the low-shrinkage hybrid yarns according to claim 1 for the production of composite materials or textile fabrics, in particular for the production of scrims.
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JP6297311B2 (en) * 2013-11-20 2018-03-20 旭化成株式会社 Cloth
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CN107227525A (en) * 2017-08-14 2017-10-03 太仓市天茂化纤有限公司 A kind of comfortable blend fibre of high strength and modulus

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US5879800A (en) 1999-03-09
EP0801159A3 (en) 1998-09-16
CN1165211A (en) 1997-11-19
US6109016A (en) 2000-08-29
DE19613965A1 (en) 1997-10-16
DE59710673D1 (en) 2003-10-09
EP0801159B1 (en) 2003-09-03
KR970070267A (en) 1997-11-07

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