EP4363642B1 - Fil electroconducteur - Google Patents

Fil electroconducteur Download PDF

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Publication number
EP4363642B1
EP4363642B1 EP22735413.1A EP22735413A EP4363642B1 EP 4363642 B1 EP4363642 B1 EP 4363642B1 EP 22735413 A EP22735413 A EP 22735413A EP 4363642 B1 EP4363642 B1 EP 4363642B1
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EP
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Prior art keywords
yarn
maximum
electrically conductive
din
thermoplastic
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German (de)
English (en)
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EP4363642A1 (fr
Inventor
Pascal FREUND
Tim Biemelt
Thomas Rademacher
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Indorama Ventures Fibers Germany GmbH
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Indorama Ventures Fibers Germany GmbH
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    • 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
    • D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
    • 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
    • D02G3/404—Yarns or threads coated with polymeric solutions

Definitions

  • the invention relates to an electrically conductive yarn with good physical and mechanical properties, a process for its production and its use.
  • thermoplastic polymers in which an electrically conductive material is incorporated into the thermoplastic polymer or a yarn made of thermoplastic polymer is provided with an electrically conductive sheath, for example in the form of a bi-component fiber. Examples of this can be found in EP-A-1559815 and EP-A-3502327 , as well as in US Patent 3,586,597 and JP-A-2006/161190 .
  • thermoplastic polymers e.g. graphite or carbon black
  • electrically conductive materials e.g. graphite or carbon black
  • the multifilament yarn present in the yarn according to the invention has a fineness-related strength of 40 to 300 cN/tex. Fineness-related strengths of 50 to 280 cN/tex, in particular 60 to 260 cN/tex, are particularly preferred.
  • the multifilament yarn present in the yarn according to the invention has an elongation at break of a maximum of 25%, preferably a maximum of 20%.
  • the multifilament yarn present in the yarn according to the invention has a thermal shrinkage of a maximum of 6%, preferably a maximum of 3%.
  • the multifilament yarn according to the invention has a titer in the range from 100 to 1200 dtex, particularly preferably 250 to 500 dtex.
  • the dtex specification refers to fibers made of organic polymers, in particular thermoplastic polymers, particularly preferably polyester.
  • the multifilament yarn according to the invention preferably has 10 to 500 individual filaments.
  • the multifilament yarn according to the invention is electrically non-conductive.
  • electrically non-conductive means that the yarn has an electrical conductivity of ⁇ 10 -8 S/m.
  • the multifilament yarn according to the invention is preferably a multifilament yarn made of aramids, preferably so-called high-modulus aramids, polyesters, preferably so-called high-strength polyester multifilaments, polyamides, preferably so-called high-strength polyamide multifilaments, glass, mineral fibers (basalt), and based on so-called hybrid multifilament yarns which comprise two or more of the aforementioned materials.
  • the term high-strength stands for a fineness-related strength of at least 50 cN/tex, in particular of at least 60 cN/tex, particularly preferably of at least 70 cN/tex.
  • the multifilament yarn present in the yarn according to the invention preferably has a Young's modulus of at least 0.3 GPa, particularly preferably at least 0.5 GPa, in particular at least 0.8 GPa, particularly preferably at least 2 GPa or at least 2.5 GPa.
  • the multifilament yarn according to the invention is particularly preferably a multifilament yarn made of a thermoplastic polymer
  • thermoplastic polymer refers to a plastic that can be deformed (thermoplastically) in a certain temperature range, preferably in the range of 25°C to 350°C. This process is reversible, i.e. it can be repeated as often as desired by cooling and reheating to the molten state, as long as the material has not been damaged too much by overheating (so-called thermal decomposition) or by mechanical stress during shaping. This is what distinguishes thermoplastic polymers from thermosets and elastomers.
  • thermoplastic polymers used according to the invention are polymers from the group acrylonitrile-ethylene-propylene (diene) styrene copolymer, acrylonitrile-methacrylate copolymer, acrylonitrile-methyl methacrylate copolymer, chlorinated acrylonitrile, polyethylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene-propylene-styrene copolymer, cellulose acetobutyrate, cellulose acetopropionate, hydrated cellulose, carboxymethyl cellulose, cellulose nitrate, cellulose propionate, cellulose triacetate, polyvinyl chloride, ethylene-acrylic acid copolymer, ethylene-butyl acrylate copolymer, ethylene chlorotrifluoroethylene copolymer, ethylene-ethlyacrylate copolymer, ethylene methacrylate copolymer
  • thermoplastic polymers melt-spinnable synthetic polycondensates are preferred.
  • suitable thermoplastic polymers are melt-spinnable synthetic biopolymers.
  • synthetic biopolymer refers to a material that consists at least predominantly of biogenic raw materials (renewable raw materials). This distinguishes it from conventional, petroleum-based materials or plastics, such as polyethylene (PE), polypropylene (PP) and polyvinyl chloride (PVC).
  • PE polyethylene
  • PP polypropylene
  • PVC polyvinyl chloride
  • melt-spinnable synthetic polycondensates are preferred among the thermoplastic polymers. These are aliphatic polyesters, arylaliphatic polyesters, aromatic polyesters and their co-/ter-polymers, which are produced from polyols and aliphatic and/or aromatic dicarboxylic acids or their derivatives (anhydrides, esters) by polycondensation, whereby the polyols can be substituted or unsubstituted, and the polyols can be linear or branched polyols.
  • Preferred polyols are polyols having 2 to 8 carbon atoms, polyalkylene ether glycols having 2 to 8 carbon atoms and cycloaliphatic diols having 4 to 12 carbon atoms.
  • Examples of polyols that may be used include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, diethylene glycol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3
  • Preferred polyols include 1,4-butanediol, 1,3-propanediol, ethylene glycol, 1,6-hexanediol, diethylene glycol, isosorbitol and 1,4-cyclohexanedimethanol.
  • Preferred aliphatic dicarboxylic acids include substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from the group of aliphatic dicarboxylic acids having 2 to 12 carbon atoms and cycloaliphatic dicarboxylic acids having 5 to 10 carbon atoms, where the cycloaliphatic dicarboxylic acids may also have heteroatoms in the ring.
  • the substituted non-aromatic dicarboxylic acids typically contain 1 to 4 substituents selected from halogen, C6-C10 aryl and C1-C4 alkoxy.
  • Non-limiting examples of aliphatic and cycloaliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, 2,5-norbornanedicarboxylic acid.
  • Preferred aromatic dicarboxylic acids include substituted or unsubstituted aromatic dicarboxylic acids selected from the group of aromatic dicarboxylic acids having 6 to 12 carbon atoms, wherein these dicarboxylic acids may also have heteroatoms in the aromatic ring and/or in the substituent.
  • the substituted aromatic dicarboxylic acids may typically have 1 to 4 substituents selected from halogen, C6-C10 aryl and C1-C4 alkoxy.
  • Non-limiting examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and furandicarboxylic acid.
  • the multifilament yarn according to the invention has a diameter in the range of 200 ⁇ m to 600 ⁇ m, whereby this information refers to a multifilament yarn made of non-organic fibers, in particular carbon, glass, mineral fibers (basalt).
  • PET polyethylene terephthate
  • PBT polybutylene terephthate
  • PTT polytrimethylene terephthalate
  • PEN polyethylene naphthalate
  • polyesters are PET and PEN with a glass transition temperature of at least 70°C.
  • polyesters which contain at least 95 mol % polyethylene terephthalate (PET).
  • polyesters in particular polyethylene terephthalate, have a molecular weight corresponding to a specific viscosity ( ⁇ spec ) of at least 0.8 dl/g, in particular of at least 0.9 dl/g, each measured on solutions with 1 g/l polymer in dichloroacetic acid at 25°C.
  • ⁇ spec specific viscosity
  • polyester multifilament yarns are, for example, EP-A-0173221 and the passages cited therein.
  • Such high-strength polyester multifilament yarns are also known as tire cord and are used in technical products where high strength is required.
  • thermoplastic, polymer material is melted and fed into a spinning beam in a liquid state using an extruder. From this spinning beam, the melted material is fed to so-called spinnerets.
  • the spinneret usually has a spinneret plate with several holes from which the individual capillaries (filaments) of the fiber are extruded.
  • wet or solvent spinning processes are also used to produce spinning fibers. Instead of the melt, a highly viscous solution of a synthetic polymer is extruded through nozzles with fine holes. Both processes are referred to by experts as so-called multi-position spinning processes.
  • the polymer fibers produced in this way are subjected to fiber post-processing to achieve the desired mechanical strength.
  • This can involve modifying or finishing polymer fibers for the respective end application or for the necessary intermediate treatment steps, e.g. stretching and/or crimping, usually by applying suitable finishing agents or finishing agents. Sizes that are applied to the surface of the finished polymer fiber or the polymer fiber to be treated.
  • Additives such as antistatic agents or colored pigments, may be added to the thermoplastic polymer, usually by incorporation into the molten thermoplastic polymer during the multi-station spinning process of the polymer fiber.
  • thermoplastic multifilament yarn in particular the polyester multifilament yarn, is provided with a commercially available spinning oil which decouples the multifilament yarn core from the thermoplastic sheath.
  • the spinning oil is applied to the multifilament yarn before the sheathing of the multifilament yarn.
  • the spinning oil used is commercially available spinning oil.
  • Examples of corresponding commercial spinning oils are distillates (petroleum) consisting of dewaxed heavy paraffinic solvents (50-70%), mineral oils (25-50%), ethoxylated fatty alcohol (2.5-30%), C8-18 even-numbered amides (2.5-10%) and C18-unsaturated, N,Nbis(hydroxyethyl) C9-C11-alcohol ethoxylate ( ⁇ 2.5%).
  • ethylene glycol 2.5-10%), diisooctyl sodium sulfosuccinate (1-2.5%) and/or sodium alkanesulfonate (1- ⁇ 2.5%) may be included.
  • the sheath present in the yarn according to the invention is in contact with the multifilament yarn. This means that at least 90% of the surface of the multifilament yarn is in direct contact with the sheath or at least 90% of the surface of the multifilament yarn is in indirect contact with the sheath, provided that the previously described treatment with the spinning oil has taken place.
  • the sheath has a thickness of at least 10 ⁇ m, preferably at least 20 ⁇ m, particularly preferably at least 50 ⁇ m.
  • the thickness is not restricted in terms of the upper limit.
  • the maximum thickness is usually 300 ⁇ m, so that the thickness is in the range from 10 ⁇ m to 300 ⁇ m, preferably 50 ⁇ m to 300 ⁇ m, in particular in the range from 100 ⁇ m to 150 ⁇ m.
  • the sheath has an electrical conductivity of at least 150 S/m.
  • the electrically conductive material used in the sheath has an electrical conductivity of at least 3 ⁇ 10 2 S/m, preferably at least 1 ⁇ 10 6 S/m.
  • the sheath comprises 55 to 99% by weight of thermoplastic elastomer and 1 to 45% by weight of electrically conductive material, preferably 85 to 99% by weight of thermoplastic elastomer and 1 to 15% by weight of electrically conductive material, particularly preferably 90 to 99% by weight of thermoplastic elastomer and 1 to 10% by weight of electrically conductive material, in particular 94 to 99% by weight of thermoplastic elastomer and 1 to 6% by weight of electrically conductive material.
  • the sheath can also contain conventional additives, in particular those that facilitate the processability of the sheathing compound. The compound described above is referred to below as the sheath component.
  • thermoplastic elastomer refers to a thermoplastic elastomer according to DIN ES ISO 18064:2021-04 (replaces DIN EN ISO 18064:2015-03)
  • thermoplastic elastomer used according to the invention can be deformed (thermoplastically) in a certain temperature range, preferably in the range from 25°C to 350°C. This process is reversible, i.e. it can be repeated as often as desired by cooling and reheating to the molten state, as long as the material has not been damaged too much by overheating (so-called thermal decomposition) or by mechanical stress during shaping.
  • thermoplastic elastomer is usually obtained by combining thermoplastic with an elastomer, this can usually be done in two different ways, block polymers or polymer blends.
  • block polymers as thermoplastic elastomers are TPS, TPU, TPA and TPC.
  • TPS stands for styrene block copolymers, in particular styrene/butadiene/styrene (SBS), or styrene/ethylene-butylene/styrene (SEBS) or styrene/ethylene-propylene/styrene (SEPS) or styrene/isoprene/styrene (SIS) based styrene block copolymers.
  • SBS styrene/butadiene/styrene
  • SEBS styrene/ethylene-butylene/styrene
  • SEPS styrene/ethylene-propylene/styrene
  • SIS styrene/isoprene/styrene block copolymers.
  • These block copolymers have hard and soft segments, with the styrene group forming the hard segment and the aliphatic groups, in particular ali
  • TPS are characterized by a hardness of 10 Shore A to 70 Shore D.
  • Preferred within the TPS are styrene/butadiene/styrene (SBS), styrene/ethylene-butylene/styrene (SEBS), styrene/ethylene-propylene/styrene (SEPS) or styrene/isoprene/styrene (SIS) with a hardness of 75 Shore A to 40 Shore D.
  • TPS styrene/butadiene/styrene
  • SEBS styrene/ethylene-butylene/styrene
  • SEPS styrene/ethylene-propylene/styrene
  • SIS styrene/isoprene/styrene
  • styrene/butadiene/styrene SBS
  • SEBS styrene/ethylene-butylene/styrene
  • SEPS styrene/ethylene-propylene/styrene
  • SIS styrene/isoprene/styrene
  • SBS styrene/butadiene/styrene
  • SEBS styrene/ethylene-butylene/styrene
  • SEPS styrene/ethylene-propylene/styrene
  • SIS styrene/isoprene/styrene
  • TPSs include Elastron ® G and Elastron ® D, Kraton ® (Kraton Polymers), Septon ® (Kuraray), Styroflex ® (BASF), Thermolast ® (Kraiburg TPE), ALLRUNA ® (ALLOD Werkstoff GmbH & Co.KG) or Saxomer ® TPE-S (PCW), as well as Pre-Elect ® TPE (Premix).
  • the TPS elastomers mentioned above have particularly good conductivity and are also advantageous in processing. Yarns according to the invention with this sheath component have a particularly smooth surface.
  • TPU stands for thermoplastic polyurethane, i.e. a thermoplastic elastomer based on polyurethane. Such TPUs are characterized by a hardness of approximately 60 Shore A. Commercially available TPUs include Elastollan ® (BASF) or Desmopan ® , Texin ® , Utechllan ® (Covestro).
  • BASF Elastollan ®
  • Desmopan ® Desmopan ®
  • Texin ® Texin ®
  • Utechllan ® Covestro
  • TPA stands for thermoplastic polyether polyamide, ie a polyamide-based block polymer. Such TPAs are characterized by a hardness of 60 Shore A to 70 Shore D. Commercially available TPAs include PEBAX ® (Arkema), VESTAMID ® E (Evonik Industries).
  • TPC stands for thermoplastic polyester elastomer, ie a block copolymer on a copolyester basis. Such TPCs are characterized by a hardness of 80 Shore A to 70 Shore D. Commercially available TPCs include Hytrel ® (Du Pont), Keyflex ® (LG Chem), Skypel ® (SK Chemicals). Examples of suitable polymer blends as thermoplastic elastomers are TPO and TPV.
  • TPO stands for thermoplastic polyolefins, a mixture of a polyolefin-based plastic (usually PP or PE) and an elastomer such as EPDM. In contrast to TPV, TPO is not or only partially cross-linked.
  • TPOs are polymer mixtures that can be made hard or soft depending on their composition. Such TPOs are characterized by a hardness of 55 Shore A to 70 Shore D. Commercially available TPOs include Elastron ® TPO, Saxomer ® TPE-O (PCW).
  • TPV stands for thermoplastic polyolefin vulcanizates, a mixture of a polyolefin-based plastic (mainly PP) and elastomer such as EPDM. In contrast to TPO, the elastomer in TPV is cross-linked or vulcanized. TPV is characterized by a hardness of 35 Shore A to 50 Shore D. Commercially available TPVs include Elastron ® V, Sarlink ® (DSM), Santoprene ® (Exxon).
  • thermoplastic elastomer is characterized by a Vicat softening temperature VST (50°C/10N) of at least 50°C, preferably at least 60°C, in particular at least 100°C.
  • VST Vicat softening temperature
  • thermoplastic elastomer is characterized by a melting temperature in the range 140 to 190°C, in particular in the range 150 to 175°C.
  • thermoplastic elastomer is characterized by a thermal shrinkage of a maximum of 3%, preferably a maximum of 2%, particularly preferably a maximum of 1%.
  • the thermoplastic elastomer in the form of the sheath component has a melt flow rate of a maximum of 13 g/10 min (190°C), in particular a maximum of 11 g/10 min (190°C), particularly preferably a maximum of 10 g/10 min (190°C).
  • the thermoplastic elastomer in the form of the sheath component has a melt flow rate of maximum 50 g/10 min (230°C), in particular of a maximum of 30 g/10 min (230°C), particularly preferably of a maximum of 20 g/10 min (230°C).
  • the thermoplastic elastomer is a TPS and stands for styrene block copolymers, in particular styrene/butadiene/styrene (SBS), or styrene/ethylene-butylene/styrene (SEBS) or styrene/ethylene-propylene/styrene (SEPS) or styrene/isoprene/styrene (SIS) based styrene block copolymers, which in the form of the shell component have a melt flow rate of a maximum of 30 g/10 min (230°C), in particular of a maximum of 20 g/10 min (230°C), particularly preferably of a maximum of 13 g/10 min (230°C).
  • SBS styrene/butadiene/styrene
  • SEBS styrene/ethylene-butylene/styrene
  • SEPS styrene/ethylene-prop
  • thermoplastic elastomer has a hardness of 75 Shore A to 40 Shore D.
  • thermoplastic elastomer has a water absorption (23°C) of maximum 0.8%.
  • thermoplastic elastomer has a tensile stress at break of min. 10MPa and max. 28MPa.
  • a TPS styrene block copolymer selected from the group styrene/butadiene/styrene (SBS), styrene/ethylene-butylene/styrene (SEBS), styrene/ethylene-propylene/styrene (SEPS) or styrene/isoprene/styrene (SIS) is used as the thermoplastic elastomer, with the thermoplastic elastomer styrene/ethylene-butylene/styrene (SEBS) being particularly preferred, or a TPC thermoplastic polyester elastomer, i.e. a block copolymer based on a copolyester, is used as the thermoplastic elastomer.
  • SBS styrene/butadiene/styrene
  • SEBS styrene/ethylene-butylene/styrene
  • SEPS styren
  • the electrically conductive material present in the sheath has an electrical conductivity of at least 3 ⁇ 10 2 S/m, preferably at least 1 ⁇ 10 6 S/m.
  • the electrically conductive material is preferably a particulate material, for example a powder or granulate.
  • non-spherical particles including rod-shaped, fiber-shaped, plate-shaped or branched particles, are also possible.
  • the introduction of the electrically conductive material into the casing makes it possible to add larger particles that usually interfere with the production of spun threads in the extrusion process.
  • the electrically conductive material can also have particles larger than 2 ⁇ m, preferably larger than 3 ⁇ m, in particular particles with a spherical size of more than 2 ⁇ m, preferably larger than 3 ⁇ m.
  • Such particle sizes cannot be used in conventional thread spinning processes, since a filter is usually used in front of the spinning beam.
  • the presence of such large particles of electrically conductive material makes it easier to overcome the electrical percolation threshold. With the help of the present invention, large particles of electrically conductive material can therefore also be introduced into the yarn according to the invention.
  • thermoplastic sheath Preferred electrically conductive materials for the thermoplastic sheath are, for example, US-A-6,228,492 ; US-A-6,528,572 ; US-A-2003/158,323 ; US-A-6,621,970 ; CN-A-1431342 ; US-A-2003/236,588 and US-A-5,840,425 revealed.
  • thermoplastic sheath are suitable carbon nanotubes such as in US-A-6,099,960 ; US-A-6,280,697 ; US-A-2002/172,639 ; US-A-2003/102,222 ; US-A-2002/113,335 and US-A-2003/102,444 , revealed.
  • thermoplastic sheath Particularly preferred electrically conductive materials for the thermoplastic sheath are so-called CNTs (Carbon Nano Tubes) with an average diameter in the range of 8 to 12 nm, preferably in the range of 9 to 10 nm, determined by means of transmission electron microscopy (TEM),
  • CNTs Carbon Nano Tubes
  • TEM transmission electron microscopy
  • thermoplastic sheath Particularly preferred electrically conductive materials for the thermoplastic sheath are so-called CNTs (carbon nano tubes) with an average diameter in the range of 8 to 12 nm, preferably in the range of 9 to 10 nm, and an average length in the range of 1 to 3 ⁇ m, preferably in the range of 1 to 2 ⁇ m, determined by means of transmission electron microscopy (TEM).
  • CNTs carbon nano tubes
  • thermoplastic sheath Particularly preferred electrically conductive materials for the thermoplastic sheath are so-called graphenes, in particular graphene with a height of ⁇ 10nm and a lateral extension of 1.5 ⁇ m, determined by means of transmission electron microscopy (TEM).
  • graphenes in particular graphene with a height of ⁇ 10nm and a lateral extension of 1.5 ⁇ m, determined by means of transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the sheath is applied to the multifilament yarn by means of extrusion from the melt.
  • the multifilament yarn is pulled through a ring-shaped extrusion nozzle, around which another, larger extrusion nozzle is installed, which applies the melted sheath component to the multifilament yarn.
  • the yarn thickness is determined by the thickness of the core yarn, the difference in diameter of the extrusion nozzles and the yarn take-off speed.
  • the multi-component yarn is then cooled in a water bath and wound up.
  • the introduced (electrically conductive) materials can, in contrast to conventional spinning processes, have sizes of >3 ⁇ m in one or more dimensions without permanently disrupting the manufacturing process.
  • the electrically conductive material used according to the invention can also form aggregates in the jacket.
  • These aggregates from the particulate material for example a powder or granulate, can be determined using optical methods.
  • a film is formed from the jacket component and the aggregate size is determined using optical methods. The determination can be carried out, for example, using an FSA100 analyzer from OCS Optical Control Systems GmbH, Witten, Germany.
  • the individual defect size can, in individual cases, be up to 500 ⁇ m and usually 90% of the defect locations are smaller than 100 ⁇ m.
  • the average numerical defect size is typically up to 50 ⁇ m.
  • thermoplastics of the multifilament core and sheath additives in the thermoplastics of the multifilament core and sheath
  • thermoplastic polymers described above have conventional additives. These are usually antioxidants, pigments, stabilizers, surfactants, waxes, flow promoters, solid solvents, plasticizers and other materials, e.g. nucleating agents, which are added to improve the processability of the thermoplastic composition.
  • the additives mentioned above are not the electrically conductive material used according to the invention.
  • the electrically conductive yarn according to the invention with a core-sheath structure consisting of a multifilament yarn core and an electrically conductive sheath has, on the one hand, good mechanical properties and, on the other hand, good electrical conductivity.
  • the yarn according to the invention preferably has a diameter in the range of 0.1 mm to 2.5 mm.
  • the yarn according to the invention preferably has 10 to 500 individual filaments in the multifilament yarn core.
  • the yarn according to the invention is electrically non-conductive in the multifilament yarn core.
  • the yarn according to the invention preferably has a maximum tensile strength in the range of 1500 to 3600 cN, in particular 1700 to 3600 cN, particularly preferably 2000 to 3600 cN.
  • the yarn according to the invention preferably has a fineness-related strength in the range from 35 to 100 cN/tex, in particular from 50 to 100 cN/tex.
  • the fineness-related strength of the yarn according to the invention is thus lower than the fineness-related strength of the core, since the sheath material is included in the determination of the fineness-related strength, but does not make a significant contribution to the strength.
  • the yarn according to the invention preferably has a maximum bending force in the range from 0.5 to 20 cN, in particular 1 to 20 cN, particularly preferably from 2 to 20 cN, particularly preferably 5 to 20 cN.
  • the yarn according to the invention preferably has a flexural modulus in the range from 5 to 200 daN/mm 2 , in particular from 10 to 200 daN/mm 2 , particularly preferably 50 to 200 daN/mm 2 , particularly preferably 100 to 200 daN/mm 2 , particularly preferably in the range from 120 to 180 daN/mm 2 .
  • the yarn according to the invention preferably has a thermal shrinkage of a maximum of 5%.
  • the yarn according to the invention is electrically non-conductive in the multifilament yarn core.
  • electrically non-conductive means an electrical conductivity of ⁇ 10 -8 S/m.
  • the yarn according to the invention is electrically conductive in the sheath and has an electrical conductivity of at least 150 S/m.
  • the sheath of the yarn according to the invention has a thickness of at least 10 ⁇ m, preferably at least 20 ⁇ m, particularly preferably at least 50 ⁇ m.
  • the thickness is not restricted in terms of the upper limit.
  • the maximum thickness is usually 300 ⁇ m, so that the thickness is in the range from 10 ⁇ m to 300 ⁇ m, preferably 50 ⁇ m to 300 ⁇ m, in particular in the range from 100 ⁇ m to 150 ⁇ m.
  • the sheathing of the yarn according to the invention comprises 55 to 99 wt.% thermoplastic elastomer and 1 to 45 wt.% electrically conductive material, preferably 85 to 99 wt.% thermoplastic elastomer and 1 to 15 wt.% electrically conductive material, particularly preferably 90 to 99 wt.% thermoplastic elastomer and 1 to 10 wt.% electrically conductive material, in particular 94 to 99 wt.% thermoplastic elastomer and 1 to 6 wt.% electrically conductive material.
  • the coating may contain conventional additives, in particular those that facilitate the processability of the coating compound.
  • the present invention further relates to textile fabrics, in particular nonwovens, woven fabrics, knitted fabrics, meshes, cables containing the yarn according to the invention.
  • the yarns according to the invention can be used in sensor applications, for example as pressure sensors in tires, and in bio-sensors in textiles. Furthermore, the yarns according to the invention can be used as antistatic material, for example in conveyor belts and sieves. Another application can be as a cable in data transmission or the yarn can be used in flexible electronic applications, for example as intelligent clothing or as textile heating material.
  • the present invention further relates to a process for producing the electrically conductive yarn according to the invention.
  • the extrusion of the sheath consisting essentially of thermoplastic elastomer and electrically conductive material, is usually carried out at temperatures in the range of 180 to 250°C, but at least 30°C above the melting temperature of the thermoplastic elastomer of the sheath.
  • the extrusion of the sheath is carried out in such a way that the Sheath material has no or only a low orientation, ie it has predominantly amorphous structures and only small crystalline parts.
  • the lower orientation can be determined by DSC or wide-angle diffraction. Further methods can be found in the Dissertation by s. Bogner (2002) Institute for Textile and Fiber Research Stuttgart .
  • the multifilament yarn to be coated is kept under tension. Depending on the viscosity of the molten coating, this is also built up - at least partially - by the braking effect of the molten component.
  • a typical tensile stress is, for example, 5-15 cN. It is also advantageous if the difference between the melting points of the core and the coating is at least 15°C, preferably at least 25°C, in particular at least 30-80°C.
  • the material forming the sheath is usually dried beforehand and then fed into the extruder, whereby the extruder has several heating zones and a cooling system in the feed. In addition to the heating zones in the extruder, there may also be additional heating zones outside in the direction of the spinning head.
  • the melted sheath material is fed laterally via a nozzle combination onto the yarn (multifilament thread). This is followed by cooling, preferably in a water bath, and relaxation in a "chill unit", whereby the sheathed yarn usually runs over several godets without tension and is then wound up.
  • the resulting weight of the sheathed yarn can lead to uneven running, which can be remedied by applying a slight tension.
  • a slight tension is usually applied across two godets, whereby the different speeds of the two godets are in the range of ⁇ 0.5%.
  • the electrically conductive yarn according to the invention has the properties according to the invention without further stretching, so that damage caused by breaking up the percolating additive network is avoided.
  • the special properties of the multifilament core in particular the high specific strength, the low elongation at break and the high Young's modulus, allow a mechanical tension to be applied that can be maintained during the sheathing.
  • the other special properties of the multifilament core in particular the orientation and the low thermal shrinkage, mean that no Thermoshrinkage is triggered and forces that cause damage to the percolating additive network in the coating are avoided. In addition, a very uniform thickness of the coating is maintained.
  • Multifilament yarn count
  • the titre is determined according to DIN EN ISO1973 for fibres made of organic polymers.
  • the diameter is determined using optical methods using a microscope. Suitable microscopes are SEM, digital microscope, light microscope.
  • the determination of the Young's modulus is carried out together with the determination of the maximum tensile force or the maximum tensile force elongation.
  • the elongation at break is determined according to DIN EN ISO 2062:04/2010.
  • the thermal shrinkage of the multifilament yarn (core) and the sheath is determined at 180°C according to the historical DIN 53866 T3 (03/1987).
  • the thickness of the sheath material is determined using optical methods, i.e. examining the cross-section using a microscope. Suitable microscopes are SEM, digital microscope, light microscope.
  • the electrical conductivity of the electrically conductive material is determined using a powder conductivity measuring station in which the powdered material is filled into a cylinder and compressed by a piston at a pressure of 30 MPa.
  • the electrical resistance is measured between two gold electrodes located on the top of the piston and on the bottom of the cylinder.
  • the resistance measurements are carried out using 4-point technology (resistance less than 1000 Ohm) or 2-point technology (resistance greater than 1000 Ohm), whereby the switchover is carried out programmatically based on the measured data.
  • the device is controlled as well as the data acquisition and evaluation is carried out by a customized software based on Agilent VEE Version 9.3.
  • the electrical conductivity of the electrically conductive sheath material is determined according to DIN 54345-5:07/1985.
  • the determination of the fineness-related strength is carried out according to DIN EN ISO 2062:04/2010.
  • Shore A and Shore D hardness are carried out according to ISO 868 (DIN EN ISO 868:2003-10).
  • the Vicat softening temperature (A50) is determined according to ISO 306 at 50°C/10N (DIN EN ISO 306:2014-03).
  • the melting temperature is determined according to ISO 11357-1/-3 at 10°C/min. (DIN EN ISO 11357-1:2017-02 and DIN EN ISO 11357-3:2018-07) Melt-Flow Rate
  • the melt mass flow rate is determined according to DIN EN ISO 1133 (2012) at 190°C and 230°C (21.6 kg).
  • the water absorption is determined at 23°C according to DIN EN ISO 62 (2008).
  • the maximum tensile force is determined according to DIN EN ISO 2062:04/2010.
  • the yarn is placed on a suitable measuring head on 2 supports.
  • the natural curvature points downwards.
  • the bending pin moves downwards and pushes the yarn through. At the end of the test section, the bending pin moves upwards again. The force is recorded. The maximum bending force and possibly the force at 10° deflection are evaluated.
  • the flexural modulus is determined according to the bending force.
  • the present invention is illustrated by the following example without being limited thereby.
  • the compound used for the sheath is a SEBS TPS with 20-40 wt.% Carbon black as an electrically conductive additive.
  • the compound has relatively large agglomerates of up to 90 ⁇ m in diameter, is black and in granulate form. Its melting point is 152.2 °C.
  • the compound Before processing, the compound is dried at 60 °C for at least 4 hours and fed to the extruder without contact with air.
  • the core yarn is a 280 dtex f 48 high-strength yarn with an elongation at break of 17.6%, a maximum tensile force of 18.3 N and a maximum relative tensile force of 683 mN/tex.
  • the yarn is twisted Z60.
  • a spinneret combination of 0.3 mm inner and 0.65 mm outer nozzle is used.
  • the yarn is fed through the inner of the two spinnerets and the spinning head and through the water bath and over the gallettes to the winding unit.
  • the spinnerets are screwed tightly into the spinning head and winding is started.
  • the previously dried electrically conductive compound is fed into the extruder and heated there in 3 heating zones to approx. 210 °C until the correct viscosity is reached.
  • the melt is fed onto the running yarn via the extruder; the start of the coating is clearly visible by the color change of the yarn from white to black.
  • the extruder speed is adjusted depending on the winding speed so that the yarn reaches the maximum diameter of 0.65 mm and then does not increase any further.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Multicomponent Fibers (AREA)

Claims (26)

  1. Fil électriquement conducteur ayant une structure âme-enveloppe comprenant :
    (i) une âme constituée d'au moins un fil multifilament,
    (ii) une enveloppe comprenant un mélange de
    (iia) élastomère thermoplastique ; et
    (iib) au moins un matériau électriquement conducteur,
    caractérisé en ce que
    (iii) le fil multifilament présent sous forme d'une âme
    (iiia) présente une résistance mécanique liée à la finesse selon la norme DIN EN ISO 2062:04/2010 de 40 à 300 cN/tex,
    (iiib) présente un allongement à la rupture selon la norme DIN EN ISO 2062:04/2010 de 25 % au maximum,
    (iiic) présente un retrait thermique à 180°C selon la norme historique DIN 53866 T3 (03/1987) de 6 % au maximum
    (iiid) a un titre de 100 à 1200 dtex pour un fil multifilament de polymères organiques
    ou
    a un diamètre compris entre 200 et 600 µm pour un fil multifilament en matériaux non organiques,
    (iv) l'enveloppe
    (iva) est en contact avec le noyau et l'entoure complètement,
    (ivb) a une épaisseur d'au moins 10 µm,
    (ivc) présente une conductivité électrique selon DIN 54345-5:07/1985 d'au moins 150 S/m,
    (ivd) le matériau électriquement conducteur présente une conductivité électrique déterminée comme dans la description d'au moins 3×102 S/m,
    (ive) comprend de 1 à 45 % en poids de matériau électriquement conducteur,
    (ivf) comprend 99 à 55 % en poids d'élastomère thermoplastique,
    (ivg) le matériau de l'enveloppe présente un retrait thermique à 180°C selon la norme historique DIN 53866 T3 (03/1987) de 6 % maximum.
  2. Fil selon la revendication 1, caractérisé en ce que la résistance liée à la finesse du fil multifilament dans l'âme est de 50 à 280 cN/tex, de préférence de 60 à 260 cN/tex.
  3. Fil selon la revendication 1 ou 2, caractérisé en ce que le fil multifilament présente dans l'âme un allongement à la rupture de 20 % maximum.
  4. Fil selon la revendication 1, 2 ou 3, caractérisé en ce que le fil multifilament est électriquement non conducteur dans l'âme et présente une conductivité électrique < 10-8 S/m.
  5. Fil selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que le fil multifilament est dans l'âme un fil multifilament d'aramides, de polyesters, de polyamides, de verre, de fibres minérales, ou de mélanges de deux ou plusieurs des matériaux mentionnés ci-dessus.
  6. Fil selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce que le fil multifilament comprend dans l'âme un ou plusieurs polymères thermoplastiques, de préférence les polymères thermoplastiques comprennent des polycondensats synthétiques filables à l'état fondu, notamment des polyesters aliphatiques, des polyesters arylaliphatiques, des polyesters aromatiques ainsi que leurs copolymères / terpolymères.
  7. Fil selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que le fil multifilament est constitué dans l'âme d'un polyester, de préférence d'un polyester à base d'acides dicarboxyliques aromatiques, et qui présente
    (i) une résistance mécanique liée à la finesse de 40 à 300 cN/tex, en particulier de 60 à 100 cN/tex,
    (ii) un titre compris entre 100 et 1200 dtex, de préférence entre 250 et 500 dtex, et
    (iii) un allongement à la rupture d'au plus 25 %, de préférence d'au plus 20 %, et
    (iv) présente un retrait thermique d'au plus 6 %, de préférence d'au plus 3 %.
  8. Fil selon une ou plusieurs des revendications 1 à 7, caractérisé en ce que l'enveloppe est en contact direct avec au moins 90 % de la surface du fil multifilament dans l'âme.
  9. Fil selon une ou plusieurs des revendications 1 à 8, caractérisé en ce que l'enveloppe comprend 85 à 99 % en poids d'élastomère thermoplastique et 1 à 15 % en poids de matériau électriquement conducteur, de préférence 90 à 99 % en poids d'élastomère thermoplastique et 1 à 10 % en poids de matériau électriquement conducteur, en particulier 94 à 99 % en poids d'élastomère thermoplastique et 1 à 6 % en poids de matériau électriquement conducteur.
  10. Fil selon une ou plusieurs des revendications 1 à 9, caractérisé en ce que l'enveloppe comprend un ou plusieurs élastomères thermoplastiques choisis dans le groupe des polyoléfines thermoplastiques (TPO), des vulcanisats de polyoléfines thermoplastiques (TPV), des copolymères séquencés de styrène (TPS), du polyuréthane thermoplastique (TPU), des polyéthers polyamides thermoplastiques (TPA) et/ou des polyesters élastomères thermoplastiques (TPC).
  11. Fil selon une ou plusieurs des revendications 1 à 10, caractérisé en ce que l'enveloppe comprend un ou plusieurs élastomères thermoplastiques dont la température de ramollissement Vicat VST selon ISO 306 à 50°C/10N (DIN EN ISO 306:2014-03) est d'au moins 50°C, de préférence d'au moins 60°C, en particulier d'au moins 100°C.
  12. Fil selon une ou plusieurs des revendications 1 à 11, caractérisé en ce que l'enveloppe comprend un ou plusieurs élastomères thermoplastiques dont la température de fusion selon la norme ISO 11357-1/-3 à 10°C/min se situe dans la plage de 140 à 190°C, en particulier dans la plage de 150 à 175°C.
  13. Fil selon une ou plusieurs des revendications 1 à 12, caractérisé en ce que l'élastomère thermoplastique sous forme du composant d'enveloppe présente un Melt Flow Rate selon DIN EN ISO 1133 (2012) à 190°C (21,6 kg) de 13 g/10 min au maximum, en particulier de 11 g/10 min au maximum, de préférence de 10 g/10 min au maximum.
  14. Fil selon une ou plusieurs des revendications 1 à 13, caractérisé en ce que l'élastomère thermoplastique sous forme du composant d'enveloppe présente un Melt Flow Rate selon DIN EN ISO 1133 (2012) à 230°C (21,6 kg) de 50 g/10 min au maximum, en particulier de 30 g/10 min au maximum, de préférence de 20 g/10 min au maximum.
  15. Fil selon une ou plusieurs des revendications 1 à 14, caractérisé en ce que l'enveloppe comprend un ou plusieurs matériaux électriquement conducteurs choisis dans le groupe des nanotubes de carbone (CNT) et/ou du graphène.
  16. Fil selon une ou plusieurs des revendications 1 à 15, caractérisé en ce que l'enveloppe comprend un ou plusieurs matériaux électriquement conducteurs, et en ce que ces matériaux comprennent des particules ayant une taille de particule supérieure à 2 µm.
  17. Fil selon une ou plusieurs des revendications 1 à 16, caractérisé en ce que le diamètre est compris entre 0,1 mm et 2,5 mm.
  18. Fil selon une ou plusieurs des revendications 1 à 17, caractérisé en ce que le fil présente un allongement à la rupture selon DIN EN ISO 2062:01/2010 de 20% maximum, de préférence de 15% maximum.
  19. Fil selon une ou plusieurs des revendications 1 à 18, caractérisé en ce que le fil présente une force de traction maximale selon DIN EN ISO 2062:04/2010 dans la plage de 1500 à 3600 cN, de préférence de 1700 à 3600 cN, en particulier de 2000 à 3600 cN.
  20. Fil selon une ou plusieurs des revendications 1 à 19, caractérisé en ce que le fil présente une force de flexion maximale déterminée comme décrit à la page 21 de la description dans la plage de 0,5 à 20 cN, de préférence de 1 à 20 cN, en particulier de 2 à 20 cN, de préférence encore de 5 à 20 cN.
  21. Fil selon une ou plusieurs des revendications 1 à 20, caractérisé en ce que le fil présente un module de flexion déterminé comme décrit à la page 21 de la description dans la plage de 5 à 200 daN/mm2, de préférence de 10 à 200 daN/mm2, en particulier de 50 à 200 daN/mm2, de préférence de 100 à 200 daN/mm2, en particulier dans la plage de 120 à 180 daN/mm2.
  22. Fil selon une ou plusieurs des revendications 1 à 21, caractérisé en ce que le fil présente un retrait thermique à 180°C selon la norme historique DIN 53866 T3 (03/1987) de 5 % maximum.
  23. Fil selon une ou plusieurs des revendications 1 à 22, caractérisé en ce que l'enveloppe présente une épaisseur d'au moins 20 µm, de préférence d'au moins 50 µm.
  24. Procédé de fabrication du fil défini dans les revendications 1 à 23, comprenant les étapes consistant à :
    a) introduire un fil multifilament avec
    (i) une résistance mécanique liée à la finesse selon la norme DIN EN ISO 2062:04/2010 de 40 à 300 cN/tex et
    (ii) un allongement à la rupture selon la norme DIN EM ISO 2062:04/2010 de 25 % maximum et
    (iii) un retrait thermique à 180°C selon la norme historique DIN 53866 T3 (03/1987) de 6 % maximum, et
    (iv) un titre de 100 à 1200 dtex pour un fil multifilament de polymères organiques
    ou
    un diamètre compris entre 200 et 600 µm pour un fil multifilament de matières non organiques,
    dans l'ouverture d'une filière d'extrusion ronde,
    b) gainage du fil multifilament introduit selon l'étape a) au moyen d'une filière d'extrusion ronde par extrusion d'un mélange de
    (v) 55 à 99 % en poids d'élastomère thermoplastique ; et
    (vi) 45 à 1 % en poids de matériau électriquement conducteur,
    (vii) un matériau conducteur de l'électricité ayant une conductivité électrique déterminée comme décrit dans la description d'au moins 3×102 S/m,
    (viii) le mélange formant l'enveloppe présente une conductivité électrique selon DIN 54345-5:07/1985 d'au moins 150 S/m et
    (ix) le matériau de l'enveloppe présente un retrait thermique à 180°C selon la norme historique DIN 53866 T3 (03/1987) de 6 % maximum,
    c) refroidissement du fil gainé, de préférence à la température ambiante (25°C), où le fil, après refroidissement,
    (x) présente un gainage électriquement conducteur d'une épaisseur d'au moins 10 µm,
    d) enroulement du fil sur un support approprié, de préférence sous la forme d'une bobine.
  25. Utilisation du fil défini dans les revendications 1 à 23 pour la fabrication (i) de produits textiles plats, en particulier de nappes, de tissus, de tricots, de mailles, de grilles, (ii) de câbles, (iii) de capteurs, (iv) comme matériau antistatique, en particulier dans, par exemple, des bandes de montage ou de transport ou des tamis, (v) dans la transmission de données ou (vi) dans des applications électroniques flexibles.
  26. Produit textile plat contenant un ou plusieurs fils définis dans les revendications 1 à 23.
EP22735413.1A 2021-06-28 2022-06-24 Fil electroconducteur Active EP4363642B1 (fr)

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EP21182095 2021-06-28
PCT/EP2022/067391 WO2023274884A1 (fr) 2021-06-28 2022-06-24 Fil electroconducteur

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US3586597A (en) * 1967-11-20 1971-06-22 Teijin Ltd Cloth having durable antistatic properties for use in garments and underwear
DE3431831A1 (de) 1984-08-30 1986-03-13 Hoechst Ag, 6230 Frankfurt Hochfestes polyestergarn und verfahren zu seiner herstellung
US6099960A (en) 1996-05-15 2000-08-08 Hyperion Catalysis International High surface area nanofibers, methods of making, methods of using and products containing same
US5840425A (en) 1996-12-06 1998-11-24 Basf Corp Multicomponent suffused antistatic fibers and processes for making them
US6228492B1 (en) 1997-09-23 2001-05-08 Zipperling Kessler & Co. (Gmbh & Co.) Preparation of fibers containing intrinsically conductive polymers
US6280697B1 (en) 1999-03-01 2001-08-28 The University Of North Carolina-Chapel Hill Nanotube-based high energy material and method
EP1279068B1 (fr) 2000-05-04 2014-07-09 QuNano AB Procédé et dispositif pour la fabrication de nanostructures
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