Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

• the present invention relates to filaments having very high electrical conductivities and excellent mechanical properties.
• These threads in particular in the form of monofilaments, can be used, for example, in screens or in conveyor belts.
• polyester fibers for technical applications are in most cases subjected to high mechanical and / or thermal stresses during use.
• the material must have good dimensional stability and constancy of force-elongation properties over as long as possible usage periods.
• the material must not be electrostatically charged during processing and during use.
• polyester-based manmade fibers have proven successful in such environments, when used in humid-hot environments, polyesters are prone to mechanical abrasion in addition to hydrolytic degradation.
• abrasion can have a variety of causes.
• the sheet forming screen or forming fabric is pulled in paper machines for dewatering suction boxes with the result of increased Siebverschl constituentes.
• screen wear occurs due to differences in speed between the paper web and the screen surface or between the screen surface and the surface of the drying drums.
• Tissue wear also occurs in other technical fabrics due to abrasion; e.g. in conveyor belts by grinding over fixed surfaces, in filter fabrics by mechanical cleaning and in screen printing fabrics by passing a squeegee over the screen surface.
• Multi-ply fabrics are used in the forming fabrics of modern paper machines.
• vacuum boxes are used on the underside of the sieve to accelerate the dewatering of the paper web by means of negative pressure.
• the contact surfaces of the edges of these suction boxes with the forming fabric are usually made of ceramic to prevent excessive wear on the suction boxes.
• monofilaments of polyamide e.g. made of polyamide 6 or polyamide 6.6. Otherwise, monofilaments of polyethylene terephthalate (hereinafter referred to as "PET"), of which the forming wire essentially consists, are predominantly used because of the higher dimensional stability.
• PET polyethylene terephthalate
• a proven design is the so-called interchangeable shot on the underside of the sieve: Here, an excess of a polyamide monofilament with the following PET monofilaments is used alternately. This achieves a compromise between abrasion resistance and dimensional stability.
• thermoplastic polyurethane TPU
• thermoplastic polyester such as polyethylene terephthalate isophthalate
• thermoplastic polyurethane having melting points of 200 to 230 ° C were used (see, eg EP-A-674.029 ).
• polyester compositions of crystalline thermoplastic polyester resins, polyester elastomers and sorbitan esters are made DE 691 23 510 T2 known. These are characterized by good moldability, in particular by a good release ability.
• polyester compositions containing an aromatic polycarbonate, a polyester derived from alkanediol and benzene dicarboxylic acids, and a polyester urethane elastomer or a polyether imide ester elastomer are known. These have improved flow properties while maintaining good mechanical properties.
• a finished thread is coated with a mixture of nano-carbon tubes and a polymer. Since the coated thread is not stretched further, the carbon bridges of the amorphous coating are not ruptured, resulting in very good electrical conductivities.
• the object of the present invention is to provide filaments which have excellent electrical conductivity, good mechanical properties and excellent abrasion resistance.
• threads are generally understood to mean fibers of finite length (staple fibers), fibers of infinite length (filaments) and multifilaments composed thereof or secondary-spun yarns of staple fibers.
• the melt-spun threads are preferably used in the form of monofilaments.
• modulus of elasticity is understood to mean the secant modulus of the force-strain characteristic between 0 and 1% elongation.
• elastic elongation is understood as meaning the linear progression of the force-strain characteristic from its origin to the deviation from the linearity.
• An elastic elongation of 1.5% thus corresponds to a linear course of the force-strain curve from 0% to 1.5% elongation; an elastic elongation of 4% consequently a linear curve of the force-elongation characteristic of 0% to 4%.
• thread-forming thermoplastic polymers are used according to the invention which, after spinning, stretching and, if appropriate, relaxing, give threads having the above-described moduli of elasticity and elastic elongations.
• thermoplastic polymers of component a) may be of any nature, as long as they are melt-spinnable and allow the production of filaments with the above defined elastic strains and elastic moduli.
• thermoplastic polymers examples include polyolefins, such as polyethylene, polypropylene or copolymers containing ethylene and / or propylene units in conjunction with other alpha-olefin units copolymerized therewith, such as alpha-butylene, alpha-pentylene, alpha-hexylene or alpha-octylene; Polyesters such as polycarbonate or aliphatic / aromatic polyesters; Polyamides, such as aliphatic or aliphatic / aromatic polyamides; or polyether esters, ie polymers which have at least ether and ester groups and, as a rule, aromatic divalent radicals, such as phenylene, in the recurring chain, for example TPE-E; or polyacrylonitrile or polyacrylonitrile copolymers with other ethylenically unsaturated comonomers such as acrylic or methacrylic acid.
• polyolefins such as polyethylene, polypropylene or copolymers containing
• Polyamide, polybutylene terephthalate, polypropylene terephthalate or polyether esters are preferably used as component a).
• polyamides are aliphatic or aliphatic / aromatic polyamides, e.g. Polycaprolactam, poly (hexamethylene-1,6-diaminadipamide), poly (hexamethylene-1,6-diamine-sebacic acid diamide), poly (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly (hexamethylene) 1,6-diamine isopthalklarediamid).
• polycaprolactam poly (hexamethylene-1,6-diaminadipamide), poly (hexamethylene-1,6-diamine-sebacic acid diamide), poly (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly (hexamethylene) 1,6-diamine isopthalklarediamid).
• the polyamides used according to the invention usually have viscosity numbers according to DIN 53727 of 120 to 350, preferably 150 to 320 cm 3 / g (measured at 25 ° C in sulfuric acid).
• thermoplastic polyesters which are preferably used as component a) in the threads according to the invention are likewise known per se. However, polyesters are to be selected which allow the production of yarns having the elastic moduli and elastic elongation values given above.
• polycarbonate or, in particular, aliphatic / aromatic polyesters of the types polybutylene terephthalate and / or polypropylene terephthalate, optionally containing amounts of up to 40% by weight, preferably up to 15% by weight, based on the total amount of component a), of other polyesters, such as polyethylene terephthalate, may be mixed.
• thermoplastic and elastomeric polyether esters are thermoplastic and elastomeric polyether esters. These polyether esters are known per se. If these polyether esters are used, they may be identical to polymers of component b), i. there may be cases in which threads contain only component a) and no additional component b).
• thermoplastic and elastomeric polyether esters are copolymers which comprise, in addition to polyethylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polybutylene terephthalate units, further units derived from aromatic and / or aliphatic and / or cycloaliphatic dicarboxylic acids, in particular adipic acid, secacic acid, terephthalic acid , Cyclohexanedicarboxylic acid or isophthalic acid, and derived from polyalkylene glycols, in particular polyethylene glycols.
• thermoplastic and elastomeric polyether esters are preferably diols, polyether diols and dicarboxylic acids, or correspondingly constructed polyester-forming derivatives.
• Main acid constituent of the copolyesters are terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may be suitable, preferably para or trans permanent aromatic compounds such as 2,6-naphthalene-dicarboxylic acid or 4,4'-biphenyldicarboxylic acid , as well as isophthalic acid.
• Aliphatic dicarboxylic acids such as adipic acid or sebacic acid, are preferably used in combination with aromatic dicarboxylic acids.
• Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol or mixtures thereof.
• Preferred are aliphatic diols having from two to four carbon atoms, especially ethylene glycol and butanediol.
• Further preferred are cycloaliphatic diols such as 1,4-cyclohexanedimethanol.
• the soft segments of this copolyester are formed by recurring structural units derived from polyether diols and dicarboxylic acids.
• the polyether diols are polyalkylene glycols, such as polyethylene glycol, polypropylene glycol or polybutylene glycol.
• Copolyether esters which have recurring structural units which are derived from an aromatic dicarboxylic acid and an aliphatic diol and a polyalkylene glycol are preferably used as component a).
• thermoplastic and elastomeric polyether esters have recurring structural units derived from terephthalic acid, ethylene glycol and polyethylene glycol, terephthalic acid, butylene glycol and polyethylene glycol, terephthalic acid, butylene glycol and polybutylene glycol, naphthalenedicarboxylic acid, ethylene glycol and polyethylene glycol, naphthalenedicarboxylic acid, butylene glycol and polyethylene glycol, from Naphthalenedicarboxylic acid, butylene glycol and polybutylene glycol, terephthalic acid, isophthalic acid, ethylene glycol and polyethylene glycol, terephthalic acid, isophthalic acid, butylene glycol and polyethylene glycol, and terephthalic acid, isophthalic acid, butylene glycol and polybutylene glycol.
• the polyesters of component a) used according to the invention usually have solution viscosities (IV values) of at least 0.60 dl / g, preferably from 0.60 to 1.05 dl / g, more preferably from 0.62 to 0.93 dl / g (measured at 25 ° C in dichloroacetic acid (DCE)).
• IV values solution viscosities
• Threads of polyesters or polyether esters with a content of free carboxyl groups of less than or equal to 3 meq / kg are preferred.
• These preferably contain a means for occluding free carboxyl groups, for example a carbodiimide and / or an epoxide compound.
• Such treated polyester yarns are stabilized against hydrolytic degradation and are particularly suitable for use in humid-hot environments, especially in paper machines or as a filter.
• thermoplastic and elastomeric block copolymers of component b) can be of very different types. Such block copolymers are known to the person skilled in the art.
• components b) are thermoplastic and elastomeric polyurethanes (TPE-U), thermoplastic and elastomeric polyesters (TPE-E), thermoplastic and elastomeric polyamides (TPE-A), thermoplastic and elastomeric polyolefins (TPE-O) and thermoplastic and elastomeric styrene Block copolymers (TPE-S).
• TPE-U thermoplastic and elastomeric polyurethanes
• TPE-E thermoplastic and elastomeric polyesters
• TPE-A thermoplastic and elastomeric polyamides
• TPE-O thermoplastic and elastomeric polyolefins
• TPE-S thermoplastic and elastomeric styrene Block copolymers
• thermoplastic and elastomeric block copolymers b) can be composed of a wide variety of monomer combinations. As a rule, these are blocks of so-called hard and soft segments.
• the soft segments are typically derived from polyalkylene glycol ethers in TPE-U, TPE-E and TPE-A.
• the hard segments are typically derived from short chain diols or diamines in TPE-U, TPE-E and TPE-A. In addition to the diols or diamines, the hard and Soft segments of aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or diisocyanates constructed.
• thermoplastic polyolefins are block copolymers comprising blocks of ethylene-propylene-butadiene and of polypropylene (EPDM / PP) or of nitrile-butadiene and of polypropylene (NBR / PP).
• Particularly preferred components b) are thermoplastic and elastomeric styrene block copolymers.
• block copolymers which have blocks of styrene-ethylene and of propylene-styrene (SEPS) or of styrene-ethylene and of butadiene-styrene (SEBS) or of styrene and of butadiene (SBS).
• thermoplastic block copolymer and elastomeric block copolymer are block copolymers which behave at room temperature comparable to the conventional elastomers, but can be plastically deformed under heat supply and thus exhibit a thermoplastic behavior.
• thermoplastic and elastomeric block copolymers have in some areas physical crosslinking points (e.g., minor valence forces or crystallites) that dissolve on heat without the polymer molecules decomposing.
• carbon black and / or graphite particles are used. These are carbon blacks or graphites whose primary particles are arranged in the form of aggregates, which preferably have the shape of a tang, in particular having the shape of elongated filaments.
• the carbon blacks used according to the invention consist of nanoscale primary particles. These are generally spherical and typically have diameters in the range of 10 to 300 nm. Owing to the strong anisotropy of the aggregates of carbon black particles or the graphite platelets used in accordance with the invention, formation takes place during the spinning of the thread in the longitudinal direction aligned aggregates which form electrically conductive paths along the longitudinal axis of the thread. In the unstretched thread these aggregates are partially present in a näulter form and are stretched by stretching in the thread longitudinal direction, but not torn. In this way, the electrically conductive paths are obtained in the thread.
• Particularly preferably used components c) are carbon blacks, which are present in the form of elongate aggregates made up of a plurality of primary particles in contact with one another and the drawn thread has an electrical conductivity of at least 0.5 ⁇ 10 -6 Siemens / cm, preferably at least 1 , 0 * 10 -5 Siemens / cm, measured in the longitudinal direction of the thread.
• the amounts of components a), b) and c) in the threads according to the invention can be selected within wide limits.
• the threads typically contain from 20 to 70% by weight of component a), from 15 to 40% by weight of component b) and from 5 to 50% by weight of component c), in each case based on the total mass of the thread.
• the combination of components a), b) and c) used according to the invention gives the filaments not only excellent abrasion resistance, but also good textile-technological properties, in particular good dynamic properties and excellent dimensional stability, as well as excellent electrical conductivity.
• the components a), b) and c) required for producing the threads according to the invention are known per se, some are commercially available or can be prepared by processes known per se.
• the threads according to the invention may contain, in addition to components a), b) and c), further auxiliaries d).
• processing aids antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
• processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
• antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
• pigments or matting agents examples include organic dye pigments or titanium dioxide.
• viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
• the threads according to the invention can be in any desired form, for example as multifilaments, as staple fibers, as secondary spun yarns, also in the form of twisted yarns, or in particular as monofilaments.
• the threads according to the invention are present as multicomponent threads.
• these are side-on threads or, in particular, core-sheath threads.
• the sheath preferably consists of a composition comprising components a), b), c) and optionally d) and the core consists of a filament-forming polymer which determines the mechanical properties, mainly the strength and elongation at break, of the total filament.
• a particularly preferred combination is a core-sheath thread whose core is made of polyamide, selected polyester or elastomeric polyetherester, preferably composed of polybutylene terephthalate, polypropylene terephthalate, polyamide 6 or mixtures of these polymers and whose shell comprises components b), c) and optionally d) in combination with a thermoplastic polymer, preferably a thermoplastic polyester or polyamide, in particular polyethylene terephthalate homopolymers, polyethylene terephthalate copolymer or Polyamide 6 contains.
• a thermoplastic polymer preferably a thermoplastic polyester or polyamide, in particular polyethylene terephthalate homopolymers, polyethylene terephthalate copolymer or Polyamide 6 contains.
• the weight ratio of core to sheath is 95: 5 to 20:80, preferably 75:25 to 45:55, more preferably 70:30 to 50:50.
• the titer of the threads according to the invention can vary within wide limits. Examples are 1 to 45,000 dtex, in particular 100 to 4,000 dtex.
• the cross-sectional shape of the threads according to the invention may be arbitrary, for example round, oval or n-cornered, where n is greater than or equal to 3.
• the threads of the invention can be prepared by methods known per se.
• composition comprising a thermoplastic polymer, components b), c) and optionally d) or containing components a), b), c) and optionally d) is preferably used in the form of a masterbatch.
• the threads according to the invention are drawn one or more times during production.
• a polyester produced by solid phase condensation is used.
• the hot polymer filament is cooled, e.g. in a cooling bath, preferably in a water bath, and then wound up or peeled off.
• the removal speed is greater than the injection rate of the polymer melt.
• the yarn produced in this way is then re-stretched one or more times, optionally fixed and wound up, as is known from the prior art for the abovementioned melt-spinnable polymers.
• the threads according to the invention are preferably used for the production of textile surface constructions, in particular of woven fabrics, spiral fabrics, laid or knitted fabrics. These textile surface constructions are preferably used in screens.
• Textile surface constructions containing the threads according to the invention are likewise the subject of this invention.
• the threads according to the invention can be used in all industrial fields. They are preferably used in applications in which increased wear and static electricity due to mechanical stress are to be expected. Examples thereof are the use in screen fabrics and filter cloths for gas and liquid filters, in dry belts, for example for the production of food, in packaging containers or in hoses for conveying small particles. These uses are also the subject of the present invention.
• filaments of the invention in the form of monofilaments relates to their use as conveyor belts or as components of conveyor belts.
• filaments of the invention in the form of monofilaments relates to their use as conveyor belts or as components of conveyor belts.
• the threads according to the invention can also be used in screens intended for use in paper machines.
• the components for the core were melted in the extruder.
• the components for the shell in the form of a masterbatch (Deltacom PET 1917 EC3, Delta Plastics principless- und glassesgesellschaft mbH, Weeze, Germany) made of polyethylene terephthalate (“PET”), thermoplastic Elastomer, conductivity carbon black and additives were mixed and melted in another extruder.
• PET polyethylene terephthalate
• thermoplastic Elastomer thermoplastic Elastomer
• conductivity carbon black additives
• the melted spun masses from both extruders were spun, drawn and drawn into a bicomponent spinneret with a hole diameter of 1.0 mm at a flow rate of 488 g / min and a take-off speed of 31 m / min into monofilaments with a core-shell structure heat-set in the hot-air duct at 255 ° C under heat-shrinkage.
• the masterbatch consisted of 50% by weight of the PET type described above, and 27% by weight of a thermoplastic elastomeric styrene block copolymer, 20% by weight of a conductivity carbon black and 3% by weight of processing stabilizer, lubricant, steric hindered amine and silane.
• Example 3 nuclear material Polyamide 6 polybutylene terephthalate Polyetherester 1) Proportion of core: sheath (wt.%) 90:10 90:10 75: 25 Diameter ( ⁇ m) 453 401 254 Titre (dtex) 1856 1616 638 Tensile strength (cN / tex) 38.4 10.4 30.2 Modulus of elasticity (GPa) 4.0 2.7 1.1 Elastic elongation (%) 2 2 19 Elongation at break (%) 41.7 16.7 69.5 el.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Multicomponent Fibers (AREA)
• Woven Fabrics (AREA)
• Artificial Filaments (AREA)
• Belt Conveyors (AREA)
• Filtering Materials (AREA)

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• 2007
  • 2007-02-24 DE DE200710009118 patent/DE102007009118A1/de not_active Ceased
• 2008
  • 2008-01-25 EP EP08001371A patent/EP1961845A3/fr not_active Withdrawn
  • 2008-02-21 JP JP2008039489A patent/JP2008214846A/ja not_active Withdrawn

Patent Citations (7)

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