EP1413653A2 - Conductive, soil-resistant core-sheath fibre with high resistance to chemicals, its production process and use - Google Patents
Conductive, soil-resistant core-sheath fibre with high resistance to chemicals, its production process and use Download PDFInfo
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- EP1413653A2 EP1413653A2 EP03021088A EP03021088A EP1413653A2 EP 1413653 A2 EP1413653 A2 EP 1413653A2 EP 03021088 A EP03021088 A EP 03021088A EP 03021088 A EP03021088 A EP 03021088A EP 1413653 A2 EP1413653 A2 EP 1413653A2
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- European Patent Office
- Prior art keywords
- melt
- core
- sheath
- polymer
- spun fiber
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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
- 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
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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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
Definitions
- the present invention relates to conductive dirt-repellent core-sheath fibers, in particular monofilaments, which can be used in particular in technical fabrics.
- melt-spinnable fluoropolymers have good thermal stability, good chemical resistance and dirt-repellent properties. Attempts have already been made to process melt-spinnable fluoropolymers into fibers, multi- and monofilaments in order to use them to produce textile surfaces for technical applications with the above-mentioned properties of fluoropolymers.
- a disadvantage of melt-spinnable fluoropolymers is the high creep behavior. Fibers and filaments made from this material therefore have only low tensile strengths and are not dimensionally stable.
- fluoropolymers with polymers with good mechanical properties, e.g. with polyethylene terephthalate (hereinafter also called "PET").
- PET polyethylene terephthalate
- fluoropolymers are often incompatible with other polymers and generally do not mix.
- a two-phase mixture is often formed in which the fluoropolymers form spatial islands.
- the proportion by weight of fluoropolymer that can be metered in is therefore often limited, since the boundary layers of the polymers adhere to one another only poorly. In fibers, this property manifests itself as a "tendency to splice".
- Fibers made of synthetic polymers and fabrics made from them have the disadvantage, however, that they can become charged with static electricity.
- Conductive fibers for the production of textile fabrics, such as fabrics for technical use, or for other purposes, e.g. for brushes have always been the target of numerous developments.
- a flame retardant, electrically conductive fabric which contains electrically conductive and flame-retardant electrically non-conductive fibers.
- the electrically conductive fibers can contain electrically conductive particles such as carbon black or metal particles, have metal coatings or consist of electrically conductive materials such as polyanilines. Polyester and polyolefins are described as fiber materials.
- DE-A-39 38 414 describes high-strength fabrics made of synthetic fibers, which are woven in the form of electrically conductive fibers in warp and weft, and still contain electrically non-conductive fibers.
- the electrically conductive fibers consist of polyolefins and contain graphite or carbon black.
- EP-A-160,320 describes core-sheath monofilaments for use in hair brushes made from selected polymers.
- the core contains nylon or polyester which comprise at least 60% by weight of polybutylene terephthalate units.
- the jacket contains special nylon types or copolyether esters.
- DE-U-86/06334 discloses core sheath fibers, the core of which consists of thermoplastic, preferably polyamide, and the sheath of which is made of electrically conductive plastic, preferably of polyamide, which contains carbon black or metals.
- JP-A-07 / 278,956 describes electrically conductive copolyesters which mainly contain polybutylene terephthalate units and which are doped with carbon black. Core-sheath fibers made from this material are also described, in which the core consists of aromatic polyester.
- electrically conductive heterofilaments are known, which can be configured, for example, as core-sheath fibers.
- PET and other polyesters or PET / nylon are described as examples of core and sheath polymers.
- WO-A-01 / 20,076 discloses nonwovens with a high dielectric constant. Mixtures of polyvinylidene fluoride and polypropylene are proposed as fiber material. The products made from it are characterized by an extended half-life of electrostatic charges and can be used as electrostatic filters.
- US-A-6,085,061 describes a brush for cleaning electrostatically charged surfaces.
- Core-sheath fibers whose core is electrically conductive and whose sheath is made of polyvinylidene fluoride can be used as fiber materials.
- DE-A-44 12 396 discloses melt-spun undrawn, electrically non-conductive fibers with a core-sheath structure, the sheath of which contain fluoropolymers.
- Polycarbonate is used as the core polymer.
- This fiber is used as an optical fiber and is due to its low strength for technical textiles such as technical fabrics, not suitable.
- high reflection at the boundary layer and the lowest possible attenuation of the electromagnetic wave are important. Both properties can only be achieved by using a high-purity coating.
- JP-A-2001-127,218 describes a semiconducting fiber made of a fluoropolymer containing carbon black. This fiber has no core-sheath structure and is used for the production of non-wovens, for example by the melt-blow process. The fiber is not drawn.
- the present invention was based on the object of combining the application-related advantages of the materials known for fiber production without having to accept the disadvantages known from the use of the individual materials.
- adhesion problems normally occur at the interface between two polymers. This applies in particular when using fluoropolymers known to have poor adhesion with other polymers. Surprisingly, it has been shown that very good adhesion to the polymer core can be achieved when using a fluoropolymer doped with electrically conductive particles.
- Another object of the present invention is therefore to provide core-sheath fibers with good adhesion between the individual layers.
- the present invention thus provides fibers, in particular monofilaments, which combine high chemical and antistatic properties thermal resistance and good mechanical dimensional stability and high tensile strength.
- the invention relates to a melt-spun fiber with a core-sheath structure and a tensile strength of at least 15 cN / tex, the core of which contains a synthetic thermoplastic polymer that is not a fluoropolymer, and the sheath of which contains at least one melt-spinnable fluoropolymer and particles of electrically conductive material.
- the synthetic thermoplastic polymers forming the core can be of any nature as long as they are melt-spinnable and give the fiber the properties desired for the particular application. Fluoropolymers are not included in the synthetic thermoplastic polymers, although in addition to these polymers the core may also contain fluoropolymers as a blend component.
- thermoplastic materials are polyolefins, such as polyethylene, polypropylene or copolymers containing ethylene and / or propylene units in combination with other alpha-olefin units copolymerized therewith, such as alpha-butylene, alpha-pentylene, alpha-hexylene or alpha-octylene; Polyesters such as polycarbonate, aliphatic / aromatic polyesters or fully aromatic polyesters; Polyamides, such as aliphatic or alphatic / aromatic polyamides (nylon types) or fully aromatic polyamides (aramids); or polyether ketones, that is to say polymers which have at least ether and ketone groups and generally aromatic divalent radicals, such as phenylene, in the repeating chain, many combinations of these groups being possible, for example PEK, PEEK or PEKK; or polyarylene sulfides, preferably polyphenylene sulfide; or polyether esters, that is to say polymers which have at least
- the core of the core-sheath fibers according to the invention preferably contains polyamides and in particular polyester.
- thermoplastic polyamides which are preferably used in the compositions according to the invention are known per se.
- thread-forming polyamides such as aliphatic or aliphatic / aromatic polyamides, such as e.g. Polycaprolactam, poly- (hexamethylene-1,6-diaminadipic acid diamide), poly- (hexamethylene-1,6-diamine-sebacic acid diamide), poly- (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly- (hexamethylene -1,6-diamine isopthalklarediamid); or also completely aromatic polyamides, such as poly (phenylene-1,4-diamine-terephthalic acid diamide) or poly- (phenylene-1,4-diamine-isophthalic acid diamide).
- aliphatic or aliphatic / aromatic polyamides such as e.g. Polycaprolactam, poly- (hexamethylene-1,6-diaminadipic acid diamide), poly- (hexamethylene-1,6-diamine-sebacic
- the polyamides used according to the invention usually have viscosity numbers according to DIN 53727 of 120 to 350, preferably 150 to 320 cm 3 / g (measured at 25 ° C. in sulfuric acid).
- thermoplastic polyesters and / or aromatic liquid-crystalline polyesters used with particular preference in the compositions according to the invention are known per se.
- thread-forming polyesters such as polycarbonate or aliphatic / aromatic polyesters, such as, for example, polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or in particular polyethylene terephthalate, but also completely aromatic, liquid-crystalline polyesters, such as polyoxibenzonaphtoate.
- Modules of thread-forming polyesters are preferably diols and dicarboxylic acids or correspondingly constructed oxycarboxylic acids.
- the main acid component of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para or trans-aromatic compounds, such as 2,6-naphthalene dicarboxylic acid or 4,4'-biphenyldicarboxylic acid , but also p-hydroxy-benzoic acid.
- aliphatic Dicarboxylic acids such as adipic acid or sebacic acid, are preferably used in combination with aromatic dicarboxylic acids.
- Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic and / or aromatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol but also hydroquinone.
- thermoplastic polyesters are selected in particular from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate containing polybutylene glycol, terephthalic acid and naphthalene acid and naphthalene units.
- thermoplastic polyesters are aromatic, liquid-crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
- polyesters which are to be used in hot and humid environments, such as monofilaments when used in paper machines and which contain polyester as the core component
- these polyesters are preferably stabilized against hydrolytic degradation by adding polyester stabilizers.
- Such stabilized fibers show a significant reduction in the degradation tendency of the polyester, so that lifetimes of monofilaments can be achieved, which are equivalent to those of monofilaments based on extremely resistant fiber materials, such as polyarylene sulfides or oxides.
- Fibers containing polyester stabilized in the core are particularly preferred, particularly preferably carbodiimides.
- the polyesters 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 0.62-0.93 dl / g ( measured at 25 ° C in dichloroacetic acid (DCE)).
- IV values solution viscosities
- the fluoropolymers forming the jacket can also be of any nature as long as they are melt-spinnable.
- the fluoropolymers used according to the invention are poly (fluoroolefin) homopolymers and / or copolymers derived from ethylenically unsaturated fluorine-containing olefin monomers and other monomers copolymerizable therewith. Such polymers are also known per se.
- melt-spinnable copolymers of tetrafluoroethylene with other alpha-olefins such as ethylene, propylene, butylene, hexylene or octylene.
- Homopolymers or copolymers can also be used which are derived from other fluorine-containing monomers, for example from mono-, di- or trifluoroethylene, from vinyl fluoride or in particular from vinylidene fluoride.
- melt-spinnable copolymers of tetrafluoroethylene with at least one alpha-olefin, preferably with ethylene is particularly preferred.
- PVDF Polyvinylidene fluoride
- the invention therefore also relates to a heterofilament fiber containing at least two components, the first component being an electrical insulator and one thermoplastic polymer that is not a fluoropolymer and the second component comprises polyvinylidene fluoride.
- the particles of electrically conductive material present in the sheath of the melt-spun fiber according to the invention can be of any nature as long as they give the sheath an increased electrical conductivity.
- These can be particles of carbon, for example carbon fibers, carbon black or graphite; from metals, for example from copper, silver, aluminum or iron; made of metal alloys, for example bronze; or act from conductive plastics, for example from polyanilines or from polypyrrole.
- the particles can be in any form, for example in the form of fibers or in the form of round or irregular particles.
- the content of the electrically conductive particles in the jacket should be selected so that there is a significant increase in the electrical conductivity of the plastic material. Typical amounts are in the range of up to 50% by weight, preferably 2 to 15% by weight, based on the amount of the jacket material.
- Melt-spun fibers in which the sheath contains between 2% by weight and 15% by weight, in particular between 4% by weight and 9% by weight, of electrically conductive particles are particularly preferred.
- the core-sheath fibers according to the invention can be in any form, for example as multifilaments, as staple fibers or in particular as monofilaments.
- the titer of the core-sheath fibers according to the invention can also vary within wide ranges. Examples of this are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
- Monofilaments are particularly preferred.
- Monofilaments whose cross-sectional shape is round, oval or n-angular are particularly preferred, n greater than or equal to 3.
- the staple lengths for staple fibers can also vary widely, for example between 30 and 70 mm.
- the core of the core-sheath fiber according to the invention forms the mechanical carrier of the fiber, while the sheath mainly determines the usage properties, such as antistatic behavior and sliding behavior.
- a commercially available PET raw material can preferably be used as the core.
- a fluoropolymer based on PVDF is particularly preferably used for the jacket, which was previously processed into a spinnable mixture, in particular with carbon black.
- the proportion by weight of component A) forming the core to component B) forming the shell is, based on the total amount of these components, 50 to 95% by weight, preferably 60 to 80% by weight, for component A) and 50 to 80% by weight for component B) 5% by weight, preferably 40 to 20% by weight.
- the core-shell fibers according to the invention can be produced by methods known per se.
- the two polymers or mixtures containing these polymers are preferably dried immediately before being fed into the extruder, melted in the extruder and filtered through a spin pack.
- the fluoropolymer is provided with the electrically conductive particles. This is usually done before the fluoropolymer is fed to the extruder, but can also be done immediately before the spin pack. Masterbatches containing the fluoropolymer and electrically conductive particles can also be used.
- the molten polymer thread is cooled in a spinning bath, for example a water bath, and then wound up or drawn off.
- the pulling-off speed is greater than the spraying speed of the polymer melt and thus causes the thread formed to stretch.
- the heterofilament spun thread thus produced is then preferably subjected to post-drawing, particularly preferably in several stages, in particular a two- or three-stage post-drawing, with a total drawing ratio of 1: 3 to 1: 8, preferably 1: 4 to 1: 6.
- heat setting preferably follows, using temperatures of 130 to 280 ° C; work is carried out at a constant length or a shrinkage of up to 30% is permitted.
- the spinning take-off speed is usually 10-40 m per minute.
- thermoplastic polymer of the core and the fluoropolymer of the shell are spun into a bicomponent monofilament in a core-shell structure, surprisingly a very good core-shell adhesion is shown.
- the conductivity of the jacket can be lost during stretching, but can be restored by heat treatment and the shrinkage caused thereby, preferably above the melting point of the jacket material, but below the melting temperature of the core.
- the surface properties are mainly determined by the conductively doped fluoropolymer.
- the fibers according to the invention are distinguished by very good dirt repellency, good chemical resistance and electrical conductivity.
- the combination with the fluoropolymer leads to fibers with improved sliding properties compared to fibers made of pure thermoplastic polymer. These fibers show increased dirt repellency compared to fibers made from pure thermoplastic polymer.
- the fibers according to the invention can contain auxiliaries.
- auxiliaries are processing aids, stabilizers, 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.
- stabilizers and antioxidants are the polyester stabilizers already mentioned above, phosphorus compounds, such as phosphoric acid esters or carbodiimides.
- pigments or matting agents examples include organic dye pigments or titanium dioxide.
- viscosity modifiers are polyvalent carboxylic acids and their esters or polyvalent alcohols.
- the fibers according to the invention are preferably used for the production of textile fabrics, such as woven fabrics, knitted fabrics, knitted fabrics, laid fabrics and nonwovens.
- Textile fabrics containing monofilaments according to the invention are particularly suitable for technical purposes, such as for filters, as screen printing materials or in particular as paper machine screens.
- the monofilaments according to the invention have good textile-physical properties and are easy to weave.
- the fabrics have the usual dimensional stability of the core-forming thermoplastic polymers.
- Fabrics made from these monofilaments are ideally suited for technical fabrics, particularly in the filtration of aggressive media, where there is also a risk of electrostatic charging; i.e. especially in solid-gaseous and solid-liquid filtration.
- the invention also relates to the use of the fibers for the production of textile fabrics which are used in environments with high chemical and / or physical stress, in particular as paper machine screens or as technical fabrics, such as those e.g. in filtration, for the production of conveyor belts or as reinforcing inserts.
- the fibers are used as monofilaments and in particular as weft threads in the fabric.
- the use of the monofilaments according to the invention as paper machine screens can be in the forming section, the press section or in particular in the dryer section respectively. In the dryer section, the monofilaments according to the invention are used in particular as spiral screens.
- the fibers used according to the invention in particular in the form of monofilaments, usually have a titer range from 10 to 4500 tex, an elastic modulus from 2.0 to 8.0 N / tex, a tenacity-related strength from 15 to 50 cN / tex Elongation at break from 15 to 45% and a hot air shrinkage at 180 ° C from 1.0 to 20.0%.
- Core-shell fibers made of polyethylene terephthalate and polyvinylidene fluoride containing carbon black
- PET polyethylene terephthalate
- PVDF polyvinylidene fluoride
- the core-sheath monofilament obtained had the following properties: titres 2890 dtex strength 24 cN / tex HLS (hot air shrink 10 'at 160 ° C) 2.5% loop strength > 20 cN / tex elongation 44% BZD (reference elongation at 12 cN / tex) 8.5% BZD (reference elongation at 15 cN / tex) 13% EGG. Resistance (10 mm clamping length) 8 * 10 5 (ohms) EGG. Resistance (150 mm clamping length) 9 * 10 6 (ohms)
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Abstract
Description
Die vorliegende Erfindung betrifft leitfähige schmutzabweisende Kern-Mantel-Fasern, insbesondere Monofilamente, die sich insbesondere in technischen Geweben einsetzen lassen.The present invention relates to conductive dirt-repellent core-sheath fibers, in particular monofilaments, which can be used in particular in technical fabrics.
Es ist bekannt, dass Fluorpolymere eine gute thermische Stabilität, gute Chemikalienresistenz und schmutzabweisende Eigenschaften haben. Es ist bereits versucht worden, schmelzspinnbare Fluorpolymere zu Fasern, Multi- und Monofilamenten zu verarbeiten, um daraus textile Flächen für technische Anwendungen mit den oben genannten Eigenschaften von Fluorpolymeren herzustellen. Nachteilig bei schmelzspinnbaren Fluorpolymeren ist das hohe Kriechverhalten. Fasern und Filamente aus diesem Material haben deshalb nur geringe Zugfestigkeiten und sind nicht formstabil.It is known that fluoropolymers have good thermal stability, good chemical resistance and dirt-repellent properties. Attempts have already been made to process melt-spinnable fluoropolymers into fibers, multi- and monofilaments in order to use them to produce textile surfaces for technical applications with the above-mentioned properties of fluoropolymers. A disadvantage of melt-spinnable fluoropolymers is the high creep behavior. Fibers and filaments made from this material therefore have only low tensile strengths and are not dimensionally stable.
Es ist auch bereits versucht worden, Fluorpolymere mit Polymeren mit guten mechanischen Gebrauchseigenschaften zu kombinieren, z.B. mit Polyethylenterephthalat (nachfolgend auch "PET" genannt). Dabei ist allerdings festzustellen, dass Fluorpolymere mit anderen Polymeren oft unverträglich sind und sich in der Regel nicht vermischen. Es entsteht also häufig ein Zweiphasengemisch, in dem die Fluorpolymeren räumliche Inseln bilden. Der Gewichtsanteil an Fluorpolymer, der zudosiert werde kann, ist somit häufig begrenzt, da die Grenzschichten der Polymere nur schlecht aneinander haften. In Fasern macht sich diese Eigenschaft als "Spleißneigung" bemerkbar.Attempts have also been made to combine fluoropolymers with polymers with good mechanical properties, e.g. with polyethylene terephthalate (hereinafter also called "PET"). It should be noted, however, that fluoropolymers are often incompatible with other polymers and generally do not mix. A two-phase mixture is often formed in which the fluoropolymers form spatial islands. The proportion by weight of fluoropolymer that can be metered in is therefore often limited, since the boundary layers of the polymers adhere to one another only poorly. In fibers, this property manifests itself as a "tendency to splice".
Monofilamente aus PET und statistischen Copolymeren aus Ethylen und Tetrafluorethylen ("ETFE") sind seit Jahren kommerziell erhältlich. Häufig weisen diese Fasern zur Hydrolysestabilisierung einen niedrigen Carboxylendgruppengehalt auf, und sind zum Verschluß der Carboxylendgruppen mit Carbodiimiden stabilisiert. Der Verschluß von Carboxylgruppen mittels Carbodiimiden ist z.B. in den EP-A-417,717 und EP-A-503,421 beschrieben.Monofilaments made of PET and statistical copolymers of ethylene and tetrafluoroethylene ("ETFE") have been commercially available for years. Often point these fibers have a low carboxyl end group content to stabilize hydrolysis, and are stabilized with carbodiimides to close the carboxyl end groups. The closure of carboxyl groups by means of carbodiimides is described, for example, in EP-A-417,717 and EP-A-503,421.
Technische Gewebe, die aus diesen Monofilamenten hergestellt werden, haben weitgehend die mechanischen Eigenschaften eines PET Monofilaments, jedoch mit erhöhter Hydrolyseresistenz und verbesserter Schmutzabweisung. Temperaturstabilität und Chemikalienbeständigkeit dieser Fasern entsprechen wegen des relativ geringen Anteils an Fluorpolymeren im wesentlichen den Werten des reinen PET. Die erhöhte Spleißneigung kann sich allerdings bei mechanischen Belastungen bemerkbar machen, z.B. beim Anschlag des Webriets.Technical fabrics made from these monofilaments largely have the mechanical properties of a PET monofilament, but with increased resistance to hydrolysis and improved dirt repellency. The temperature stability and chemical resistance of these fibers essentially correspond to the values of pure PET because of the relatively low proportion of fluoropolymers. However, the increased tendency to splice can be noticeable with mechanical loads, e.g. at the attack of the Webriet.
Fasern aus synthetischen Polymeren und daraus hergestellte Gewebe haben allerdings den Nachteil, dass sie sich durch Reibung mit statischer Elektrizität aufladen können. Leitfähige Fasern zur Herstellung von textilen Flächengebilden, wie Geweben für technischen Einsatz, oder für andere Einsatzzwecke, z.B. für Bürsten, waren von jeher Ziel zahlreicher Entwicklungen.Fibers made of synthetic polymers and fabrics made from them have the disadvantage, however, that they can become charged with static electricity. Conductive fibers for the production of textile fabrics, such as fabrics for technical use, or for other purposes, e.g. for brushes have always been the target of numerous developments.
Aus der DE-A-198 26 120 ist ein flammhemmendes, elektrisch leitfähiges Gewebe bekannt, das elektrisch leitfähige und flammfest ausgerüstete elektrisch nicht-leitfähige Fasern enthält. Die elektrisch leitfähigen Fasern können elektrisch leitfähige Teilchen, wie Ruß oder Metallteilchen, enthalten, Metallüberzüge aufweisen oder aus elektrisch leitfähigen Materialien, wie Polyanilinen, bestehen. Als Fasermaterialien werden Polyester und Polyolefine beschrieben.From DE-A-198 26 120 a flame retardant, electrically conductive fabric is known, which contains electrically conductive and flame-retardant electrically non-conductive fibers. The electrically conductive fibers can contain electrically conductive particles such as carbon black or metal particles, have metal coatings or consist of electrically conductive materials such as polyanilines. Polyester and polyolefins are described as fiber materials.
Aus der DE-U-86 238 79 sind Garne für die Herstellung von Spiralbändern bekannt, die mit einer Schicht aus härtbaren Polymeren ummantelt sind. Diese Schicht enthält elektrisch leitfähigen Kohlenstoff. Als Polymere für die Mantelschicht werden Melaminharze, Epoxide, Phenolharze oder Polyurethane beispielhaft genannt.From DE-U-86 238 79 yarns for the production of spiral tapes are known, which are coated with a layer of curable polymers. This layer contains electrically conductive carbon. Melamine resins, epoxies, phenolic resins or polyurethanes are mentioned as examples of polymers for the cladding layer.
Die DE-A-39 38 414 beschreibt hochfeste Gewebe aus Kunstfasern, wobei diese in Form von elektrisch leitfähigen Fasern in Kette und Schuss eingewebt sind, und weiterhin elektrisch nicht-leitfähige Fasern enthalten. Die elektrisch leitfähigen Fasern bestehen aus Polyolefinen und enthalten Graphit oder Ruß.DE-A-39 38 414 describes high-strength fabrics made of synthetic fibers, which are woven in the form of electrically conductive fibers in warp and weft, and still contain electrically non-conductive fibers. The electrically conductive fibers consist of polyolefins and contain graphite or carbon black.
Die EP-A-160,320 beschreibt Kern-Mantel-Monofilamente zum Einsatz in Haarbürsten aus ausgewählten Polymeren. Der Kern enthält Nylon oder Polyester, die mindestens 60 Gew.% Polybutylenterephthalat-Einheiten umfassen. Der Mantel enthält spezielle Nylon-Typen oder Copolyetherester.EP-A-160,320 describes core-sheath monofilaments for use in hair brushes made from selected polymers. The core contains nylon or polyester which comprise at least 60% by weight of polybutylene terephthalate units. The jacket contains special nylon types or copolyether esters.
Aus der DE-U-86/06334 sind Kern-Mantelfasern bekannt, deren Kern aus thermoplastischem Kunststoff, vorzugsweise aus Polyamid, und deren Mantel aus elektrisch leitfähigem Kunststoff, vorzugsweise aus Polyamid, das Ruß oder Metalle eingelagert enthält, besteht.DE-U-86/06334 discloses core sheath fibers, the core of which consists of thermoplastic, preferably polyamide, and the sheath of which is made of electrically conductive plastic, preferably of polyamide, which contains carbon black or metals.
Die JP-A-07/278,956 beschreibt elektrisch leitfähige Copolyester, die hauptsächlich Polybutylenterephthalat-Einheiten enthalten und die mit Ruß dotiert sind. Es werden auch Kern-Mantel-Fasern aus diesem Material beschrieben, bei denen der Kern aus aromatischem Polyester besteht.JP-A-07 / 278,956 describes electrically conductive copolyesters which mainly contain polybutylene terephthalate units and which are doped with carbon black. Core-sheath fibers made from this material are also described, in which the core consists of aromatic polyester.
Aus der WO-A-98/14,647 sind elektrisch leitfähige Heterofilamente bekannt, die beispielsweise als Kern-Mantel-Fasern ausgestaltet sein können. Als Beispiele für Kern- und Mantel-Polymere werden PET und andere Polyester oder PET / Nylon beschrieben.From WO-A-98 / 14,647 electrically conductive heterofilaments are known, which can be configured, for example, as core-sheath fibers. PET and other polyesters or PET / nylon are described as examples of core and sheath polymers.
Die WO-A-01/20,076 offenbart Nonwovens mit hoher Dielektrizitätskonstante. Als Fasermaterial werden Mischungen aus Polyvinylidenfluorid und Polypropylen vorgeschlagen. Die daraus hergestellten Produkte zeichnen sich durch eine verlängerte Halbwertszeit von elektrostatischen Ladungen aus und lassen sich als elektrostatische Filter einsetzen.WO-A-01 / 20,076 discloses nonwovens with a high dielectric constant. Mixtures of polyvinylidene fluoride and polypropylene are proposed as fiber material. The products made from it are characterized by an extended half-life of electrostatic charges and can be used as electrostatic filters.
Die US-A-6,085,061 beschreibt eine Bürste zum Reinigen von elektrostatisch geladenen Oberflächen. Als Fasermaterialien können Kern-Mantel-Fasern zum Einsatz kommen, deren Kern elektrisch leitend ist und deren Mantel aus Polyvinylidenfluorid besteht.US-A-6,085,061 describes a brush for cleaning electrostatically charged surfaces. Core-sheath fibers whose core is electrically conductive and whose sheath is made of polyvinylidene fluoride can be used as fiber materials.
Aus der DE-A-44 12 396 sind schmelzgesponnene unverstreckte, elektrisch nicht leitfähige Fasern mit Kern-Mantel-Struktur, deren Mantel Fluorpolymere enthalten, bekannt. Als Kernpolymer wird Polycarbonat eingesetzt. Diese Faser wird als optische Faser eingesetzt und ist wegen der niedrigen Festigkeiten für technische Textilien, wie z.B. technische Gewebe, nicht geeignet. Außerdem kommt es bei einem Lichtwellenleiter auf hohe Reflexion an der Grenzschicht und möglichst geringe Dämpfung der elektromagnetischen Welle an. Beide Eigenschaften können nur durch Verwendung einer hochreinen Beschichtung erreicht werden.DE-A-44 12 396 discloses melt-spun undrawn, electrically non-conductive fibers with a core-sheath structure, the sheath of which contain fluoropolymers. Polycarbonate is used as the core polymer. This fiber is used as an optical fiber and is due to its low strength for technical textiles such as technical fabrics, not suitable. In addition, with an optical waveguide, high reflection at the boundary layer and the lowest possible attenuation of the electromagnetic wave are important. Both properties can only be achieved by using a high-purity coating.
In der JP-A-2001-127,218 wird eine halbleitende Faser aus einem Ruß enthaltenden Fluorpolymer beschrieben. Diese Faser hat keine Kern-Mantel-Struktur und wird zur Herstellung von Non-Wovens eingesetzt, beispielsweise durch das melt-blow Verfahren. Die Faser ist nicht verstreckt.JP-A-2001-127,218 describes a semiconducting fiber made of a fluoropolymer containing carbon black. This fiber has no core-sheath structure and is used for the production of non-wovens, for example by the melt-blow process. The fiber is not drawn.
Ausgehend von diesem Stand der Technik lag der vorliegenden Erfindung die Aufgabe zugrunde, die anwendungstechnischen Vorteile der für die Faserherstellung bekannten Materialien zu kombinieren, ohne die mit dem Einsatz der einzelnen Materialen bekannten Nachteile in Kauf nehmen zu müssen.Starting from this prior art, the present invention was based on the object of combining the application-related advantages of the materials known for fiber production without having to accept the disadvantages known from the use of the individual materials.
Dem Fachmann ist bekannt, dass an der Grenzschicht zweier Polymere normalerweise Haftungsprobleme auftreten. Insbesondere gilt dies beim Einsatz von bekanntermaßen schlecht haftenden Fluorpolymeren mit anderen Polymeren. Überraschenderweise hat sich gezeigt, dass bei Einsatz eines mit elektrisch leitfähigen Teilchen dotierten Fluorpolymeren eine sehr gute Haftung mit dem Polymerkern zu erzielen ist.It is known to the person skilled in the art that adhesion problems normally occur at the interface between two polymers. This applies in particular when using fluoropolymers known to have poor adhesion with other polymers. Surprisingly, it has been shown that very good adhesion to the polymer core can be achieved when using a fluoropolymer doped with electrically conductive particles.
Eine weitere Aufgabe der vorliegenden Erfindung besteht somit in der Bereitstellung von Kern-Mantel-Fasern mit guter Haftung zwischen den einzelnen Schichten.Another object of the present invention is therefore to provide core-sheath fibers with good adhesion between the individual layers.
Mit der vorliegenden Erfindung werden somit Fasern bereit gestellt, insbesondere Monofilamente, die antistatische Eigenschaften kombiniert mit hoher chemischer und thermischer Beständigkeit und guter mechanischer Formstabilität sowie hoher Zugfestigkeit aufweisen.The present invention thus provides fibers, in particular monofilaments, which combine high chemical and antistatic properties thermal resistance and good mechanical dimensional stability and high tensile strength.
Die Erfindung betrifft eine schmelzgesponnene Faser mit Kern-Mantel Struktur und einer Zugfestigkeit von mindestens 15 cN/tex, deren Kern ein synthetisches thermoplastisches Polymer enthält, das kein Fluorpolymer ist, und deren Mantel mindestens ein schmelzspinnbares Fluorpolymer und Teilchen aus elektrisch leitfähigem Material enthält.The invention relates to a melt-spun fiber with a core-sheath structure and a tensile strength of at least 15 cN / tex, the core of which contains a synthetic thermoplastic polymer that is not a fluoropolymer, and the sheath of which contains at least one melt-spinnable fluoropolymer and particles of electrically conductive material.
Die den Kern bildenden synthetischen thermoplastischen Polymere können beliebiger Natur sein, solange diese schmelzspinnbar sind und der Faser die für den jeweiligen Anwendungszweck gewünschten Eigenschaften verleihen. Fluorpolymere sind von den synthetischen thermoplastischen Polymeren nicht umfasst, obgleich der Kern neben diesen Polymeren auch Fluorpolymere als Mischungskomponente enthalten kann.The synthetic thermoplastic polymers forming the core can be of any nature as long as they are melt-spinnable and give the fiber the properties desired for the particular application. Fluoropolymers are not included in the synthetic thermoplastic polymers, although in addition to these polymers the core may also contain fluoropolymers as a blend component.
Beispiele für synthetische thermoplastische Materialien sind Polyolefine, wie Polyethylen, Polypropylen oder Copolymere enthaltend Ethylen- und/oder Propyleneinheiten in Verbindung mit anderen damit copolymerisierten alpha-Olefin-Einheiten, wie alpha-Butylen, alpha-Pentylen, alpha-Hexylen oder alpha-Octylen; Polyester, wie Polycarbonat, aliphatisch / aromatische Polyester oder vollständig aromatische Polyester; Polyamide, wie aliphatische oder alphatisch / aromatische Polyamide (Nylon-Typen) oder vollständig aromatische Polyamide (Aramide); oder Polyetherketone, also Polymere, die mindestens Ether- und Ketongruppen und in der Regel aromatische zweiwertige Reste, wie Phenylen, in der wiederkehrenden Kette aufweisen, wobei viele Kombinationen dieser Gruppen möglich sind, beispielsweise PEK, PEEK oder PEKK; oder Polyarylensulfide, vorzugsweise Polyphenylensulfid; oder Polyetherester, also Polymere, die mindestens Ether- und Estergruppen und in der Regel aromatische zweiwertige Reste, wie Phenylen, in der wiederkehrenden Kette aufweisen, beispielsweise TPE-E; oder Polyacrylnitril oder Polyacrylnitril-Copolymere mit anderen ethylenisch-ungesättigten Comonomeren, wie Acryl- oder Methacrylsäure.Examples of synthetic thermoplastic materials are polyolefins, such as polyethylene, polypropylene or copolymers containing ethylene and / or propylene units in combination with other alpha-olefin units copolymerized therewith, such as alpha-butylene, alpha-pentylene, alpha-hexylene or alpha-octylene; Polyesters such as polycarbonate, aliphatic / aromatic polyesters or fully aromatic polyesters; Polyamides, such as aliphatic or alphatic / aromatic polyamides (nylon types) or fully aromatic polyamides (aramids); or polyether ketones, that is to say polymers which have at least ether and ketone groups and generally aromatic divalent radicals, such as phenylene, in the repeating chain, many combinations of these groups being possible, for example PEK, PEEK or PEKK; or polyarylene sulfides, preferably polyphenylene sulfide; or polyether esters, that is to say polymers which have at least ether and ester groups and generally aromatic divalent radicals, such as phenylene, in the repeating chain, for example TPE-E; or polyacrylonitrile or polyacrylonitrile copolymers with other ethylenically unsaturated comonomers, such as acrylic or methacrylic acid.
Vorzugsweise enthält der Kern der erfindungsgemäßen Kern-Mantel-Fasern Polyamide und insbesondere Polyester.The core of the core-sheath fibers according to the invention preferably contains polyamides and in particular polyester.
Die in den erfindungsgemäßen Zusammensetzungen bevorzugt zum Einsatz kommenden thermoplastischen Polyamide sind an sich bekannt.The thermoplastic polyamides which are preferably used in the compositions according to the invention are known per se.
Beispiele dafür sind fadenbildende Polyamide, wie aliphatische oder aliphatisch / aromatische Polyamide, wie z.B. Polycaprolactam, Poly-(hexamethylen-1,6-diaminadipinsäurediamid), Poly-(hexamethylen-1,6-diamin-sebacinsäure-diamid), Poly-(hexamethylen-1,6-diamin-terephthalsäure-diamid) oder Poly-(hexamethylen-1,6-diamin-isopthalsäurediamid); oder auch vollständig aromatische Polyamide, wie Poly-(phenylen-1,4-diamin-terephthalsäurediamid) oder Poly-(phenylen-1,4-diaminisophtalsäurediamid).Examples of these are thread-forming polyamides, such as aliphatic or aliphatic / aromatic polyamides, such as e.g. Polycaprolactam, poly- (hexamethylene-1,6-diaminadipic acid diamide), poly- (hexamethylene-1,6-diamine-sebacic acid diamide), poly- (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly- (hexamethylene -1,6-diamine isopthalsäurediamid); or also completely aromatic polyamides, such as poly (phenylene-1,4-diamine-terephthalic acid diamide) or poly- (phenylene-1,4-diamine-isophthalic acid diamide).
Die erfindungsgemäß eingesetzten Polyamide weisen üblicherweise Viskositätszahlen nach DIN 53727 von 120 bis 350, vorzugsweise 150 bis 320 cm3/g auf (gemessen bei 25°C in Schwefelsäure).The polyamides used according to the invention usually have viscosity numbers according to DIN 53727 of 120 to 350, preferably 150 to 320 cm 3 / g (measured at 25 ° C. in sulfuric acid).
Die in den erfindungsgemäßen Zusammensetzungen besonders bevorzugt zum Einsatz kommenden thermoplastischen Polyester und/oder aromatischen flüssigkristallinen Polyester sind an sich bekannt.The thermoplastic polyesters and / or aromatic liquid-crystalline polyesters used with particular preference in the compositions according to the invention are known per se.
Beispiele dafür sind fadenbildende Polyester, wie Polycarbonat oder aliphatisch / aromatische Polyester, wie z.B. Polybutylenterephthalat, Polycyclohexandimethylterephthalat, Polyethylennaphthalat oder insbesondere Polyethylenterephthalat, aber auch vollständig aromatische, flüssig-kristalline Polyester, wie Polyoxibenzonaphtoat. Bausteine von fadenbildenden Polyestern sind vorzugsweise Diole und Dicarbonsäuren, bzw. entsprechend aufgebaute Oxycarbonsäuren. Hauptsäurebestandteil der Polyester ist Terephthalsäure oder Cyclohexandicarbonsäure, aber auch andere aromatische und/oder aliphatische bzw. cycloaliphatische Dicarbonsäuren können geeignet sein, vorzugsweise para- oder trans-ständige aromatische Verbindungen, wie z.B. 2,6-Naphthalin-dicarbonsäure oder 4,4'-Biphenyldicarbonsäure, aber auch p-Hydroxy-benzoesäure. Aliphatische Dicarbonsäuren, wie z.B. Adipinsäure oder Sebacinsäure werden vorzugsweise in Kombination mit aromatischen Dicarbonsäuren eingesetzt.Examples of these are thread-forming polyesters, such as polycarbonate or aliphatic / aromatic polyesters, such as, for example, polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or in particular polyethylene terephthalate, but also completely aromatic, liquid-crystalline polyesters, such as polyoxibenzonaphtoate. Modules of thread-forming polyesters are preferably diols and dicarboxylic acids or correspondingly constructed oxycarboxylic acids. The main acid component of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para or trans-aromatic compounds, such as 2,6-naphthalene dicarboxylic acid or 4,4'-biphenyldicarboxylic acid , but also p-hydroxy-benzoic acid. aliphatic Dicarboxylic acids, such as adipic acid or sebacic acid, are preferably used in combination with aromatic dicarboxylic acids.
Typische geeignete zweiwertige Alkohole sind aliphatische und/oder cycloaliphatische und/oder aromatische Diole, beispielsweise Ethylenglykol, Propandiol, 1,4-Butandiol, 1,4-Cyclohexandimethanol aber auch Hydrochinon. Bevorzugt sind aliphatische Diole, die zwei bis vier Kohlenstoffatome aufweisen, insbesondere Ethylenglykol; weiterhin bevorzugt sind cycloaliphatische Diole, wie 1,4-Cyclohexandimethanol.Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic and / or aromatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol but also hydroquinone. Aliphatic diols which have two to four carbon atoms, in particular ethylene glycol, are preferred; cycloaliphatic diols, such as 1,4-cyclohexanedimethanol, are also preferred.
Bevorzugte thermoplastische Polyester werden inbesondere ausgewählt aus der Gruppe bestehend aus Polyethylenterephthalat, Polyethylennaphthalat, Polybutylennaphthalat, Polypropylenterephthalat, Polybutylenterephthalat, Polycyclohexandimethanol-terephthalat, Polycarbonat oder einem Copolykondensat enthaltend Polybutylenglykol-, Terephthalsäure- und Naphthalindicarbonsäureeinheiten.Preferred thermoplastic polyesters are selected in particular from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate containing polybutylene glycol, terephthalic acid and naphthalene acid and naphthalene units.
Weitere bevorzugte thermoplastische Polyester aromatische, flüssigkristalline Polyester, inbesondere Polyester enthaltend p-Hydroxybenzoateinheiten.Further preferred thermoplastic polyesters are aromatic, liquid-crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
Insbesondere bei Fasern die in feucht-heißen Umgebungen eingesetzt werden sollen, wie bei Monofilamenten beim Einsatz in Papiermaschinen, und die als Kernkomponente Polyester enthalten, werden diese Polyester vorzugsweise durch Zugabe von Polyesterstabilisatoren gegenüber hydrolytischem Abbau stabilisiert.Particularly in the case of fibers which are to be used in hot and humid environments, such as monofilaments when used in paper machines and which contain polyester as the core component, these polyesters are preferably stabilized against hydrolytic degradation by adding polyester stabilizers.
Derartige stabilisierte Fasern zeigen eine signifikante Verringerung der Abbauneigung des Polyesters, so dass Lebensdauern von Monofilamenten erzielt werden können, die denen von Monofilamenten auf der Basis von äußerst beständigen Fasermaterialien, wie Polyarylensulfiden oder -oxiden, gleichwertig sind.Such stabilized fibers show a significant reduction in the degradation tendency of the polyester, so that lifetimes of monofilaments can be achieved, which are equivalent to those of monofilaments based on extremely resistant fiber materials, such as polyarylene sulfides or oxides.
Besonders bevorzugt werden Fasern enthaltend im Kern stabilisierte Polyester, besonders bevorzugt Carbodiimide.Fibers containing polyester stabilized in the core are particularly preferred, particularly preferably carbodiimides.
Die erfindungsgemäß eingesetzten Polyester 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 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 0.62-0.93 dl / g ( measured at 25 ° C in dichloroacetic acid (DCE)).
Die den Mantel bildendenden Fluorpolymere können ebenfalls beliebiger Natur sein, solange diese schmelzspinnbar sind.The fluoropolymers forming the jacket can also be of any nature as long as they are melt-spinnable.
Die erfindungsgemäß eingesetzten Fluorpolymeren sind Poly-(fluorolefin)-Homopolymere und/oder -Copolymere abgeleitet von ethylenisch-ungesättigten fluorhaltigen Olefin-Monomeren und anderen damit copolymerisierbaren Monomeren. Derartige Polymere sind ebenfalls an sich bekannt.The fluoropolymers used according to the invention are poly (fluoroolefin) homopolymers and / or copolymers derived from ethylenically unsaturated fluorine-containing olefin monomers and other monomers copolymerizable therewith. Such polymers are also known per se.
Beispiele dafür sind schmelzspinnbare Copolymere von Tetrafluorethylen mit anderen alpha-Olefinen, wie Ethylen, Propylen, Butylen, Hexylen oder Octylen.Examples of these are melt-spinnable copolymers of tetrafluoroethylene with other alpha-olefins, such as ethylene, propylene, butylene, hexylene or octylene.
Es sind auch Homo- oder Copolymere einsetzbar, die sich von anderen fluorhaltigen Monomeren ableiten, beispielsweise von Mono-, Di- oder Trifluorethylen, von Vinylfluorid oder insbesondere von Vinylidenfluorid.Homopolymers or copolymers can also be used which are derived from other fluorine-containing monomers, for example from mono-, di- or trifluoroethylene, from vinyl fluoride or in particular from vinylidene fluoride.
Besonders bevorzugt setzt man schmelzspinnbare Copolymere von Tetrafluorethylen mit mindestens einem alpha-Olefin, vorzugsweise mit Ethylen, ein.It is particularly preferred to use melt-spinnable copolymers of tetrafluoroethylene with at least one alpha-olefin, preferably with ethylene.
Ganz besonders bevorzugt wird als Mantelkomponente Polyvinylidenfluorid ("PVDF") eingesetzt.Polyvinylidene fluoride ("PVDF") is very particularly preferably used as the jacket component.
Beim Verspinnen von Polyestern, insbesondere von PET, mit PVDF zu einem Bikomponenten-Monofilament in Kern-Mantel Struktur zeigt sich überraschend eine sehr gute Kern-Mantel Haftung.When spinning polyesters, in particular PET, with PVDF to form a bicomponent monofilament in a core-shell structure, surprisingly a very good core-shell adhesion is shown.
Die Erfindung betrifft daher auch eine Heterofilamentfaser enthaltend mindestens zwei Komponenten, wobei die erste Komponente ein elektrischer Isolator ist und ein thermoplastisches Polymer umfasst, das kein Fluorpolymer ist, und die zweite Komponente Polyvinylidenfluorid umfasst.The invention therefore also relates to a heterofilament fiber containing at least two components, the first component being an electrical insulator and one thermoplastic polymer that is not a fluoropolymer and the second component comprises polyvinylidene fluoride.
Die im Mantel der erfindungsgemäßen schmelzgesponnenen Faser vorhandenen Teilchen aus elektrisch leitfähigem Material können beliebiger Natur sein, solange diese dem Mantel eine erhöhte elektrische Leitfähigkeit verleihen.The particles of electrically conductive material present in the sheath of the melt-spun fiber according to the invention can be of any nature as long as they give the sheath an increased electrical conductivity.
Dabei kann es sich um Teilchen aus Kohlenstoff, beispielsweise um Kohlefasern, Ruß oder Graphit; aus Metallen, beispielsweise aus Kupfer, Silber, Aluminium oder Eisen; aus Metalllegierungen, beispielsweise aus Bronze; oder aus leitfähigen Kunststoffen, beispielsweise aus Polyanilinen oder aus Polypyrrol, handeln.These can be particles of carbon, for example carbon fibers, carbon black or graphite; from metals, for example from copper, silver, aluminum or iron; made of metal alloys, for example bronze; or act from conductive plastics, for example from polyanilines or from polypyrrole.
Die Teilchen können in beliebiger Form vorliegen, beispielsweise in Faserform oder in Form von runden oder irregulären Partikeln.The particles can be in any form, for example in the form of fibers or in the form of round or irregular particles.
Der Gehalt der elektrisch leitfähigen Teilchen im Mantel ist so zu wählen, dass sich eine deutliche Erhöhung der elektrischen Leitfähigkeit des Kunststoffmaterials ergibt. Typische Mengen bewegen sich im Bereich von bis zu 50 Gew. %, vorzugsweise 2 bis 15 Gew. %, bezogen auf die Menge des Mantelmaterials.The content of the electrically conductive particles in the jacket should be selected so that there is a significant increase in the electrical conductivity of the plastic material. Typical amounts are in the range of up to 50% by weight, preferably 2 to 15% by weight, based on the amount of the jacket material.
Besonders bevorzugt werden schmelzgesponnene Fasern, worin der Mantel zwischen 2 Gew. % und 15 Gew. %, insbesondere zwischen 4 Gew. % und 9 Gew. % elektrisch leitfähige Partikel enthält.Melt-spun fibers in which the sheath contains between 2% by weight and 15% by weight, in particular between 4% by weight and 9% by weight, of electrically conductive particles are particularly preferred.
Die erfindungsgemäßen Kern-Mantel-Fasern können in beliebiger Form vorliegen, beispielsweise als Multifilamente, als Stapelfasern oder insbesondere als Monofilamente.The core-sheath fibers according to the invention can be in any form, for example as multifilaments, as staple fibers or in particular as monofilaments.
Der Titer der erfindungsgemäßen Kern-Mantel-Fasern kann ebenfalls in weiten Bereichen schwanken. Beispiele dafür sind 100 bis 45.000 dtex, insbesondere 400 bis 7.000 dtex.The titer of the core-sheath fibers according to the invention can also vary within wide ranges. Examples of this are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
Besonders bevorzugt sind Monofilamente.Monofilaments are particularly preferred.
Besonders bevorzugt werden Monofilamente, deren Querschnittsform rund, oval oder n-eckig ist, wobei n größer gleich 3 ist.Monofilaments whose cross-sectional shape is round, oval or n-angular are particularly preferred, n greater than or equal to 3.
Die Stapellängen bei Stapelfasern können ebenfalls in weiten Bereichen schwanken, beispielsweise zwischen 30 bis 70 mm.The staple lengths for staple fibers can also vary widely, for example between 30 and 70 mm.
Der Kern der erfindungsgemäßen Kern-Mantel-Faser bildet den mechanischen Träger der Faser, während der Mantel hauptsächlich die Gebrauchseigenschaften, wie antistatisches Verhalten und Gleitverhalten, bestimmt.
Als Kern kann vorzugsweise ein handelsüblicher PET-Rohstoff verwendet werden.The core of the core-sheath fiber according to the invention forms the mechanical carrier of the fiber, while the sheath mainly determines the usage properties, such as antistatic behavior and sliding behavior.
A commercially available PET raw material can preferably be used as the core.
Für den Mantel wird besonders bevorzugt ein Fluorpolymer auf Basis von PVDF verwendet, das zuvor insbesondere mit Ruß zu einem verspinnbaren Gemisch verarbeitet wurde.A fluoropolymer based on PVDF is particularly preferably used for the jacket, which was previously processed into a spinnable mixture, in particular with carbon black.
Gewichtsanteil der den Kern bildenden Komponente A) zur den Mantel bildenden Komponente B) beträgt, bezogen auf die Gesamtmenge dieser Komponenten, für Komponente A) 50 bis 95 Gew. %, vorzugsweise 60 bis 80 Gew. %, und für Komponente B) 50 bis 5 Gew. %, vorzugsweise 40 bis 20 Gew. %.The proportion by weight of component A) forming the core to component B) forming the shell is, based on the total amount of these components, 50 to 95% by weight, preferably 60 to 80% by weight, for component A) and 50 to 80% by weight for component B) 5% by weight, preferably 40 to 20% by weight.
Die Herstellung der erfindungsgemäßen Kern-Mantel-Fasern kann nach an sich bekannten Verfahren erfolgen.The core-shell fibers according to the invention can be produced by methods known per se.
Diese Verfahren umfassen die Maßnahmen:
- i) Auswahl eines ersten Polymeren, das ein synthetisches thermoplastisches Polymer und kein Fluorpolymer ist und das einen ersten Schmelzpunkt aufweist,
- ii) Auswahl eines zweiten Polymeren, das ein schmelzspinnbares Fluorpolymer ist, das einen zweiten Schmelzpunkt aufweist, der wenigstens 20°C unterhalb des ersten Schmelzpunktes liegt, und das Teilchen aus elektrisch leitfähigem Material enthält,
- iii) Koextrusion des ersten Polymeren und des zweiten Polymeren durch eine Heterofilament-Spinndüse bei einer Spinntemperatur oberhalb des ersten Schmelzpunktes, so dass sich eine Bikomponentenfaser mit einem Kern aus dem ersten Polymeren und einem Mantel aus dem zweiten Polymeren ausbildet, und
- iv) Verstrecken des gebildeten Kern-Mantel Filaments zur Vergrößerung der Zugfestigkeit.
- i) selection of a first polymer which is a synthetic thermoplastic polymer and not a fluoropolymer and which has a first melting point,
- ii) selection of a second polymer which is a melt-spinnable fluoropolymer which has a second melting point which is at least 20 ° C. below the first melting point and which contains particles of electrically conductive material,
- iii) coextrusion of the first polymer and the second polymer through a heterofilament spinneret at a spinning temperature above the first Melting point, so that a bicomponent fiber with a core of the first polymer and a sheath of the second polymer is formed, and
- iv) stretching the core-sheath filament formed to increase the tensile strength.
Die beiden Polymeren bzw. Mischungen enthaltend diese Polymeren werden vorzugsweise unmittelbar vor der Zuführung in den Extruder getrocknet, in dem Extruder aufgeschmolzen und durch ein Spinnpack filtriert. Das Fluorpolymere wird mit den elektrisch leitfähigen Teilchen versehen. Dieses erfolgt üblicherweise vor der Zuführung des Fluorpolymeren zum Extruder, kann aber auch unmittelbar vor dem Spinnpack erfolgen. Es können auch Masterbatches enthaltend das Fluorpolymer und elektrisch leitfähige Teilchen zum Einsatz kommen.The two polymers or mixtures containing these polymers are preferably dried immediately before being fed into the extruder, melted in the extruder and filtered through a spin pack. The fluoropolymer is provided with the electrically conductive particles. This is usually done before the fluoropolymer is fed to the extruder, but can also be done immediately before the spin pack. Masterbatches containing the fluoropolymer and electrically conductive particles can also be used.
Nach dem Verpressen der Polymerschmelzen durch eine Heterofilament-Spinndüse wird der geschmolzene Polymerfaden in einem Spinnbad, beispielsweise einem Wasserbad, abgekühlt und anschließend aufgewickelt oder abgezogen. Die Abziehgeschwindigkeit ist dabei größer als die Spritzgeschwindigkeit der Polymerschmelze und bewirkt somit ein Verstrecken des gebildeten Fadens.After the polymer melts have been pressed through a heterofilament spinneret, the molten polymer thread is cooled in a spinning bath, for example a water bath, and then wound up or drawn off. The pulling-off speed is greater than the spraying speed of the polymer melt and thus causes the thread formed to stretch.
Der so hergestellte Heterofilament-Spinnfaden wird anschließend vorzugsweise einer Nachverstreckung, besonders bevorzugt in mehreren Stufen, insbesondere einer zwei- oder dreistufigen Nachverstreckung, mit einem Gesamtverstreckungsverhältnis von 1 : 3 bis 1 : 8, vorzugsweise 1 : 4 bis 1 : 6, unterzogen.The heterofilament spun thread thus produced is then preferably subjected to post-drawing, particularly preferably in several stages, in particular a two- or three-stage post-drawing, with a total drawing ratio of 1: 3 to 1: 8, preferably 1: 4 to 1: 6.
Nach der Verstreckung schließt sich vorzugsweise eine Thermofixierung an, wobei Temperaturen von 130 bis 280°C zum Einsatz kommen; dabei wird bei konstanter Länge gearbeitet oder es wird ein Schrumpf von bis zu 30 % zugelassen.After stretching, heat setting preferably follows, using temperatures of 130 to 280 ° C; work is carried out at a constant length or a shrinkage of up to 30% is permitted.
Als besonders vorteilhaft für die erfindungsgemäßen Monofilamente hat es sich erwiesen, wenn bei einer Schmelzetemperatur im Bereich von 285 bis 315°C und bei einem Spinnverzug von 1 : 2 bis 1 : 6 gearbeitet wird.It has proven to be particularly advantageous for the monofilaments according to the invention when working at a melt temperature in the range from 285 to 315 ° C. and with a spinning delay of 1: 2 to 1: 6.
Die Spinnabzugsgeschwindigkeit beträgt üblicherweise 10 - 40 m pro Minute.The spinning take-off speed is usually 10-40 m per minute.
Beim Verspinnen des thermoplastischen Polymeren des Kern und des Fluorpolymers des Mantels zu einem Bikomponenten-Monofilament in Kern-Mantel Struktur zeigt sich überraschend eine sehr gute Kern-Mantel Haftung.When the thermoplastic polymer of the core and the fluoropolymer of the shell are spun into a bicomponent monofilament in a core-shell structure, surprisingly a very good core-shell adhesion is shown.
Die Leitfähigkeit des Mantels kann beim Verstrecken verloren gehen, kann aber durch eine Wärmebehandlung und den dadurch ausgelösten Schrumpf, vorzugsweise oberhalb des Schmelzpunktes des Mantelmaterials, aber unterhalb der Schmelztemperatur des Kerns, wieder hergestellt werden.The conductivity of the jacket can be lost during stretching, but can be restored by heat treatment and the shrinkage caused thereby, preferably above the melting point of the jacket material, but below the melting temperature of the core.
Durch das leitfähig dotierte Fluorpolymer werden die Oberflächeneigenschaften hauptsächlich bestimmt. Die erfindungsgemäßen Fasern zeichnen sich durch sehr gute Schmutzabweisung, gute Chemikalienbeständigkeit und elektrische Leitfähigkeit aus.The surface properties are mainly determined by the conductively doped fluoropolymer. The fibers according to the invention are distinguished by very good dirt repellency, good chemical resistance and electrical conductivity.
Die Kombination mit dem Fluorpolymeren führt zu Fasern mit verbesserten Gleiteigenschaften verglichen mit Fasern aus reinem thermoplastischem Polymer. Diese Fasern zeigen im Vergleich zu Fasern aus reinem thermoplastischem Polymer eine erhöhte Schmutzabweisung.The combination with the fluoropolymer leads to fibers with improved sliding properties compared to fibers made of pure thermoplastic polymer. These fibers show increased dirt repellency compared to fibers made from pure thermoplastic polymer.
Die erfindungsgemäßen Fasern können neben den Komponenten A) und B) Hilfsstoffe enthalten. Beispiele dafür sind Verarbeitungshilfsmittel, Stabilisatoren, Antioxidantien, Weichmacher, Gleitmittel, Pigmente, Mattierungsmittel, Viskositätsmodifizierer oder Kristallisationbeschleuniger.In addition to components A) and B), the fibers according to the invention can contain auxiliaries. Examples of these are processing aids, stabilizers, 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 Stabilisatoren und Antioxidantien sind die bereits oben erwähnten Polyesterstabilisatoren, Phosphorverbindungen, wie Phosphorsäureester oder Carbodiimide.Examples of stabilizers and antioxidants are the polyester stabilizers already mentioned above, phosphorus compounds, such as phosphoric acid esters or carbodiimides.
Beispiele für Pigmente oder Mattierungsmittel sind organische Farbstoffpigmente oder Titandioxid.Examples of pigments or matting agents are organic dye pigments or titanium dioxide.
Bespiele für Viskositätsmodifizierer sind mehrwertige Carbonsäuren und deren Ester oder mehrwertige Alkohole.Examples of viscosity modifiers are polyvalent carboxylic acids and their esters or polyvalent alcohols.
Die erfindungsgemäßen Fasern, insbesondere die Monofilamente, werden vorzugsweise zur Herstellung von textilen Flächengebilden, wie Geweben, Gewirken, Gestricken, Gelegen und Nonwovens eingesetzt.The fibers according to the invention, in particular the monofilaments, are preferably used for the production of textile fabrics, such as woven fabrics, knitted fabrics, knitted fabrics, laid fabrics and nonwovens.
Textile Flächengebilde enthaltend erfindungsgemäße Monofilamente eignen sich insbesondere für technische Einsatzzwecke, wie für Filter, als Siebdruckmaterialien oder insbesondere als Papiermaschinensiebe.Textile fabrics containing monofilaments according to the invention are particularly suitable for technical purposes, such as for filters, as screen printing materials or in particular as paper machine screens.
Die erfindungsgemäßen Monofilamente haben gute textilphysikalische Eigenschaften und lassen sich leicht verweben. Die Gewebe haben die übliche Formstabilität der den Kern bildenden thermoplastischen Polymeren.The monofilaments according to the invention have good textile-physical properties and are easy to weave. The fabrics have the usual dimensional stability of the core-forming thermoplastic polymers.
Gewebe aus diesen Monofilamenten eigenen sich hervorragend für technische Gewebe, insbesondere in der Filtration aggressiver Medien, bei denen auch die Gefahr elektrostatischer Aufladung besteht; d.h. insbesondere in der fest-gasförmig und fest-flüssig Filtration.Fabrics made from these monofilaments are ideally suited for technical fabrics, particularly in the filtration of aggressive media, where there is also a risk of electrostatic charging; i.e. especially in solid-gaseous and solid-liquid filtration.
Die Erfindung betrifft auch die Verwendung der Fasern zur Herstellung von textilen Flächengebilden, die in Umgebungen mit starker chemischer und/oder physikalischer Beanspruchung eingesetzt werden, insbesondere als Papiermaschinensiebe oder als technische Gewebe, wie sie z.B. in der Filtration, zur Herstellung von Förderbändern oder als Verstärkungseinlagen eingesetzt werden. Hier kommen die Fasern als Monofilamente und insbesondere als Schussfäden im Gewebe zum Einsatz.The invention also relates to the use of the fibers for the production of textile fabrics which are used in environments with high chemical and / or physical stress, in particular as paper machine screens or as technical fabrics, such as those e.g. in filtration, for the production of conveyor belts or as reinforcing inserts. Here the fibers are used as monofilaments and in particular as weft threads in the fabric.
Der Einsatz der erfindungsgemäßen Monofilamente als Papiermaschinensiebe kann in der Forming-Partie, der Preßpartie oder insbesondere in der Trockenpartie erfolgen. In der Trockenpartie kommen die erfindungsgemäßen Monofilamente insbesondere als Spiralsiebe zum Einsatz.The use of the monofilaments according to the invention as paper machine screens can be in the forming section, the press section or in particular in the dryer section respectively. In the dryer section, the monofilaments according to the invention are used in particular as spiral screens.
Für diese Anwendungen haben die erfindungsgemäß eingesetzten Fasern, insbesondere in Form von Monofilamenten, üblicherweise einen Titerbereich von 10 bis 4500 tex, einen Elastizitätsmodul von 2,0 bis 8,0 N/tex, eine feinheitsbezogene Festigkeit von 15 bis 50 cN/tex, eine Bruchdehnung von 15 bis 45 % und einen Heißluftschrumpf bei 180°C von 1,0 bis 20,0 %.For these applications, the fibers used according to the invention, in particular in the form of monofilaments, usually have a titer range from 10 to 4500 tex, an elastic modulus from 2.0 to 8.0 N / tex, a tenacity-related strength from 15 to 50 cN / tex Elongation at break from 15 to 45% and a hot air shrinkage at 180 ° C from 1.0 to 20.0%.
Das nachfolgende Beispiel erläutert die Erfindung ohne diese zu begrenzen.The following example explains the invention without limiting it.
Die Komponenten Polyethylenterephthalat ("PET") (70 Gew. %) und Polyvinylidenfluorid (als Masterbatch enthaltend 9 Gew.% Leitfähigkeitsruß; Palmarole EXP 184/14; 30 Gew. %) wurden in zwei Extrudern mit getrennter Temperaturführung aufgeschmolzen (PET bei 282°C Schmelztemperatur (Kernmaterial) bzw. PVDF bei 240°C Schmelztemperatur (Mantelmaterial) und durch eine 20 Loch Spinndüse mit einem Lochdurchmesser von 1,40 mm und einer Abzugsgeschwindigkeit von 15 m/min zu einem Kern-Mantel-Monofilament versponnen, zweifach verstreckt (erste Verstreckung im Wasserbad bei 80°C; zweite Verstreckung im Heißluftkanal bei 150°C), sowie im Heißluftkanal bei 205°C thermofixiert. Die Gesamtverstreckung betrug 4,1 : 1. Der Enddurchmesser des Kern-Mantel Monofilaments betrug 0,500 mm.The components polyethylene terephthalate ("PET") (70% by weight) and polyvinylidene fluoride (as masterbatch containing 9% by weight of conductive carbon black; Palmarole EXP 184/14; 30% by weight) were melted in two extruders with separate temperature control (PET at 282 ° C Melting temperature (core material) or PVDF at 240 ° C melting temperature (jacket material) and spun through a 20-hole spinneret with a hole diameter of 1.40 mm and a take-off speed of 15 m / min to form a core-jacket monofilament, stretched twice ( first stretching in a water bath at 80 ° C; second stretching in the hot air duct at 150 ° C.) and heat-set in the hot air duct at 205 ° C. The total stretching was 4.1: 1. The final diameter of the core-sheath monofilament was 0.500 mm.
Das erhaltene Kern-Mantel-Monofilament wies folgende Eigenschaften auf:
Claims (13)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10249585A DE10249585B4 (en) | 2002-10-24 | 2002-10-24 | Conductive, stain resistant core-sheath fiber with high chemical resistance, process for its preparation and use |
DE10249585 | 2002-10-24 |
Publications (3)
Publication Number | Publication Date |
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EP1413653A2 true EP1413653A2 (en) | 2004-04-28 |
EP1413653A3 EP1413653A3 (en) | 2004-10-06 |
EP1413653B1 EP1413653B1 (en) | 2009-02-11 |
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Application Number | Title | Priority Date | Filing Date |
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EP03021088A Expired - Lifetime EP1413653B1 (en) | 2002-10-24 | 2003-09-18 | Conductive, soil-resistant core-sheath fibre with high resistance to chemicals, its production process and use |
Country Status (9)
Country | Link |
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US (1) | US20040078903A1 (en) |
EP (1) | EP1413653B1 (en) |
JP (1) | JP2004143659A (en) |
AT (1) | ATE422570T1 (en) |
DE (2) | DE10249585B4 (en) |
DK (1) | DK1413653T3 (en) |
ES (1) | ES2321389T3 (en) |
PL (1) | PL363021A1 (en) |
PT (1) | PT1413653E (en) |
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AT503675B1 (en) * | 2006-05-15 | 2008-09-15 | Lenzing Plastics Gmbh | CHEMICALLY RESISTANT AND FORM-RESISTANT MONOFILAMENTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE |
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JP4773920B2 (en) * | 2006-10-18 | 2011-09-14 | 帝人ファイバー株式会社 | Screen filament monofilament |
JP4773919B2 (en) * | 2006-10-18 | 2011-09-14 | 帝人ファイバー株式会社 | Polyester monofilament for screens with excellent anti-static properties |
EP2231390A4 (en) * | 2007-12-14 | 2012-12-05 | 3M Innovative Properties Co | Fiber aggregate |
BRPI1006414A2 (en) | 2009-03-26 | 2016-02-10 | Bl Technologies Inc | reinforcement structure for a hollow fiber membrane, hollow fiber membrane, method for producing a reinforcement structure and method for producing a hollow fiber reinforcement membrane |
US9061250B2 (en) | 2009-06-26 | 2015-06-23 | Bl Technologies, Inc. | Non-braided, textile-reinforced hollow fiber membrane |
CN103097008B (en) | 2010-09-15 | 2015-12-09 | Bl科技公司 | The method of yarn enhanced hollow-fibre membrane is manufactured around solvable core body |
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CN103911685A (en) * | 2014-04-29 | 2014-07-09 | 厦门怡龙谷新材料科技有限公司 | Novel composite monofilament with skin core structure and large diameter, as well as manufacturing method and application thereof |
DE102015101449A1 (en) * | 2015-02-02 | 2016-08-04 | AstenJohnson PGmbH | Industrial fabric, process for producing a nonwoven fabric and use of an industrial fabric |
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US20220316099A1 (en) * | 2019-06-03 | 2022-10-06 | Kent State University | Liquid crystal clad fibers |
TWI718819B (en) * | 2019-12-19 | 2021-02-11 | 財團法人工業技術研究院 | Conductive fiber and method for fabricating the same |
CN112481736A (en) * | 2020-12-28 | 2021-03-12 | 南通新帝克单丝科技股份有限公司 | Polyvinylidene fluoride polyester composite monofilament and preparation method thereof |
TWI830258B (en) * | 2022-06-17 | 2024-01-21 | 立綺實業有限公司 | A core-sheath fiber and fabric thereof |
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Also Published As
Publication number | Publication date |
---|---|
PL363021A1 (en) | 2004-05-04 |
PT1413653E (en) | 2009-04-29 |
EP1413653A3 (en) | 2004-10-06 |
EP1413653B1 (en) | 2009-02-11 |
DE10249585B4 (en) | 2007-10-04 |
DK1413653T3 (en) | 2009-05-11 |
JP2004143659A (en) | 2004-05-20 |
ES2321389T3 (en) | 2009-06-05 |
DE10249585A1 (en) | 2004-05-13 |
DE50311164D1 (en) | 2009-03-26 |
US20040078903A1 (en) | 2004-04-29 |
ATE422570T1 (en) | 2009-02-15 |
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