EP1961844A2 - Electrically conductive filaments, fabrics made of these filaments and their use - Google Patents
Electrically conductive filaments, fabrics made of these filaments and their use Download PDFInfo
- Publication number
- EP1961844A2 EP1961844A2 EP20080001370 EP08001370A EP1961844A2 EP 1961844 A2 EP1961844 A2 EP 1961844A2 EP 20080001370 EP20080001370 EP 20080001370 EP 08001370 A EP08001370 A EP 08001370A EP 1961844 A2 EP1961844 A2 EP 1961844A2
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- EP
- European Patent Office
- Prior art keywords
- thread
- thermoplastic
- polyester
- component
- thread according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
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- 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
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- 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
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- 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 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 fibers of finite length (staple fibers), fibers of infinite length (filaments) and understood composite multifilaments or staple fibers secondarily spun yarns.
- 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 to mean the linear progression of the force-strain characteristic.
- An elastic elongation of up to 0.5% thus corresponds to a linear course of the force-strain curve in the range of 0 to 0.5% elongation.
- the force-elongation characteristic of the threads according to the invention shows a non-linear course.
- polyester of component a thread-forming polyesters according to the invention are used which, after spinning, stretching and, if appropriate, relaxing, give threads with the moduli of elasticity and elastic strains described above.
- these are polyethylene naphthalate homopolymers or copolymers containing ethylene naphthalate units. These polymers are thus derived from ethylene glycol and optionally further alcohols and naphthalenedicarboxylic acid or its polyester-forming derivatives, such as naphthalenedicarboxylic acid esters or 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. Main acid component of the polyesters is naphthalenedicarboxylic acid, optionally together with minor proportions, preferably up to 15 mol%, based on the total amount of dicarboxylic acids, other aromatic and / or aliphatic and / or cycloaliphatic dicarboxylic acids, preferably with para- or trans-standing aromatic compounds, such as terephthalic acid or 4,4'-biphenyldicarboxylic acid, and preferably with isophthalic acid and / or with aliphatic dicarboxylic acids, such as with adipic acid or sebacic acid ,
- Further preferred components a) are aromatic, liquid-crystalline polyesters, such as Polyoxibenzonaphtoat or polyhydroxy benzoate, which are optionally copolymerized with diols and dicarboxylic acids, or correspondingly constructed oxycarboxylic acids.
- aromatic, liquid-crystalline polyesters such as Polyoxibenzonaphtoat or polyhydroxy benzoate, which are optionally copolymerized 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 may be used. 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, in addition to polynaphthalate units, have further units derived from alkylene glycols, in particular ethylene glycol, and aliphatic and / or aromatic dicarboxylic acids, such as adipic acid, secacic acid, terephthalic acid or isophthalic acid.
- Particularly preferred components a) are polyethylene naphthalate homopolymers or copolyesters containing recurring structural units of the polyethylene naphthalate, repeating structural units of the polyethylene adipate, polyethylene sebacate, polyethylene isophthalate or in particular of the polyethylene terephthalate.
- 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, particularly preferably from 0.62 to 0.93 dl / g, (measured at 25 ° C in dichloroacetic acid (DCE)).
- IV values solution viscosities
- Threads of polyesters 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 finished polyester yarns are stabilized against hydrolytic degradation and are particularly suitable for use in hot, humid environments, e.g. 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 derived for the TPE-U, the TPE-E and the TPE-A typically from short-chain diols or diamines. In addition to the diols or diamines, the hard and soft segments of aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or diisocyanates are built up.
- 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. Due to the strong anisotropy
- the aggregates of carbon black particles or graphite platelets used according to the invention form longitudinally aligned aggregates during the spinning of the thread, 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 consists of polyester, preferably of polynaphthylene terephthalate and / or the other above for component a) enumerated as preferred polymers and / or polymer blends, and whose coat the components b), c ) and optionally d) in combination with a thermoplastic polymer, preferably a thermoplastic polyester, especially polynaphthylene terephthalate and / or other above for component a) enumerated as preferred polymers and / or polymer blends and / or polyethylene terephthalate homopolymers or polyethylene terephthalate copolymers.
- a thermoplastic polymer preferably a thermoplastic polyester, especially polynaphthylene terephthalate and / or other above for component a) enumerated as preferred polymers and / or polymer blends and / or polyethylene terephthalate homopolymers or polyethylene tere
- 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.
- the threads according to the invention can also be used in screens intended for use in paper machines.
- the components for the core 95% by weight of polyethylene naphthalate (“PEN”) and 5% by weight of polybutylene terephthalate (“PBT”), were in the extruder melted.
- the components for the shell in the form of a masterbatch (Deltacom PET 1917 EC3, Delta Plastics principless- und yearsgesellschaft mbH, Weeze, Germany) of polyethylene terephthalate (“PET”), thermoplastic elastomer, conductivity soot and additives were mixed and melted in another extruder ,
- PET polyethylene terephthalate
- thermoplastic elastomer thermoplastic elastomer
- conductivity soot additives were mixed and melted in another extruder .
- the melted spinning masses from both extruders were conveyed by means of gear pumps in a bicomponent spinner, spun into monofilaments and quenched in the spinning wheel, then re-drawn one or more times, optionally fixed and ceremoniessspult, as known from the
- the diameter of the monofilament produced was 169 ⁇ m.
- the monofilament had a shell content of 30% by weight and a core content of 70% by weight.
- the textile technological data of the monofilaments obtained are shown in the following table.
- PEN a type with an IV value of 0.72 dl / g was used.
- 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.
- Table ⁇ / u> example 1 Tensile strength (cN / tex) 43.8 Modulus of elasticity (GPa) 17.5 Elastic elongation (%) 0.5 Elongation at break (%) 18.5 Titre (dtex) 311 el. resistance 1) (S / cm) 1.0 * 10 -5 el. resistance 2) (S / cm) 7,0 * 10 -5 1) before the first dilution: 2) after 100 dilutions to 0.5% each
- the monofilament was clamped under slight tension between two clamps and silvered at two positions. At the silvered points electrical terminals were attached, which were connected to a resistance meter (Metra Hit 15 S, measuring range up to 30 M ⁇ ).
- the clamp spacing was chosen between 10 mm and 300 mm. By default, a clamp distance of 100 mm has been used.
- the resistance was measured per cm, ie ⁇ / cm.
- the conductance is the reciprocal resistance for 1 centimeter monofilament length.
Abstract
Description
Die vorliegende Erfindung betrifft Fäden mit sehr hohen elektrischen Leitfähigkeiten und ausgezeichneten mechanischen Eigenschaften. Diese Fäden, insbesondere in der Form von Monofilamenten, lassen sich beispielsweise in Sieben oder in Förderbändern einsetzen.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.
Es ist bekannt, dass Polyesterfasern für technische Anwendungen in den meisten Fällen beim Gebrauch hohen mechanischen und oder thermischen Belastungen unterworfen werden. Hinzu kommen in vielen Fällen Belastungen durch chemische und andere Umgebungseinflüsse, denen das Material einen ausreichenden Widerstand entgegensetzen muss. Bei all diesen Belastungen muss das Material eine gute Dimensionsstabiliät und Konstanz der Kraft-Dehnungseigenschaften über möglichst lange Benutzungszeiträume aufweisen. Außerdem darf das Material sich während Verarbeitung und bei der Anwendung nicht elektrostatisch aufladen.It is known that polyester fibers for technical applications are in most cases subjected to high mechanical and / or thermal stresses during use. In addition, in many cases, exposure to chemical and other environmental influences to which the material must oppose sufficient resistance. For all these loads, the material must have good dimensional stability and constancy of force-elongation properties over as long as possible usage periods. In addition, the material must not be electrostatically charged during processing and during use.
Ein Beispiel für technische Anwendungen, bei denen die Kombination guter mechanischer, thermischer, chemischer und elektrischer Beanspruchungen vorliegt, ist der Einsatz von Monofilamenten in Filtern, Sieben oder als Förderbänder. Dieser Einsatz verlangt Monofilamente mit ausgezeichneten mechanischen Eigenschaften, wie hohem Anfangsmodul, Reißfestigkeit, Knoten- und Schlingenfestigkeit, sowie mit einer hohen Abriebfestigkeit verbunden mit einer hohen Hydrolyseresistenz, um den hohen Beanspruchungen bei deren Einsatz zu widerstehen und um eine ausreichende Standzeit der Siebe oder Förderbänder zu gewährleisten.An example of technical applications involving the combination of good mechanical, thermal, chemical and electrical stresses is the use of monofilaments in filters, screens or as conveyor belts. This application requires monofilaments with excellent mechanical properties, such as high initial modulus, tear strength, knot and loop strength, as well as high abrasion resistance combined with a high resistance to hydrolysis in order to withstand the high stresses of their use and sufficient service life of the screens or conveyor belts guarantee.
In der industriellen Produktion, wie bei der Herstellung oder Verarbeitung von Papieren, werden Filter oder Förderbänder in Prozessen eingesetzt, die bei erhöhten Temperaturen ablaufen und in denen feucht-heiße Umgebungen vorliegen. Chemiefasern auf Polyesterbasis haben sich in solchen Umgebungen zwar bewährt, beim Einsatz in feucht-heißen Umgebungen neigen Polyester neben hydrolytischem Abbau auch zum mechanischen Abrieb.In industrial production, such as in the manufacture or processing of papers, filters or conveyor belts are used in processes that occur at elevated temperatures and in hot humid environments. Although 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.
Bei technischen Einsätzen kann Abrieb die unterschiedlichsten Ursachen haben. So wird das Blattbildungssieb oder Formiersieb in Papiermaschinen zur Entwässerung über Saugkästen gezogen mit der Folge eines erhöhten Siebverschleißes. In der Trockenpartie der Papiermaschine tritt Siebverschleiß durch Geschwindigkeitsdifferenzen zwischen Papierbahn und Sieboberfläche bzw. zwischen Sieboberfläche und Oberfläche der Trockentrommeln auf. Auch in anderen technischen Geweben tritt Gewebeverschleiß durch Abrieb auf; so z.B. in Transportbändern durch Schleifen über feststehende Oberflächen, in Filtergeweben durch das mechanische Abreinigen und in Siebdruckgeweben durch das Führen einer Rakel über die Sieboberfläche.In technical applications, abrasion can have a variety of causes. Thus, the sheet forming screen or forming fabric is pulled in paper machines for dewatering suction boxes with the result of increased Siebverschleißes. In the dryer section of the paper machine, 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.
In den Formiersieben moderner Papiermaschinen werden mehrlagige Gewebe eingesetzt. Um eine möglichst schnelle Entwässerung des Papiers zu erreichen, wird auf der Siebunterseite mit Saugkästen gearbeitet, die durch Unterdruck die Entwässerung der Papierbahn beschleunigen. Die Kontaktflächen der Ränder dieser Saugkästen mit dem Forminggewebe bestehen in der Regel aus Keramik, um übermäßigen Verschleiß an den Saugkästen vorzubeugen.Multi-ply fabrics are used in the forming fabrics of modern paper machines. In order to achieve the fastest possible dewatering of the paper, 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.
Die hohen Produktionsgeschwindigkeiten, die Reibung der den Monofilen zugesetzten Füllstoffe und die Ansaugleistung der Papiermaschine führen andererseits zu einem hohen Verschleiß auf der Unterseite des mehrlagigen Formiersiebes.On the other hand, the high production speeds, the friction of the fillers added to the monofilaments and the suction power of the paper machine lead to a high level of wear on the underside of the multilayer Forming screen.
Zur Verbesserung der Abriebbeständigkeit der Siebunterseite wurde und werden heute noch Monofilamente aus Polyamid, z.B. aus Polyamid 6 oder aus Polyamid 6.6, eingesetzt. Wegen der höheren Formstabilität werden ansonsten vorwiegend Monofilamente aus Polyethylenterephthalat (nachstehend aus "PET" genannt) verwendet, aus denen das Formingsieb im wesentlichen besteht. Eine bewährte Konstruktion ist der sogenannte Wechselschuss auf der Siebunterseite: Hier wird alternierend ein Unterschuss aus einem Polyamidmonofil mit folgenden PET-Monofilen eingesetzt. Dadurch erzielt man einen Kompromiß aus Abriebbeständigkeit und Formstabilität.To improve the abrasion resistance of the underside of the sieve, 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. 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.
Die höhere Wasseraufnahme der Polyamide gegenüber PET führt beim Betrieb des Siebes zu einer Verlängerung der Schußdrähte. Dadurch drehen sich die Siebränder nach oben und das Sieb liegt nicht mehr plan in der Papiermaschine. Diesen unerwünschten Effekt bezeichnet man als "edge curling".The higher water absorption of the polyamides over PET leads to an extension of the weft wires during operation of the screen. As a result, the Siebränder turn up and the screen is no longer flat in the paper machine. This undesirable effect is called "edge curling".
Mit zahlreichen Entwicklungen wurde versucht, die Polyamid-Monofilamente durch solche aus anderen abriebbeständigen Polymeren zu ersetzen, die sowohl formstabil sind und die eine geringe Wasseraufnahme aufweisen sollen.Numerous developments have tried to replace the polyamide monofilaments with those made of other abrasion-resistant polymers, which are both dimensionally stable and should have a low water absorption.
Zu nennen sind Monofilamente aus PET-Blends, denen 10-40 % thermoplastisches Polyurethan (TPU) zugesetzt worden ist (vergl. z.B.
Weiter sind aus dem Stand der Technik Monofilamente mit Kern-Mantel Struktur bekannt, bei denen der Mantel aus einer Mischung aus thermoplastischem Polyester mit einem Schmelzpunkt von 200 bis 300°C, z.B. PET, und aus thermoplastischem, elastomeren Copolyetherester mit ausgewählten Polyetherdiol-Baugruppen als Weichsegmenten besteht, die ebenfalls verbesserte Abriebbeständigkeit aufweisen (vergl. z.B.
Weitere Polyesterzusammensetzungen aus kristallinen thermoplastischen Polyesterharzen, Polyesterelastomeren und Sorbitanester sind aus
Aus der
Während diese vorbekannten Fäden eine ausreichende Abriebbeständigkeit gewährleisten, lässt in vielen Fällen die elektrische Leitfähigkeit noch zu wünschen übrig. Es ist zwar seit langem bekannt, dass man Fäden zur Verbesserung der elektrischen Leitfähigkeit Ruß zusetzen kann. Mit den vorbekannten Lösungen lassen sich allerdings typischerweise nur elektrische Leitfähigkeiten bis zu 10-6 Siemens/cm erzielen. Beim Einsatz von vorbekannten Rußen zur Vergrößerung der elektrischen Leitfähigkeit hat sich gezeigt, dass beim Verstrecken der erzeugten Fäden die durch den Ruß gebildeten leitfähigen Pfade unterbrochen werden und dass dadurch eine deutliche Absenkung der elektrischen Leitfähigkeit eintritt.While these prior art threads provide sufficient abrasion resistance, in many cases the electrical conductivity still leaves something to be desired. Although it has long been known that you can add threads to improve the electrical conductivity carbon black. With the previously known solutions, however, typically only electrical conductivities of up to 10 -6 Siemens / cm can be achieved. When using prior art carbon blacks to increase the electrical conductivity has been shown that when stretching the threads produced, the conductive paths formed by the soot are interrupted and thereby a significant reduction in electrical conductivity occurs.
In der
In der
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Fäden, die eine hervorragende elektrische Leitfähigkeit aufweisen, sowie gute mechanische Eigenschaften und ausgezeichnete Abriebbeständigkeit besitzen.The object of the present invention is to provide filaments which have excellent electrical conductivity, good mechanical properties and excellent abrasion resistance.
Es wurde jetzt überraschend gefunden, daß Fäden enthaltend eine ausgewählte Stoffkombination dieses Eigenschaftsprofil aufweisen.It has now surprisingly been found that threads containing a selected combination of substances have this property profile.
Die Erfindung betrifft schmelzgesponnene Fäden mit einem Elastizitätsmodul von größer als 14 GPa und einer elastischen Dehnung von kleiner gleich 0,5 % enthaltend
- a) einen thermoplastischen Polyester,
- b) ein thermoplastisches elastomeres Block-Copolymer, und
- c) Ruß- und/oder Graphitteilchen in der Form von entlang der Längsachse des Fadens ausgerichteten Aggregaten, welche entlang der Längsachse des Fadens elektrisch leitfähige Pfade bilden.
- 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 filament which form electrically conductive paths along the longitudinal axis of the filament.
Unter Fäden werden im Rahmen dieser Beschreibung ganz allgemein Fasern endlicher Länge (Stapelfasern), Fasern unendlicher Länge (Filamente) sowie daraus zusammengesetzte Multifilamente oder aus Stapelfasern sekundär gesponnene Garne verstanden. Bevorzugt werden die schmelzgesponnenen Fäden in Form von Monofilamenten eingesetzt.In the context of this description, threads are generally fibers of finite length (staple fibers), fibers of infinite length (filaments) and understood composite multifilaments or staple fibers secondarily spun yarns. The melt-spun threads are preferably used in the form of monofilaments.
Unter Elastizitätsmodul wird im Rahmen dieser Beschreibung der Sekantenmodul der Kraft-Dehnungs-Kennlinie zwischen 0 und 1 % Dehnung verstanden.For the purposes of this description, modulus of elasticity is understood to mean the secant modulus of the force-strain characteristic between 0 and 1% elongation.
Unter elastischer Dehnung wird im Rahmen dieser Beschreibung der lineare Verlauf der Kraft-Dehnungs-Kennlinie verstanden. Einer elastischen Dehnung von bis zu 0,5 % entspricht also ein linearer Verlauf der Kraft-Dehnungs-kennlinie im Bereich von 0 bis 0,5 % Dehnung. Bei Dehnungen von größer als 0,5 % zeigt die Kraft-Dehnungs-Kennlinie der erfindungsgemäßen Fäden einen nichtlinearen Verlauf.In the context of this description, elastic elongation is understood to mean the linear progression of the force-strain characteristic. An elastic elongation of up to 0.5% thus corresponds to a linear course of the force-strain curve in the range of 0 to 0.5% elongation. For strains of greater than 0.5%, the force-elongation characteristic of the threads according to the invention shows a non-linear course.
Als Polyester der Komponente a) werden erfindungsgemäß fadenbildende Polyester eingesetzt, die nach dem Verspinnen, Verstrecken und gegebenenfalls Relaxieren Fäden mit den oben beschriebenen Elastizitätsmoduli und elastischen Dehnungen ergeben.As polyester of component a), thread-forming polyesters according to the invention are used which, after spinning, stretching and, if appropriate, relaxing, give threads with the moduli of elasticity and elastic strains described above.
In der Regel handelt es sich dabei um Polyethylennaphthalat-Homopolymere oder um Copolymere enthaltend Ethylennaphthalateinheiten. Diese Polymeren leiten sich also ab von Ethylenglykol und gegebenenfalls weiteren Alkoholen sowie von Naphthalindicarbonsäure oder deren polyesterbildenden Derivaten, wie Naphthalindicarbonsäureestern oder -chloriden.As a rule, these are polyethylene naphthalate homopolymers or copolymers containing ethylene naphthalate units. These polymers are thus derived from ethylene glycol and optionally further alcohols and naphthalenedicarboxylic acid or its polyester-forming derivatives, such as naphthalenedicarboxylic acid esters or chlorides.
Diese thermoplastischen Polyester sind an sich bekannt. Bausteine von thermoplastischen Copolyestern a) sind vorzugsweise die oben genannten Diole und Dicarbonsäuren, bzw. entsprechend aufgebaute polyesterbildende Derivate. Hauptsäurebestandteil der Polyester ist Naphthalindicarbonsäure, gegebenenfalls zusammen mit geringeren Anteilen, vorzugsweise bis zu 15 Mol %, bezogen auf die Gesamtmenge der Dicarbonsäuren, anderer aromatischer und/oder aliphatischer und/oder cycloaliphatischer Dicarbonsäuren, vorzugsweise mit para- oder trans-ständigen aromatischen Verbindungen, wie z.B. Terephthalsäure oder 4,4'-Biphenyldicarbonsäure, sowie vorzugsweise mit Isophthalsäure und/oder mit aliphatischen Dicarbonsäuren, wie z.B. mit Adipinsäure oder Sebacinsäure.These 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. Main acid component of the polyesters is naphthalenedicarboxylic acid, optionally together with minor proportions, preferably up to 15 mol%, based on the total amount of dicarboxylic acids, other aromatic and / or aliphatic and / or cycloaliphatic dicarboxylic acids, preferably with para- or trans-standing aromatic compounds, such as terephthalic acid or 4,4'-biphenyldicarboxylic acid, and preferably with isophthalic acid and / or with aliphatic dicarboxylic acids, such as with adipic acid or sebacic acid ,
Weitere bevorzugt eingesetzte Komponenten a) sind aromatische, flüssigkristalline Polyester, wie Polyoxibenzonaphtoat oder Polyhydroxy-benzoat, die gegebenenfalls mit Diolen und Dicarbonsäuren, bzw. entsprechend aufgebaute Oxycarbonsäuren copolymerisiert sind.Further preferred components a) are aromatic, liquid-crystalline polyesters, such as Polyoxibenzonaphtoat or polyhydroxy benzoate, which are optionally copolymerized with diols and dicarboxylic acids, or correspondingly constructed oxycarboxylic acids.
Bevorzugte thermoplastische Polyester sind vollständig aromatische, flüssigkristalline Polyester, inbesondere Polyester enthaltend p-Hydroxybenzoateinheiten.Preferred thermoplastic polyesters are completely aromatic, liquid-crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
Neben Ethylenglykol können geeignete zweiwertige Alkohole eingesetzt werden. Typische Vertreter davon sind aliphatische und/oder cycloaliphatische Diole, beispielsweise Propandiol, 1,4-Butandiol, Cyclohexandimethanol oder deren Gemische.In addition to ethylene glycol, suitable dihydric alcohols may be used. Typical representatives thereof are aliphatic and / or cycloaliphatic diols, for example propanediol, 1,4-butanediol, cyclohexanedimethanol or mixtures thereof.
Beispiele für bevorzugte Komponenten a) sind Copolyester, die neben Polynaphthalat-Einheiten weitere Einheiten aufweisen, die sich von Alkylenglykolen, insbesondere Ethylenglykol, und aliphatischen und/oder aromatischen Dicarbonsäuren, wie Adipinsäure, Secacinsäure, Terephthalsäure oder Isophthalsäure, ableiten.Examples of preferred components a) are copolyesters which, in addition to polynaphthalate units, have further units derived from alkylene glycols, in particular ethylene glycol, and aliphatic and / or aromatic dicarboxylic acids, such as adipic acid, secacic acid, terephthalic acid or isophthalic acid.
Besonders bevorzugte Komponenten a) sind Polyethylennaphthalat-Homopolymere oder Copolyester enthaltend neben wiederkehrenden Struktureinheiten des Polyethylennaphtalats wiederkehrende Struktureinheiten des Polyethylenadipats, Polyethylensebacats, Polyethylenisophthalats oder insbesondere des Polyethylenterephthalats.Particularly preferred components a) are polyethylene naphthalate homopolymers or copolyesters containing recurring structural units of the polyethylene naphthalate, repeating structural units of the polyethylene adipate, polyethylene sebacate, polyethylene isophthalate or in particular of the polyethylene terephthalate.
Die erfindungsgemäß eingesetzten Polyester der Komponente a) weisen üblicherweise Lösungsviskositäten (IV-Werte) von mindestens 0,60 dl/g, vorzugsweise von 0,60 bis 1,05 dl/g, besonders bevorzugt von 0,62 - 0,93 dl/g, auf (gemessen bei 25°C in Dichloressigsäure (DCE)).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, particularly preferably from 0.62 to 0.93 dl / g, (measured at 25 ° C in dichloroacetic acid (DCE)).
Bevorzugt werden Fäden aus Polyestern mit einem Gehalt an freien Carboxylgruppen von kleiner gleich 3 mval/kg.Threads of polyesters with a content of free carboxyl groups of less than or equal to 3 meq / kg are preferred.
Diese enthalten vorzugsweise ein Mittel zum Verschluß von freien Carboxylgruppen, beispielsweise ein Carbodiimid und/oder eine Epoxidverbindung.These preferably contain a means for occluding free carboxyl groups, for example a carbodiimide and / or an epoxide compound.
Derartig ausgerüstete Polyesterfäden sind gegenüber hydrolytischem Abbau stabilisiert und eignen sich besonders zum Einsatz in feucht-heißen Umgebungen, z.B. in Papiermaschinen oder als Filter.Such finished polyester yarns are stabilized against hydrolytic degradation and are particularly suitable for use in hot, humid environments, e.g. in paper machines or as a filter.
Bei den thermoplastischen und elastomeren Block-Copolymeren der Komponente b) kann es sich um unterschiedlichste Typen handeln. Solche Block-Copolymeren sind dem Fachmann bekannt.The 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.
Beispiele für Komponenten b) sind thermoplastische und elastomere Polyurethane (TPE-U), thermoplastische und elastomere Polyester (TPE-E), thermoplastische und elastomere Polyamide (TPE-A), thermoplastische und elastomere Polyolefine (TPE-O) und thermoplastische und elastomere Styrol-Blockcopolymere (TPE-S).Examples of 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).
Die thermoplastischen und elastomeren Block-Copolymeren b) können aus unterschiedlichsten Monomerkombinationen aufgebaut sein. In der Regel handelt es sich um Blöcke aus sogenannten Hart- und Weichsegmenten. Die Weichsegmente leiten sich bei den TPE-U, den TPE-E und den TPE-A typischerweise von Polyalkylenglykolethern ab. Die Hartsegmente leiten sich bei den TPE-U, den TPE-E und den TPE-A typischerweise von kurzkettigen Diolen oder Diaminen ab. Neben den Diolen bzw. Diaminen werden die Hart- und Weichsegmente von aliphatischen, cycloaliphatischen und/oder aromatischen Dicarbonsäuren oder Diisocyanaten aufgebaut.The 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 derived for the TPE-U, the TPE-E and the TPE-A typically from short-chain diols or diamines. In addition to the diols or diamines, the hard and soft segments of aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids or diisocyanates are built up.
Beispiele für thermoplastische Polyolefine sind Block-Copolymere, die Blöcke aus Ethylen-Propylen-Butadien und aus Polypropylen (EPDM/PP) oder aus Nitril-Butadien und aus Polypropylen (NBR/PP) aufweisen.Examples of 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).
Besonders bevorzugte Komponenten b) sind thermoplastische und elastomere Styrol-Blockcopolymere. Beispiele dafür sind Block-Copolymere, die Blöcke aus Styrol-Ethylen und aus Propylen-Styrol (SEPS) oder aus aus Styrol-Ethylen und aus Butadien-Styrol (SEBS) oder aus Styrol und aus Butadien (SBS) aufweisen.Particularly preferred components b) are thermoplastic and elastomeric styrene block copolymers. Examples of these are 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).
Unter thermoplastischen und elastomeren Block-Copolymeren sind im Rahmen dieser Beschreibung Block-Copolymere zu verstehen, der sich bei Raumtemperatur vergleichbar den klassischen Elastomeren verhalten, sich jedoch unter Wärmezufuhr plastisch verformen lassen und somit ein thermoplastisches Verhalten zeigen. Diese thermoplastischen und elastomeren Block-Copolymeren haben in Teilbereichen physikalische Vernetzungspunkte (z.B. Nebenvalenzkräfte oder Kristallite), die sich bei Wärme auflösen, ohne dass sich die Polymermoleküle zersetzen.In the context of this description, 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. These 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.
Als Komponente c) kommen ausgewählte Ruß- und/oder Graphitteilchen zum Einsatz. Dabei handelt es sich um Ruße oder Graphite, deren Primärteilchen in der Form von Aggregaten angeordnet sind, die vorzugsweise die Form eines Knäuels aufweisen, insbesondere die Form langgestreckter Fäden besitzen. Die erfindungsgemäß eingesetzten Ruße bestehen aus nanoskaligen Primärteilchen. Diese sind in der Regel kugelförmig und haben typischerweise Durchmesser im Bereich von 10 bis 300 nm. Infolge der starken Anisotropie der erfindungsgemäß eingesetzten Aggregate aus Rußteilchen oder der Graphitplättchen bilden sich beim Verspinnen des Fadens in Längsrichtung ausgerichtete Aggregate, welche entlang der Längsachse des Fadens elektrisch leitfähige Pfade bilden. Im unverstreckten Faden liegen diese Aggregate teilweise in geknäulter Form vor und werden durch das Verstrecken in Fadenlängsrichtung gedehnt, aber nicht zerrissen. Auf diese Weise werden die elektrisch leitfähigen Pfade im Faden erhalten.As component c) selected 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. Due to the strong anisotropy The aggregates of carbon black particles or graphite platelets used according to the invention form longitudinally aligned aggregates during the spinning of the thread, which form electrically conductive paths along the longitudinal axis of the thread. In the unstretched thread these aggregates are partially present in a geknäulter 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.
Besonders bevorzugt eingesetzte Komponenten c) sind Ruße, die in Form von länglichen aus mehreren miteinander in Kontakt stehenden Primärteilchen aufgebauten Aggregaten im Faden vorliegen und dem verstreckten Faden der eine elektrische Leitfähigkeit von mindestens 0,5 * 10-6 Siemens/cm, vorzugsweise mindestens 1,0 * 10-5 Siemens/cm, gemessen in der Längsrichtung des Fadens, verleihen.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.
Die Mengen an Komponenten a), b) und c) in den erfindungsgemäßen Fäden können in weiten Bereichen gewählt werden. Typischerweise enthalten die Fäden 20 bis 70 Gew. % an Komponente a), 15 bis 40 Gew. % an Komponente b) und 5 bis 50 Gew. % an Komponente c), jeweils bezogen auf die Gesamtmasse des Fadens.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.
Die erfindungsgemäß eingesetzte Kombination der Komponenten a), b) und c) verleiht den Fäden neben einer ausgezeichneten Abriebbeständigkeit gute textiltechnologische Eigenschaften, insbesondere gute dynamische Eigenschaften und eine ausgezeichnete Formbeständigkeit, sowie eine hervorragende elektrische Leitfähigkeit.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.
Die zur Herstellung der erfindungsgemäßen Fäden benötigten Komponenten a), b) und c) sind an sich bekannt, teilweise kommerziell erhältlich oder können nach an sich bekannten Verfahren hergestellt werden.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.
Die erfindungsgemäßen Fäden können neben Komponenten a), b) und c) noch weitere Hilfsstoffe d) enthalten.The threads according to the invention may contain, in addition to components a), b) and c), further auxiliaries d).
Beispiele dafür sind neben dem bereits erwähnten Hydrolysestabilisator Verarbeitungshilfsmittel, Antioxidantien, Weichmacher, Gleitmittel, Pigmente, Mattierungsmittel, Viskositätsmodifizierer oder Kristallisationbeschleuniger.Examples of these are, in addition to the hydrolysis stabilizer already mentioned, processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
Beispiele für Verarbeitungshilfsmittel sind Siloxane, Wachse oder längerkettige Carbonsäuren oder deren Salze, aliphatische, aromatische Ester oder Ether.Examples of processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
Beispiele für Antioxidantien sind Phosphorverbindungen, wie Phosphorsäureester oder sterisch gehinderte Phenole.Examples of antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
Beispiele für Pigmente oder Mattierungsmittel sind organische Farbstoffpigmente oder Titandioxid.Examples of pigments or matting agents are organic dye pigments or titanium dioxide.
Beispiele für Viskositätsmodifizierer sind mehrwertige Carbonsäuren und deren Ester oder mehrwertige Alkohole.Examples of viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
Die erfindungsgemäßen Fäden können in beliebiger Form vorliegen, beispielsweise als Multifilamente, als Stapelfasern, als sekundär gesponnene Garne, auch in der Form von Zwirnen, oder insbesondere als Monofilamente.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.
In einer besonders bevorzugten Ausführungsform liegen die erfindungsgemäßen Fäden als Mehrkomponentenfäden vor. Beispiele dafür sind Seitean-Seite-Fäden oder insbesondere Kern-Mantel-Fäden. Bei letzteren besteht der Mantel vorzugsweise aus einer Zusammensetzung enthaltend Komponenten a), b), c) und gegebenenfalls d) und der Kern besteht aus einem fadenbildenden Polymer, das die mechanischen Eigenschaften, hauptsächlich die Festigkeit und Reißdehnung, des Gesamtfadens bestimmt.In a particularly preferred embodiment, the threads according to the invention are present as multicomponent threads. Examples of this are side-on threads or, in particular, core-sheath threads. In the latter, 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.
Eine besonders bevorzugte Kombination ist ein Kern-Mantel-Faden, dessen Kern aus Polyester, vorzugsweise aus Polynaphthylenterephthalat und/oder den anderen weiter oben für Komponente a) als bevorzugt aufgezählten Polymeren und/oder Polymergemischen, besteht und dessen Mantel die Komponenten b), c) und gegebenenfalls d) in Kombination mit einem thermoplastischen Polymer, bevorzugt einem thermoplastischen Polyester, insbesondere Polynaphthylenterephthalat und/oder andere weiter oben für Komponente a) als bevorzugt aufgezählte Polymere und/oder Polymergemische und/oder Polyethylenterephthalat-Homopolymere oder Polyethylenterephthalat-Copolymere enthält.A particularly preferred combination is a core-sheath thread whose core consists of polyester, preferably of polynaphthylene terephthalate and / or the other above for component a) enumerated as preferred polymers and / or polymer blends, and whose coat the components b), c ) and optionally d) in combination with a thermoplastic polymer, preferably a thermoplastic polyester, especially polynaphthylene terephthalate and / or other above for component a) enumerated as preferred polymers and / or polymer blends and / or polyethylene terephthalate homopolymers or polyethylene terephthalate copolymers.
Bei bevorzugten Kern-Mantel-Fäden beträgt das Gewichtsverhältnis von Kern und Mantel 95 : 5 bis 20 : 80, vorzugsweise 75 : 25 bis 45 : 55, insbesondere 70 : 30 bis 50 : 50.In preferred core-sheath filaments, 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.
Der Titer der erfindungsgemäßen Fäden kann in weiten Bereichen schwanken. Beispiele dafür sind 1 bis 45.000 dtex, insbesondere 100 bis 4.000 dtex.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.
Die Querschnittsform der erfindungsgemäßen Fäden kann beliebig sein, beispielsweise rund, oval oder n-eckig, wobei n größer gleich 3 ist.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.
Die erfindungsgemäßen Fäden können nach an sich bekannten Verfahren hergestellt werden.The threads of the invention can be prepared by methods known per se.
Ein typisches Herstellverfahren umfasst die Maßnahmen:
- i) Extrudieren eines Gemisches enthaltend Komponenten a), b) und c) durch eine Spinndüse,
- ii) Abziehen des gebildeten Filaments,
- iii) Verstrecken, und
- iv) gegebenenfalls Relaxieren des gebildeten Filaments.
- i) extruding a mixture comprising components a), b) and c) through a spinneret,
- ii) stripping the formed filament,
- iii) stretching, and
- iv) optionally relaxing the formed filament.
Die Herstellung von Mehrkomponentenfäden erfolgt analog. Nur werden hier die Spinnmassen, welche die unterschiedlichen Komponenten bilden, in unterschiedlichen Extrudern aufgeschmolzen und durch eine Mehrkomponenten-Spinndüse gepresst.The production of multi-component threads is analogous. Only here are the spinning masses, which form the different components, melted in different extruders and pressed through a multi-component spinneret.
Die Zusammensetzung enthaltend ein thermoplastisches Polymer, Komponenten b), c) und gegebenenfalls d) oder enthaltend Komponenten a), b), c) und gegebenenfalls d) wird vorzugsweise in Form eines Masterbatches eingesetzt.The 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.
Die erfindungsgemäßen Fäden werden bei der Herstellung ein- oder mehrfach verstreckt.The threads according to the invention are drawn one or more times during production.
Besonders bevorzugt wird zur Herstellung der Fäden als Komponente a) und/oder als Komponente des Kernfadens ein durch Festphasenkondensation hergestellter Polyester eingesetzt.Particularly preferred for the production of the threads as component a) and / or as a component of the core thread, a polyester produced by solid phase condensation is used.
Nach dem Verpressen der Polymerschmelze durch eine Spinndüse wird der heiße Polymerfaden abgekühlt, z.B. in einem Kühlbad, vorzugsweise in einem Wasserbad, und anschließend aufgewickelt oder abgezogen. Die Abziehgeschwindigkeit ist dabei größer als die Spritzgeschwindigkeit der Polymerschmelze.After pressing the polymer melt through a spinneret, 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.
Der so hergestellte Faden wird anschließend ein- oder mehrfach nachverstreckt, gegebenenfalls fixiert und aufgespult, wie aus dem Stand der Technik für die genannten schmelzspinnbaren Polymere bekannt ist.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.
Bevorzugt werden die erfindungsgemäßen Fäden zur Herstellung von textilen Flächenkonstruktionen, insbesondere von Geweben, Spiralgeweben, Gelegen oder Gestricken, eingesetzt. Diese textilen Flächenkonstruktionen werden vorzugsweise in Sieben eingesetzt.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.
Textilen Flächenkonstruktionen enthaltend die erfindungsgemäßen Fäden sind ebenfalls Gegenstand dieser Erfindung.Textile surface constructions containing the threads according to the invention are likewise the subject of this invention.
Die erfindungsgemäßen Fäden lassen sich auf allen industriellen Gebieten einsetzen. Bevorzugt kommen sie bei Anwendungen zum Einsatz, in denen mit einem erhöhten Verschleiß sowie mit der Aufladung statischer Elektrizität durch mechanische Belastung zu rechnen ist. Beispiele dafür ist der Einsatz in Siebgeweben und Filtertüchern für Gas- und Flüssigkeitsfilter, in Trockenbändern, beispielsweise zur Herstellung von Lebensmitteln, in Verpackungsbehälter oder in Schläuchen zur Förderung kleiner Teilchen. Diese Verwendungen sind ebenfalls Gegenstand der vorliegenden Erfindung.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.
Eine weitere Verwendung der erfindungsgemäßen Fäden in der Form von Monofilamenten betrifft deren Einsatz als Förderbänder oder als Komponenten von Förderbändern.Another use of the filaments of the invention in the form of monofilaments relates to their use as conveyor belts or as components of conveyor belts.
Die erfindungsgemäßen Fäden können auch in Sieben, die zum Einsatz in Papiermaschinen vorgesehen sind, eingesetzt werden.The threads according to the invention can also be used in screens intended for use in paper machines.
Diese Verwendungen sind ebenfalls Gegenstand der vorliegenden Erfindung.These uses are also the subject of the present invention.
Die nachfolgenden Beispiele erläutern die Erfindung ohne diese zu begrenzen.The following examples illustrate the invention without limiting it.
Die Komponenten für den Kern, 95 Gew. % Polyethylennaphthalat ("PEN") und 5 Gew. % Polybutylenterephthalat ("PBT"), wurden im Extruder aufgeschmolzen. Die Komponenten für den Mantel in Form eines Masterbatches (Deltacom PET 1917 EC3, Firma Delta Kunststoffe Produktions- und Handelsgesellschaft mbH, Weeze, Deutschland) aus Polyethylenterephthalat ("PET"), thermoplastischem Elastomer, Leitfähigkeitsruß und Additiven wurden in einem anderen Extruder vermischt und aufgeschmolzen. Die aufgeschmolzenen Spinnmassen aus beiden Extrudern wurden mittels Zahnradpumpen in einen Bikomponenten-Spinnkopf gefördert, zu Monofilamenten versponnen und im Spinnad abgeschreckt, anschließend ein- oder mehrfach nachverstreckt, gegebenenfalls fixiert und aufgesspult, wie aus dem Stand der Technik für die genannten schmelzspinnbaren Polymere bekannt.The components for the core, 95% by weight of polyethylene naphthalate ("PEN") and 5% by weight of polybutylene terephthalate ("PBT"), were in the extruder melted. The components for the shell in the form of a masterbatch (Deltacom PET 1917 EC3, Delta Plastics Produktions- und Handelsgesellschaft mbH, Weeze, Germany) of polyethylene terephthalate ("PET"), thermoplastic elastomer, conductivity soot and additives were mixed and melted in another extruder , The melted spinning masses from both extruders were conveyed by means of gear pumps in a bicomponent spinner, spun into monofilaments and quenched in the spinning wheel, then re-drawn one or more times, optionally fixed and aufgesspult, as known from the prior art for said melt-spinnable polymers.
Der Durchmesser des erzeugten Monofilaments betrug 169 µm. Das Monofilament wies einen Mantelanteil von 30 Gew. % auf sowie einen Kernanteil von 70 Gew. %. Die textiltechnologischen Daten der erhaltenen Monofilamente sind in der folgenden Tabelle dargestellt.The diameter of the monofilament produced was 169 μm. The monofilament had a shell content of 30% by weight and a core content of 70% by weight. The textile technological data of the monofilaments obtained are shown in the following table.
Als PEN wurde eine Type mit einem IV-Wert von 0,72 dl/g eingesetzt.As PEN, a type with an IV value of 0.72 dl / g was used.
Der Masterbatch bestand zu 50 Gew. % aus der oben beschriebenen PET-Type sowie zu 27 Gew. % aus einem thermoplastischen, elastomeren Styrol-Blockcopolymer, zu 20 Gew. % aus einem Leitfähigkeitsruß und zu 3 Gew. % aus Verarbeitungsstabilisator, Gleitmittel, sterisch gehindertem Amin und Silan.
2) nach 100 Verdehnungen auf jeweils 0,5 %
2) after 100 dilutions to 0.5% each
Die Fasereigenschaften wurde wie folgt ermittelt:
- Zugfestigkeit gemäß DIN EN/ISO 2062
- Reißdehnung gemäß DIN EN/ISO 2062
- Tensile strength according to DIN EN / ISO 2062
- Elongation at break according to DIN EN / ISO 2062
Die Bestimmung der elektrischen Leitfähigkeit erfolgte wie folgt:The determination of the electrical conductivity was as follows:
Das Monofilament wurde unter leichter Vorspannung zwischen zwei Klemmen eingespannt und an zwei Positionen versilbert. An den versilberten Stellen wurden elektrische Klemmen angebracht, die mit einem Widerstandsmessgerät (Metra Hit 15 S; Meßbereich bis 30 MΩ) verbunden waren. Als Klemmenabstand wurden zwischen 10 mm und 300 mm gewählt. Standardmäßig ist ein Klemmenabstand von 100 mm verwendet worden. Gemessen wurde der Widerstand pro cm, also Ω/cm. Der Leitwert ist der reziproke Widerstand für 1 Zentimeter Monofillänge.The monofilament was clamped under slight tension between two clamps and silvered at two positions. At the silvered points electrical terminals were attached, which were connected to a resistance meter (Metra Hit 15 S, measuring range up to 30 MΩ). The clamp spacing was chosen between 10 mm and 300 mm. By default, a clamp distance of 100 mm has been used. The resistance was measured per cm, ie Ω / cm. The conductance is the reciprocal resistance for 1 centimeter monofilament length.
Beispiel: R = 620 kΩ/10 cm entspricht R = 62 kΩ/cm entspricht L = 1,6 * 10-5 S/cm.Example: R = 620 kΩ / 10 cm corresponds to R = 62 kΩ / cm corresponds to L = 1.6 * 10 -5 S / cm.
Claims (14)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE200710009117 DE102007009117A1 (en) | 2007-02-24 | 2007-02-24 | Electrically conductive threads, fabrics produced therefrom and their use |
Publications (2)
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EP1961844A2 true EP1961844A2 (en) | 2008-08-27 |
EP1961844A3 EP1961844A3 (en) | 2009-09-02 |
Family
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EP20080001370 Withdrawn EP1961844A3 (en) | 2007-02-24 | 2008-01-25 | Electrically conductive filaments, fabrics made of these filaments and their use |
Country Status (4)
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US (1) | US20080207074A1 (en) |
EP (1) | EP1961844A3 (en) |
JP (1) | JP2008214847A (en) |
DE (1) | DE102007009117A1 (en) |
Cited By (1)
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DE102015015254A1 (en) * | 2015-11-20 | 2017-05-24 | Licence | Device for cooling |
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DE102007009119A1 (en) * | 2007-02-24 | 2008-08-28 | Teijin Monofilament Germany Gmbh | Electrically conductive threads, fabrics produced therefrom and their use |
WO2018181699A1 (en) * | 2017-03-31 | 2018-10-04 | 東レ株式会社 | Elastic monofilament and woven knitted goods |
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DE69007517T2 (en) | 1989-03-07 | 1994-10-13 | Gen Electric | Polymer blend of aromatic polycarbonate, polyester and thermoplastic elastomer, molded body made of it. |
EP0674029A1 (en) | 1994-03-25 | 1995-09-27 | Hoechst Aktiengesellschaft | Abrasion resistant polyester-polyurethane composition with enhanced safety of processing and monofilaments thereof |
EP0735165A2 (en) | 1995-03-31 | 1996-10-02 | Hoechst Trevira GmbH & Co. KG | High resistance core-sheath monofilaments for technical applications |
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CA995071A (en) * | 1972-07-14 | 1976-08-17 | Dow Badische Company | Electrically-conductive textile fiber |
JPS5149919A (en) * | 1974-10-09 | 1976-04-30 | Teijin Ltd | |
IN146424B (en) * | 1976-04-29 | 1979-06-02 | Dow Badische Co | |
US5405682A (en) * | 1992-08-26 | 1995-04-11 | Kimberly Clark Corporation | Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and elastomeric thermoplastic material |
DE10112394A1 (en) * | 2001-03-13 | 2002-10-02 | Ticona Gmbh | Conductive plastic molding compound, its use and molded articles made therefrom |
KR100615782B1 (en) * | 2004-12-31 | 2006-08-25 | 주식회사 효성 | Dope dyed flame retardant polyester fiber and textile products therefrom |
DE102007009119A1 (en) * | 2007-02-24 | 2008-08-28 | Teijin Monofilament Germany Gmbh | Electrically conductive threads, fabrics produced therefrom and their use |
-
2007
- 2007-02-24 DE DE200710009117 patent/DE102007009117A1/en not_active Ceased
-
2008
- 2008-01-25 EP EP20080001370 patent/EP1961844A3/en not_active Withdrawn
- 2008-02-21 JP JP2008040496A patent/JP2008214847A/en not_active Withdrawn
- 2008-02-21 US US12/070,783 patent/US20080207074A1/en not_active Abandoned
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DE69007517T2 (en) | 1989-03-07 | 1994-10-13 | Gen Electric | Polymer blend of aromatic polycarbonate, polyester and thermoplastic elastomer, molded body made of it. |
EP0387395A2 (en) | 1989-03-17 | 1990-09-19 | Jwi Limited | Stabilized polyurethane modified polyester forming fabric |
DE69123510T2 (en) | 1990-08-14 | 1997-04-10 | Polyplastics Co | Resin composition of a polyester, a polyester elastomer and a sorbitan ester |
EP0674029A1 (en) | 1994-03-25 | 1995-09-27 | Hoechst Aktiengesellschaft | Abrasion resistant polyester-polyurethane composition with enhanced safety of processing and monofilaments thereof |
EP0735165A2 (en) | 1995-03-31 | 1996-10-02 | Hoechst Trevira GmbH & Co. KG | High resistance core-sheath monofilaments for technical applications |
WO1998014647A1 (en) | 1996-09-30 | 1998-04-09 | Hoechst Celanese Corporation | Electrically conductive heterofil |
EP1559815A2 (en) | 2004-01-29 | 2005-08-03 | Teijin Monofilament Germany GmbH | Conductive yarn, method of manufacture and use thereof |
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DE102015015254A1 (en) * | 2015-11-20 | 2017-05-24 | Licence | Device for cooling |
Also Published As
Publication number | Publication date |
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JP2008214847A (en) | 2008-09-18 |
DE102007009117A1 (en) | 2008-08-28 |
EP1961844A3 (en) | 2009-09-02 |
US20080207074A1 (en) | 2008-08-28 |
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