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
  • D01F6/88—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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
  • Y10T442/3008—Woven fabric has an elastic quality
  • Y10T442/3024—Including elastic strand or strip

Definitions

• the present invention concerns strands having very high electrical conductivities and excellent mechanical properties. These strands, which are monofilaments in particular, are useful in screens or conveyor belts for example.
• polyester fibers for industrial applications are in most cases subjected to high mechanical and or thermal stressors in use.
• stressors due to chemical and other ambient influences, to which the material has to offer adequate resistance.
• the material has to possess good dimensional stability and constancy for its stress-strain properties over very long use periods.
• One example of industrial applications comprising a combination of high mechanical, thermal, chemical and electrical stresses is the use of monofilaments in filters, screens or as conveyor belts.
• This use requires monofilaments having excellent mechanical properties, such as high initial modulus, breaking strength, knot strength, loop strength and also high abrasion resistance coupled with high hydrolysis resistance in order that they may withstand high stresses encountered in their use and in order that the screens or conveyor belts may have an adequate use life.
• Polyester-based manufactured fibers have a proven record of good performance in such environments, but when used in hot moist environments polyesters are vulnerable to mechanical abrasion as well as hydrolytic degradation.
• Abrasion can have a wide variety of causes in industrial uses.
• the sheet-forming wire screen in papermaking machines is in the process of dewatering the paper slurry pulled over suction boxes, and this results in enhanced wear of the wire screen.
• wire screen wear occurs as a consequence of speed differences between the paper web and the wire screen surface and between the wire screen surface and the surface of the drying drums.
• Fabric wear due to abrasion also occurs in other industrial fabrics, for instance in transportation belts due to dragging across stationary surfaces, in filter fabrics due to the mechanical cleaning and in screen printing fabrics due to the movement of a squeegee across the screen surface.
• the forming wire screens of state of the art papermaking machines utilize multi-ply woven fabrics.
• suction boxes are utilized on the wire screen underside to speed paper web dewatering by means of underpressure.
• the contact surfaces of the edges of these suction boxes with the forming fabric consist in general of ceramic to prevent excessive wear of the suction boxes.
• Monofilaments made of nylon for example nylon-6 or nylon-6,6, are still being used to improve the abrasion resistance of the wire screen underside. This is where it is predominantly monofilaments made of polyethylene terephthalate (hereinafter PET) which are used because of their higher dimensional stability, and it is of them that the forming wire screen fabric consists essentially.
• PET polyethylene terephthalate
• One tried and tested construction for the wire screen underside is that of an alternating weft in which a backing weft of a nylon monofil alternates with a backing weft of PET monofil. This results in a compromise of abrasion resistance and dimensional stability.
• thermoplastic polyurethane TPU
• thermoplastic polyester for example polyethylene terephthalate isophthalate
• thermoplastic polyurethane having melting points of 200 to 230° C.
• the prior art further comprises monofilaments having a core-sheath structure in each of which the sheath consists of a mixture of thermoplastic polyester having a melting point of 200 to 300° C., for example PET, and of thermoplastic elastomeric copolyetherester having selected polyetherdiol building block groups as soft segments, that likewise exhibit improved abrasion resistance (cf. for example EP-A-735,165).
• the sheath consists of a mixture of thermoplastic polyester having a melting point of 200 to 300° C., for example PET, and of thermoplastic elastomeric copolyetherester having selected polyetherdiol building block groups as soft segments, that likewise exhibit improved abrasion resistance (cf. for example EP-A-735,165).
• polyester compositions comprising crystalline thermoplastic polyester resins, polyester elastomers and sorbitan esters are known from DE 691 23 510 T2. These are notable for good moldability, in particular for good releaseability.
• DE 690 07 517 T2 discloses polyester compositions comprising an aromatic polycarbonate, a polyester derived from alkanediol and benzene-dicarboxylic acids, and a polyesterurethane elastomer or a polyether imide ester elastomer. These combine improved flow properties with good mechanical properties.
• WO-A-98/14,647 describes an attempt to remedy this disadvantage by producing a sheath-core filament comprising a sheath polymer having a lower melting point than the core polymer. After drawing, the sheath is incipiently melted, so that the strand shrinks and interrupted bridges of electrically conductive material can re-form. This does indeed push electrical conductivity back up; however, the thermal treatment leads to a decrease in the degree of orientation of the molecular chains and hence to a reduction in the strength of the filament.
• EP-A-1,559,815 describes coating a ready-produced strand with a mixture of carbon nanotubes and a polymer. Since the coated strand is not further stretched, the carbon bridges in the amorphous coating are not ruptured, which results in very good electrical conductivities.
• the present invention has for its object to provide strands having outstanding electrical conductivity as well as good mechanical properties and excellent abrasion resistance.
• the present invention accordingly provides melt-spun strands having a modulus of elasticity of greater than 14 GPa and an elastic extension of less than or equal to 0.5%, comprising: a) a thermoplastic polyester, b) a thermoplastic elastomeric block copolymer and c) carbon black and/or graphite particles in the form of aggregates aligned along the longitudinal axis of the strand which form electrically conductive paths along the longitudinal axis of the strand.
• strands herein is to be understood as referring very generally to fibers of finite length (staple fibers), fibers of infinite length (filaments) and also multifilaments composed thereof, or yarns secondarily spun from staple fibers.
• the melt-spun strands are preferably used in the form of monofilaments.
• Modulus of elasticity herein refers to the secant modulus of the stress-strain curve between 0% and 1% strain.
• Elastic extension herein refers to the linear course of the stress-strain curve. An elastic extension of up to 0.5% thus corresponds to a linear course of the stress-strain curve in the range from 0 to 0.5% strain. In the case of strains of greater than 0.5%, the stress-strain curve of the strands of the present invention exhibits a nonlinear course.
• the polyesters used for component a) are fiber-forming polyesters which, after spinning, drawing and, if appropriate, relaxing, give strands having the above-described moduli of elasticity and elastic extensions.
• possibilities include polyethylene naphthalate homopolymers or copolymers containing ethylene naphthalate units. These polymers are therefore derived from ethylene glycol and, if appropriate, further alcohols and from naphthalenedicarboxylic acid or polyester-forming derivatives thereof, such as naphthalenedicarboxylic esters or naphthalenedicarbonyl chlorides.
• thermoplastic polyesters are known per se. Building blocks of thermoplastic copolyesters a) are preferably the abovementioned diols and dicarboxylic acids, or correspondingly constructed polyester-forming derivatives.
• the main acid constituent of the polyesters comprises naphthalenecarboxylic acid, if appropriate, together with relatively small fractions, preferably up to 15 mol %, based on the total amount of dicarboxylic acids, of other aromatic and/or aliphatic and/or cycloaliphatic dicarboxylic acids, preferably with para-or trans-disposed aromatic compounds, for example terephthalic acid or 4,4′-biphenyldicarboxylic acid, and also preferably with isophthalic acid and/or with aliphatic dicarboxylic acids, such as with adipic acid or sebacic acid.
• components a) are given to aromatic, liquid-crystalline polyesters, such as polyoxybenzonaphthoate or polyhydroxybenzoate, which are copolymerized, if appropriate, with diols and dicarboxylic acids, or correspondingly constructed oxycarboxylic acids.
• aromatic, liquid-crystalline polyesters such as polyoxybenzonaphthoate or polyhydroxybenzoate, which are copolymerized, if appropriate, with diols and dicarboxylic acids, or correspondingly constructed oxycarboxylic acids.
• thermoplastic polyesters are completely aromatic, liquid-crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
• Suitable dihydric alcohols can be used as well as ethylene glycol.
• Typical representatives thereof are aliphatic and/or cycloaliphatic diols, for example propanediol, 1,4-butanediol, cyclohexanedimethanol or mixtures thereof.
• Examples of preferred components a) are copolyesters which, as well as polynaphthalate units, contain further units which are derived from alkylene glycols, in particular ethylene glycol, and aliphatic and/or aromatic dicarboxylic acids, such as adipic acid, sebacic acid, terephthalic acid or isophthalic acid.
• Particularly preferred components a) are polyethylene naphthalate homopolymers or copolyesters containing, as well as structural repeat units of polyethylene naphthalate, structural repeat units of polyethylene adipate, polyethylene sebacate, polyethylene isophthalate or in particular of polyethylene terephthalate.
• the polyesters used according to the present invention for component a) typically have solution viscosities (IV values) of at least 0.60 dl/g, preferably of 0.60 to 1.05 dl/g, and more preferably of 0.62-0.93 dl/g (measured at 25° C. in dichloroacetic acid (DCE)).
• IV values solution viscosities
• These preferably comprise an agent for capping free carboxyl groups, for example a carbodiimide and/or an epoxy compound.
• Polyester strands thus endowed are stable to hydrolytic degradation and are particularly suitable for use in hot moist environments, for example in papermaking machines or as filters.
• thermoplastic and elastomeric block copolymers of component b) may comprise a wide variety of types. Such block copolymers are known to one skilled in the art.
• components b) are thermoplastic and elastomeric polyurethanes (TPE-Us), thermoplastic and elastomeric polyesters (TPE-Es), thermoplastic and elastomeric polyamides (TPE-As), thermoplastic and elastomeric polyolefins (TPE-Os) and thermoplastic and elastomeric styrene block copolymers (TPE-Ss).
• TPE-Us thermoplastic and elastomeric polyurethanes
• TPE-Es thermoplastic and elastomeric polyesters
• TPE-As thermoplastic and elastomeric polyamides
• TPE-Os thermoplastic and elastomeric polyolefins
• TPE-Ss thermoplastic and elastomeric styrene block copolymers
• the thermoplastic and elastomeric block copolymers b) may be constructed from a wide variety of different monomer combinations.
• the blocks in question generally comprise so-called hard and soft segments.
• Soft segments are typically derived from polyalkylene glycol ethers in the case of the TPE-Us, the TPE-Es and the TPE-As.
• Hard segments are typically derived from short-chain diols or diamines in the case of the TPE-Us, the TPE-Es and the TPE-As.
• the hard and soft segments are constructed from aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or diisocyanates.
• 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).
• Thermoplastic and elastomeric styrene block copolymers are particularly preferred components b).
• block copolymers comprising 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 and elastomeric block copolymers herein are block copolymers which have a similar room temperature behavior to conventional elastomers, but are plastically deformable on heating and thus exhibit a thermoplastic behavior. These thermoplastic and elastomeric block copolymers have subregions with physical points of crosslinking (for example, secondary valency forces or crystallites) which become unlinked on heating without the polymer molecules decomposing.
• Component c) comprises selected particles of carbon black and/or of graphite.
• the carbon blacks or graphites in question have primary particles which are arranged in the form of aggregates which preferably have the form of a clew, in particular in the form of elongated strands.
• the carbon blacks used according to the present invention consist of nanoscale primary particles. These are generally spherical and typically have diameters in the range from 10 to 300 nm. Owing to the pronounced anisotropy of the aggregates of carbon black particles or graphite platelets that are used according to the present invention, longitudinally oriented aggregates form in the course of the spinning of the strand, and form electrically conductive paths along the longitudinal axis of the strand. In the undrawn strand, these aggregates are partly present in clewed form and are extended in the longitudinal direction of the strand, but not ruptured, by the drawing operation. The electrically conductive paths in the strand thus remain intact.
• components c) are given to carbon blacks which are present in the strand in the form of elongate aggregates constructed of a plurality of primary particles in contact with one another, and which endow the drawn strand with an electrical conductivity of at least 0.5*10 ⁇ 6 siemens/cm and preferably at least 1.0*10 ⁇ 5 siemens/cm, measured in the longitudinal direction of the strand.
• the amounts of components a), b) and c) in the strands of the present invention can be chosen within wide limits.
• the strands typically contain 20% to 70% by weight of component a), 15% to 40% by weight of component b) and 5% to 50% by weight of component c), all based on the total mass of the strand.
• the combination of components a), b) and c) which is used according to the present invention endows the strands not only with excellent abrasion resistance but also with good textile-technological properties, in particular good dynamic properties and an excellent dimensional stability, and also with outstanding electrical conductivity.
• the components a), b) and c) used for producing the strands of the present invention are known per se, partly commercially available or obtainable by processes known per se.
• the strands of the present invention may further comprise further, adjunct materials d).
• Examples thereof include, in addition to the aforementioned hydrolysis stabilizer, processing aids, antioxidants, plasticizers, lubricants, pigments, delusterants, viscosity modifiers or crystallization accelerants.
• processing aids are siloxanes, waxes or comparatively long-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
• antioxidants are phosphorus compounds, such as phosphoric esters or sterically hindered phenols.
• pigments or delusterants examples include organic dye pigments or titanium dioxide.
• viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
• the strands of the present invention can be present in any desired form, for example as multifilaments, as staple fibers, as secondarily spun yarns, including in the form of threads, or particularly as monofilaments.
• the strands of the present invention are in the form of multicomponent strands.
• examples thereof are side-by-side strands or, in particular, sheath-core strands.
• the sheath in the sheath-core strands preferably consists of a composition comprising components a), b), c) and, if appropriate, d), while the core consists of a fiber-forming polymer which determines the mechanical properties, chiefly the strength and breaking extension, of the overall strand.
• a particularly preferred combination is a sheath-core strand whose core consists of polyester, preferably of polynaphthylene terephthalate and/or the other polymers and/or polymer mixtures listed above as being preferred for component a), and whose sheath contains the components b), c) and, if appropriate, d) in combination with a thermoplastic polymer, preferably a thermoplastic polyester, in particular polynaphthylene terephthalate and/or other polymers and/or polymer mixtures listed above as being preferred for component a) and/or polyethylene terephthalate homopolymers or polyethylene terephthalate copolymers.
• a thermoplastic polymer preferably a thermoplastic polyester, in particular polynaphthylene terephthalate and/or other polymers and/or polymer mixtures listed above as being preferred for component a) and/or polyethylene terephthalate homopolymers or polyethylene terephthalate copolymers.
• the weight ratio of core and sheath is in the range from 95:5 to 20:80, preferably in the range from 75:25 to 45:55 and especially in the range from 70:30 to 50:50.
• the linear density of the strands according to the present invention can vary within wide limits. Examples thereof are 1 to 45 000 dtex and especially 100 to 4000 dtex.
• the cross-sectional shape of the strands according to the present invention is freely choosable, examples being round, oval or n-gonal, where n is not less than 3.
• the strands of the present invention are obtainable by processes known per se.
• a typical production process comprises the measures of: i) extruding a mixture comprising components a), b) and c) through a spinneret die, ii) withdrawing the resulting filament, iii) drawing and iv) if appropriate, relaxing the resulting filament.
• Multicomponent strands are produced in a similar manner. Except that in this case the spinning dopes which form the different compositions are melted in different extruders and pressed through a multicomponent spinneret die.
• composition comprising a thermoplastic polymer, components b), c) and, if appropriate, d) or comprising components a), b), c) and, if appropriate, d) is preferably used in the form of a master batch.
• the strands of the present invention are subjected to drawing, in one or more stages, in the course of their production.
• strands using as component a) and/or as component of the core strand a polyester produced by solid state condensation.
• the hot strand of polymer is quenched, for example in a quench bath, preferably in a water bath, and subsequently wound up or withdrawn.
• the withdrawal speed is greater than the ejection speed of the polymer melt.
• the strand thus produced is subsequently subjected to an afterdrawing operation in one or more stages, if appropriate, set and wound up, as known from the prior art for the melt-spinnable polymers mentioned.
• the strands of the present invention are preferably used for producing textile fabrics, particularly woven fabrics, spiral fabrics, nonwoven scrims or drawn-loop knits. These textile fabrics are preferably used in screens.
• Textile fabrics comprising the strands of the present invention likewise form part of the subject matter of this invention.
• the strands of the present invention can be used in all industrial fields. They are preferably employed for applications where increased wear due to mechanical stress and also a buildup of static electricity is likely. Examples thereof are the use in screen wovens and filter cloths for gas and liquid filters, in drying belts, for example in the manufacture of food products, in packaging containers or in hoses for conveying small particles. These uses likewise form part of the subject matter of the present invention.
• a further use of the strands of the present invention in the form of monofilaments concerns their use as conveyor belts or as components of conveyor belts.
• the strands of the present invention may also be used in screens which are wire screens and intended for use papermaking machines.
• the components for the core 95% by weight of polyethylene naphthalate (PEN) and 5% by weight of polybutylene terephthalate (PBT), were melted in an extruder.
• the components for the sheath in the form of a masterbatch (Deltacom PET 1917 EC3, from Delta Kunststoffeips-und bottlesgesellschaft mbH, Weeze, Germany) of polyethylene terephthalate (PET), thermoplastic elastomer, conductivity carbon black and additives were mixed and melted in another extruder.
• the melted spinning dopes from the two extruders were fed into a bicomponent spinning head by means of geared pumps, spun to form monofilaments and quenched in the spin bath, subsequently subjected to an afterdrawing operation in one or more stages, if appropriate, set and wound up, as known from the prior art for the melt-spinnable polymers mentioned.
• the diameter of the monofilament produced was 169 ⁇ m.
• the monofilament had a sheath fraction of 30% by weight and a core fraction of 70% by weight.
• the textile-technological data of the monofilaments obtained are shown in the table which follows.
• the masterbatch consisted of 50% by weight of the PET type described above and also 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, sterically hindered amine and silane.
• the monofilament was clamped between two jaws under slight pre-tension, and silverized at two positions. Electrical clamps connected to a resistance meter (Metra Hit 15 S; measuring range up to 30 M ⁇ ) were attached at the silverized locations.
• the clamp spacing chosen was between 10 mm and 300 mm. A clamp spacing of 100 mm has been used as standard.
• the conductivity value is the reciprocal resistance for 1 centimeter of monofil length.

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• 2007
  • 2007-02-24 DE DE200710009117 patent/DE102007009117A1/de not_active Ceased
• 2008
  • 2008-01-25 EP EP20080001370 patent/EP1961844A3/de not_active Withdrawn
  • 2008-02-21 JP JP2008040496A patent/JP2008214847A/ja not_active Withdrawn
  • 2008-02-21 US US12/070,783 patent/US20080207074A1/en not_active Abandoned

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