EP1339900B1 - Multicomponent fibre - Google Patents
Multicomponent fibre Download PDFInfo
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- EP1339900B1 EP1339900B1 EP01994700A EP01994700A EP1339900B1 EP 1339900 B1 EP1339900 B1 EP 1339900B1 EP 01994700 A EP01994700 A EP 01994700A EP 01994700 A EP01994700 A EP 01994700A EP 1339900 B1 EP1339900 B1 EP 1339900B1
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- EP
- European Patent Office
- Prior art keywords
- acid
- fiber
- omega
- sheath
- polyamide
- 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.)
- Expired - Lifetime
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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
- 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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- 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
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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]
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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]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
-
- 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
- Y10T428/2973—Particular cross section
- Y10T428/2976—Longitudinally varying
Definitions
- the present invention relates to a fiber containing a along the fiber running core (I) of a polymer and a core (I) surrounding this, chemically different from core (I) Sheath (II), characterized in that sheath (II) based on a polyamide that chemically binds to the polymer chain bound sterically hindered piperidine derivative (III).
- the present invention relates to the use of a such fiber for making yarns, fabrics and carpets.
- the yarn is produced in a conventional manner by melting of the polyamide, spinning the polyamide into a fiber, Stretching and texturing of this fiber and optionally after-treatment the fiber. This is usually followed by one Cabling and heat fixation of the yarn.
- the present invention was based on the object, a fiber to provide yarns with improved crimp let produce.
- the fiber includes a fiber extending along the fiber Core (I) of a polymer.
- Suitable polymers are those which are meltable and are spinnable in a molten state, such as Polyamides, polyesters, polyolefins, preferably polyamides, polyolefins, in particular polyamides.
- Polyamides are homopolymers, copolymers, mixtures and Understood grafts of synthetic long-chain polyamides, the recurrent amide groups in having the polymer backbone.
- polyamides are nylon 6 (polycaprolactam), nylon 6,6 (polyhexamethylene adipamide), Nylon 4,6 (polytetramethylene adipamide), nylon 6,10 (polyhexamethylene sebacamide), Nylon 7 (polyeneantholactam), nylon 11 (Polyundecanolactam), nylon 12 (polydodecanolactam).
- nylon 6 polycaprolactam
- nylon 6,6 polyhexamethylene adipamide
- Nylon 4,6 polytetramethylene adipamide
- nylon 6,10 polyhexamethylene sebacamide
- Nylon 7 polyeneantholactam
- nylon 11 Polyundecanolactam
- nylon 12 polydodecanolactam
- aramids aromatic Polyamides
- poly metaphenylene isophthalamide NOMEX® Fiber, U.S. Patent 3,287,324
- polyparaphenylene terephthalamide KEVLAR® fiber, US-A-3,671,542
- the preparation of polyamides can in principle by two methods respectively.
- lactams as starting monomers or starting oligomers
- polyaddition The polymerization of lactams as starting monomers or starting oligomers is usually referred to as polyaddition.
- Such polyamides can be prepared by methods known per se, such as for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, Interscience, New York, 1977, Pp. 424-467, especially pp.
- 444-446 are selected from monomers selected from the group consisting of Lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylic acid salts, omega-aminocarboxylic acid esters, equimolar mixtures of Diamines and dicarboxylic acids, dicarboxylic acid / diamine salts, dinitriles and diamines or mixtures of such monomers.
- the lactam used is caprolactam, as diamine tetramethylenediamine, hexamethylenediamine or their mixtures and as dicarboxylic acid adipic acid, sebacic acid, Dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof one.
- lactam caprolactam as Diamine hexamethylenediamine and as dicarboxylic acid adipic acid or Terephthalic acid or mixtures thereof.
- chain regulators are compounds which have one or more, such as two, amino groups which are reactive during polyamide formation or one or more, such as two, carboxyl groups which are reactive in polyamide formation.
- Monocarboxylic acids such as alkanecarboxylic acids, for example acetic acid, propionic acid, such as benzene- or naphthalene monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C 4 -C 10 -alkanedicarboxylic acid, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, C 5 -C 8 -cycloalkanedicarboxylic acids, may advantageously be used as chain regulators for example, cyclohexane-1, 4-dicarboxylic acid, benzene or naphthalenedicarboxylic acid, for example terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, C 2 - to C 20 -, preferably C 2 - to C 12 -alkylamines, such as cyclohexylamine, C 6 -
- the polymerization or polycondensation by the process according to the invention in the presence of at least one pigment preferred Pigments are titania, with titanium dioxide preferably in the Anatase modification, or inorganic coloring compounds or organic nature.
- the pigments are preferably in an amount of 0 to 5 parts by weight, especially 0.02 to 2 parts by weight, in each case based on 100 parts by weight of polyamide, added.
- the pigments can be added to the reactor with the starting materials or separately supplied therefrom.
- Polyolefins include homopolymers, copolymers, blends and grafts of synthetic long-chain polyolefins, by polymerization of olefinically unsaturated Compounds such as ethylene, propylene, styrene, acrylic acid and their Esters, methacrylic acid and their esters, preferably propylene can be.
- olefinically unsaturated Compounds such as ethylene, propylene, styrene, acrylic acid and their Esters, methacrylic acid and their esters, preferably propylene can be.
- the fiber contains a core (I) surrounding Mantle (II) based on a polyamide that is attached to the Polymer chain chemically bound sterically hindered piperidine Derivative (III) contains.
- Polyamides are homopolymers, copolymers, mixtures and Understood grafts of synthetic long-chain polyamides, the recurrent amide groups in having the polymer backbone.
- Examples of such polyamides are nylon 6 (polycaprolactam), nylon 6,6 (polyhexamethylene adipamide), Nylon 4,6 (polytetramethylene adipamide), nylon 6,10 (polyhexamethylene sebacamide), Nylon 6,12 (polyhexamethylenedodecanedioic acid amide) Nylon 7 (polyeneantholactam), nylon 11 (polyundecanolactam), Nylon 12 (polydodecanolactam). Wear these polyamides known as the generic name nylon.
- aramids aromatic polyamides
- polyparaphenylene isophthalamide NOMEX® fiber, US-A-3,287,324
- polyparaphenylene terephthalamide KEVLAR® Fiber, US-A-3,671,542
- the preparation of polyamides can in principle by two methods respectively.
- lactams as starting monomers or starting oligomers
- polyaddition The polymerization of lactams as starting monomers or starting oligomers is usually referred to as polyaddition.
- Such polyamides can be prepared by methods known per se, such as for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, Interscience, New York, 1977, Pp. 424-467, especially pp.
- 444-446 are selected from monomers selected from the group consisting of Lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylic acid salts, omega-aminocarboxylic acid esters, equimolar mixtures of Diamines and dicarboxylic acids, dicarboxylic acid / diamine salts, dinitriles and diamines or mixtures of such monomers.
- the lactam used is caprolactam, as diamine tetramethylenediamine, hexamethylenediamine or their mixtures and as dicarboxylic acid adipic acid, sebacic acid, Dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof one.
- lactam caprolactam as Diamine hexamethylenediamine and as dicarboxylic acid adipic acid or Terephthalic acid or mixtures thereof.
- the polyamides with one or more chain regulators.
- the one or more, such as two, reactive in polyamide formation Amino groups or one or more, such as two, in polyamide formation have reactive carboxyl groups.
- Monocarboxylic acids such as alkanecarboxylic acids, for example acetic acid, propionic acid, such as benzene- or naphthalene monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C 4 -C 10 -alkanedicarboxylic acid, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, C 5 -C 8 -cycloalkanedicarboxylic acids, may advantageously be used as chain regulators
- cyclohexane-1,4-dicarboxylic acid, benzene or naphthalenedicarboxylic acid for example, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, C 2 to C 20 -, preferably C 2 - to C 12 - alkylamines, such as cyclohexylamine, C 6 -
- Such chain regulators may carry substituents, such as halogens, for example, fluorine, chlorine or bromine, sulfonic acid groups or their salts, such as lithium, sodium, potassium salts, or unsubstituted be.
- substituents such as halogens, for example, fluorine, chlorine or bromine, sulfonic acid groups or their salts, such as lithium, sodium, potassium salts, or unsubstituted be.
- sulfonated dicarboxylic acids in particular Sulfoisophthalic acid
- one of its salts such as alkali metal salts, for example, lithium, sodium, potassium salts, preferably Lithium or sodium salt, especially lithium salt.
- sheath (II) contains a polyamide which is an an Polymer chain chemically bonded sterically hindered piperidine derivative (III) contains.
- the tertiary, especially secondary amino groups of the piperidine ring systems not because of steric hindrance.
- Particularly preferred compound (III) is 4-amino-2,2,6,6-tetramethylpiperidine.
- compound (II) can be used in amounts of at most 0.8 Mol%, preferably at most 0.6 mol%, in particular at most 0.4 mol%, based on 1 mol of acid amide groups of the polyamide, use.
- the polymerization or polycondensation by the process according to the invention in the presence of at least one pigment preferred Pigments are titania, with titanium dioxide preferably in the Anatase modification, or inorganic coloring compounds or organic nature.
- the pigments are preferably in an amount of 0 to 5 parts by weight, especially 0.02 to 2 parts by weight, in each case based on 100 parts by weight of polyamide, added.
- the pigments can be added to the reactor with the starting materials or separately supplied therefrom.
- the one to the Polymer chain chemically bonded sterically hindered piperidine derivative (III) are, for example, in WO 95/28443, WO 97/05189, WO 98/50610, WO 99/46323, WO 99/48949, EP-A-822 275, EP-A-843 696 and the two German applications 10030515.6 and 10030512.1 described.
- core (I) and shell (II) are chemically different.
- core (I) and shell (II) have a different one Content of sterically bound to the polymer chain hindered piperidine derivative (III), preferably this Content in core (I) is smaller than in shell (II), in particular this content, in molar terms, in core (I) less than 50% this content in coat (II) is.
- this Content in core (I) is smaller than in shell (II), in particular this content, in molar terms, in core (I) less than 50% this content in coat (II) is.
- the production of the fibers can take place in a manner known per se, for example, in US-A-3,803,453, US-A-5,445,884, US-A-5,447,794, US-A-5,888,651, EP-A-410,415, EP-A-056,667.
- the polymer for core (I) and the polyamide for coat (II) produce separately, by means of a conveyor, like an extruder, each a melt of the polymers feed a spin pack package and spin the fiber there, in particular by quick spinning at take-off speeds of at least 4000 m / min.
- From the fibers according to the invention can be known in per se The way yarns, fabrics and carpets are made, as before described at the beginning.
- Fibers of 2700 dtex fineness and round cross section were prepared from the polyamides of Table 1, spun at a weight ratio of core (I) to sheath (II) of 70:30 and stretch textured to give the data shown in the Table. core coat Crimping [%]
- the fibers according to the invention have a better crimping than fibers according to the prior Technique consisting only of the material of sheath (II) (Comparative Example 1) or consist only of the material of core (I) (Comparative Example 2).
Description
Die vorliegende Erfindung betrifft eine Faser enthaltend einen längs der Faser verlaufenden Kern (I) aus einem Polymeren und einen diesen Kern (I) umgebenden, von Kern (I) chemisch unterschiedlichen Mantel (II), dadurch gekennzeichnet, daß Mantel (II) auf einem Polyamid basiert, das ein an die Polymerkette chemisch gebundenes sterisch gehindertes Piperidin-Derivat (III) enthält.The present invention relates to a fiber containing a along the fiber running core (I) of a polymer and a core (I) surrounding this, chemically different from core (I) Sheath (II), characterized in that sheath (II) based on a polyamide that chemically binds to the polymer chain bound sterically hindered piperidine derivative (III).
Ferner betrifft die vorliegende Erfindung die Verwendung einer solchen Faser zur Herstellung von Garnen, Geweben und Teppichen.Furthermore, the present invention relates to the use of a such fiber for making yarns, fabrics and carpets.
Die Verwendung von Polymeren, insbesondere Polyamiden, zur Herstellung von Fasern und Garnen ist allgemein bekannt, beispielsweise aus: Ullmann's Encyclopedia of Industrial Chemistry, 5. Ed., Vol. A10, VCH Verlagsgesellschaft mbH, Weinheim, Deutschland, 1987, Seite 567-579.The use of polymers, in particular polyamides, for the production of fibers and yarns is well known, for example from: Ullmann's Encyclopedia of Industrial Chemistry, 5. Ed., Vol. A10, VCH Verlagsgesellschaft mbH, Weinheim, Germany, 1987, pages 567-579.
Die Garnherstellung erfolgt in an sich bekannter Weise durch Aufschmelzen des Polyamids, Verspinnen des Polyamids zu einer Faser, Verstrecken und Texturieren dieser Faser und gegebenenfalls Nachbehandlung der Faser. Daran schließt sich üblicherweise eine Kablierung und Hitzefixierung des Garns an.The yarn is produced in a conventional manner by melting of the polyamide, spinning the polyamide into a fiber, Stretching and texturing of this fiber and optionally after-treatment the fiber. This is usually followed by one Cabling and heat fixation of the yarn.
Gemäß: Dictionary of Fiber & Textile Technology, Hoechst Celanese Corporation, Charlotte, NC 28232, USA, 1990, S. 159 dient das Texturieren, das auch das Kräuseln umfaßt, der Erhöhung der Deckkraft des Garns.According to: Dictionary of Fiber & Textile Technology, Hoechst Celanese Corporation, Charlotte, NC 28232, USA, 1990, p Texturing, which also includes curling, increasing opacity of the yarn.
Bei der Herstellung von Teppichen aus solchen Garnen ist eine hohe Kräuselung erwünscht, da mit höherer Deckkraft des Garnes weniger Garn zum Decken eines Teppichs benötigt wird.In the production of carpets from such yarns is a high crimping is desirable because with higher opacity of the yarn less yarn is needed to cover a carpet.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, eine Faser bereitzustellen, aus der sich Garne mit verbesserter Kräuselung herstellen lassen.The present invention was based on the object, a fiber to provide yarns with improved crimp let produce.
Demgemäß wurden die eingangs definierten Fasern und die Verwendung dieser Fasern zur Herstellung von Garnen, Geweben und Teppichen gefunden.Accordingly, the fibers defined above and the use these fibers for the production of yarns, fabrics and Carpets found.
Erfindungsgemäß enthält die Faser einen längs der Faser verlaufenden Kern (I) aus einem Polymeren. According to the invention, the fiber includes a fiber extending along the fiber Core (I) of a polymer.
Als Polymere kommen vorteilhaft solche in Betracht, die aufschmelzbar und in geschmolzenem Zustand verspinnbar sind, wie Polyamide, Polyester, Polyolefine, vorzugsweise Polyamide, Polyolefine, insbesondere Polyamide.Suitable polymers are those which are meltable and are spinnable in a molten state, such as Polyamides, polyesters, polyolefins, preferably polyamides, polyolefins, in particular polyamides.
Unter Polyamiden werden Homopolymere, Copolymere, Mischungen und Pfropfungen von synthetischen langkettigen Polyamiden verstanden, die als wesentlichen Bestandteil wiederkehrend Amid-Gruppen in der Polymer-Hauptkette aufweisen. Beispiele solcher Polyamide sind Nylon 6 (Polycaprolactam), Nylon 6,6 (Polyhexamethylenadipamid), Nylon 4,6 (Polytetramethylenadipamid), Nylon 6,10 (Polyhexamethylensebacamid), Nylon 7 (Polyenantholactam), Nylon 11 (Polyundecanolactam), Nylon 12 (Polydodecanolactam). Diese Polyamide tragen bekanntermaßen den generischen Namen Nylon. Unter Polyamiden werden auch die sogenannten Aramide verstanden (aromatische Polyamide), wie Poly-metaphenylen-isophthalamid (NOMEX ® Faser, US-A-3,287,324) oder Poly-paraphenylen-terephthalamid (KEVLAR ® Faser, US-A-3,671,542).Polyamides are homopolymers, copolymers, mixtures and Understood grafts of synthetic long-chain polyamides, the recurrent amide groups in having the polymer backbone. Examples of such polyamides are nylon 6 (polycaprolactam), nylon 6,6 (polyhexamethylene adipamide), Nylon 4,6 (polytetramethylene adipamide), nylon 6,10 (polyhexamethylene sebacamide), Nylon 7 (polyeneantholactam), nylon 11 (Polyundecanolactam), nylon 12 (polydodecanolactam). These polyamides As you know, the generic name is nylon. Under Polyamides are also understood as the so-called aramids (aromatic Polyamides), such as poly metaphenylene isophthalamide (NOMEX® Fiber, U.S. Patent 3,287,324) or polyparaphenylene terephthalamide (KEVLAR® fiber, US-A-3,671,542).
Die Herstellung von Polyamiden kann prinzipiell nach zwei Verfahren erfolgen.The preparation of polyamides can in principle by two methods respectively.
Bei der Polymerisation aus Dicarbonsäuren und Diaminen, wie auch bei der Polymerisation aus Aminosäuren oder deren Derivaten, wie Aminocarbonsäurenitrilen, Aminocarbonsäureamiden, Aminocarbonsäureestern oder Aminocarbonsäuresalzen, reagieren die Amino- und Carboxyl-Endgruppen der Ausgangsmonomere oder Ausgangsoligomere miteinander unter Bildung einer Amid-Gruppe und Wasser. Das Wasser kann anschließend von der Polymermasse entfernt werden. Bei der Polymerisation aus Carbonsäureamiden reagieren die Amino- und Amid-Endgruppen der Ausgangsmonomere oder Ausgangsoligomere miteinander unter Bildung einer Amid-Gruppe und Ammoniak. Der Ammoniak kann anschließend von der Polymermasse entfernt werden. Diese Polymerisationsreaktion bezeichnet man üblicherweise als Polykondensation.In the polymerization of dicarboxylic acids and diamines, as well in the polymerization of amino acids or their derivatives, such as Aminocarboxylic acid nitriles, aminocarboxylic acid amides, aminocarboxylic acid esters or aminocarboxylic acid salts, the amino and Carboxyl end groups of the starting monomers or starting oligomers with each other to form an amide group and water. The Water can then be removed from the polymer mass. In the polymerization of carboxylic acid amides, the amino and amide end groups of the starting monomers or starting oligomers with each other to form an amide group and ammonia. Of the Ammonia can then be removed from the polymer mass. This polymerization reaction is commonly referred to as Polycondensation.
Die Polymerisation aus Lactamen als Ausgangsmonomeren oder Ausgangsoligomeren bezeichnet man üblicherweise als Polyaddition.The polymerization of lactams as starting monomers or starting oligomers is usually referred to as polyaddition.
Solche Polyamide können nach an sich bekannten Verfahren, wie sie beispielsweise in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 oder in: Polymerization Processes, Interscience, New York, 1977, S. 424-467, insbesondere S. 444-446, beschrieben sind, erhalten werden aus Monomeren ausgewählt aus der Gruppe bestehend aus Lactamen, omega-Aminocarbonsäuren, omega-Aminocarbonsäurenitrilen, omega-Aminocarbonsäureamiden, omega-Aminocarbonsäuresalze, omega-Aminocarbonsäureester, äquimolaren Mischungen aus Diaminen und Dicarbonsäuren, Dicarbonsäure/Diamin-Salzen, Dinitrilen und Diaminen oder Gemischen solcher Monomere.Such polyamides can be prepared by methods known per se, such as for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, Interscience, New York, 1977, Pp. 424-467, especially pp. 444-446 are selected from monomers selected from the group consisting of Lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylic acid salts, omega-aminocarboxylic acid esters, equimolar mixtures of Diamines and dicarboxylic acids, dicarboxylic acid / diamine salts, dinitriles and diamines or mixtures of such monomers.
mit einer C2 - bis C20 -, vorzugsweise C2 - bis C14 - aliphatischen Dicarbonsäure oder deren Mono- oder Dinitrile, wie Sebacinsäure, Dodecandisäure, Adipinsäure, Sebacinsäuredinitril, Decansäuredinitril oder Adipodinitril,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 2 to C 20 , preferably C 2 to C 12 , alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine,
with a C 2 - to C 20 -, preferably C 2 - to C 14 -aliphatic dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic dinitrile or adiponitrile,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C8 - bis C20 -, vorzugsweise C8 - bis C12 - aromatischen Dicarbonsäure oder deren Derivate , beispielsweise Chloride, wie 2,6-Naphthalindicarbonsäure, vorzugsweise Isophthalsäure oder Terephthalsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 2 to C 20 , preferably C 2 to C 12 , alkyldiamine, such as fietramethylenediamine or, preferably, hexamethylenediamine,
with a C 8 - to C 20 -, preferably C 8 - to C 12 -aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C9 - bis C20 -, vorzugsweise C9 - bis C18 - arylaliphatischen Dicarbonsäure oder deren Derivate, beispielsweise Chloride, wie o-, m- oder p-Phenylendiessigsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 2 to C 20 , preferably C 2 to C 12 , alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine,
with a C 9 - to C 20 -, preferably C 9 - to C 18 - arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C2 - bis C20 -, vorzugsweise C2 - bis C14 - aliphatischen Dicarbonsäure oder deren Mono- oder Dinitrile, wie Sebacinsäure, Dodecandisäure, Adipinsäure, Sebacinsäuredinitril, Decansäuredinitril oder Adipodinitril,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 6 - to C 20 -, preferably C 6 - to C 10 -aromatic diamine, such as m- or p-phenylenediamine,
with a C 2 - to C 20 -, preferably C 2 - to C 14 -aliphatic dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic dinitrile or adiponitrile,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C8 - bis C20 -, vorzugsweise C8 - bis C12 - aromatischen Dicarbonsäure oder deren Derivate , beispielsweise Chloride, wie 2,6-Naphthalindicarbonsäure, vorzugsweise Isophthalsäure oder Terephthalsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 6 - to C 20 - preferably C 6 - to C 10 -aromatic diamine, such as m- or p-phenylenediamine,
with a C 8 - to C 20 -, preferably C 8 - to C 12 -aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C9 - bis C20 -, vorzugsweise C9 - bis C18 - arylaliphatischen Dicarbonsäure oder deren Derivate, beispielsweise Chloride, wie o-, m- oder p-Phenylendiessigsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 6 - to C 20 - preferably C 6 - to C 10 -aromatic diamine, such as m- or p-phenylenediamine,
with a C 9 - to C 20 -, preferably C 9 - to C 18 - arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 7 - to C 20 -, preferably C 8 - to C 18 - arylaliphatic diamine, such as m- or p-xylylenediamine, having a C 2 - to C 20 -, preferably C 2 - to C 14 -aliphatic Dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic dinitrile or adiponitrile,
and their dimers, trimers, tetramers, pentamers or hexamers,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 7 - to C 20 -, preferably C 8 - to C 18 - arylaliphatic diamine, such as m- or p-xylylenediamine, having a C 6 - to C 20 -, preferably C 6 - to C 10 -aromatic Dicarboxylic acid or its derivatives, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 7 to C 20 , preferably C 8 to C 18 , arylaliphatic diamine, such as m- or p-xylylenediamine, having a C 9 to C 20 , preferably C 9 to C 18 , arylaliphatic diamine Dicarboxylic acid or its derivatives, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
In einer bevorzugten Ausführungsform setzt man als Lactam Caprolactam, als Diamin Tetramethylendiamin, Hexamethylendiamin oder deren Gemische und als Dicarbonsäure Adipinsäure, Sebacinsäure, Dodecandisäure, Terephthalsäure, Isophthalsäure oder deren Gemische ein. Besonders bevorzugt ist als Lactam Caprolactam, als Diamin Hexamethylendiamin und als Dicarbonsäure Adipinsäure oder Terephthalsäure oder deren Gemische.In a preferred embodiment, the lactam used is caprolactam, as diamine tetramethylenediamine, hexamethylenediamine or their mixtures and as dicarboxylic acid adipic acid, sebacic acid, Dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof one. Particularly preferred as lactam caprolactam, as Diamine hexamethylenediamine and as dicarboxylic acid adipic acid or Terephthalic acid or mixtures thereof.
Besonders bevorzugt sind dabei solche Ausgangsmonomere oder Ausgangsoligomere, die bei der Polymerisation zu den Polyamiden Nylon 6, Nylon 6,6, Nylon 4,6, Nylon 6,10, Nylon 6,12, Nylon 7, Nylon 11, Nylon 12 oder den Aramiden Poly-metaphenylen-isophthalamid oder Poly-paraphenylen-terephthalamid, insbesondere zu Nylon 6 oder Nylon 66, führen.Particular preference is given to those starting monomers or starting oligomers, in the polymerization to the polyamides Nylon 6, Nylon 6,6, Nylon 4,6, Nylon 6,10, Nylon 6,12, Nylon 7, Nylon 11, nylon 12 or the aramid poly metaphenylene isophthalamide or polyparaphenylene terephthalamide, especially nylon 6 or nylon 66.
In einer bevorzugten Ausführungsform kann man bei der Herstellung
der Polyamide mit einem oder mehreren Kettenreglern einsetzen.
Als Kettenregler kommen vorteilhaft Verbindungen in Betracht, die
eine oder mehrere, wie zwei, bei der Polyamidbildung reaktive
Amino-Gruppen oder eine oder mehrere, wie zwei, bei der Polyamidbildung
reaktive Carboxyl-Gruppen aufweisen.In a preferred embodiment, one can use in the preparation of the polyamides with one or more chain regulators.
Suitable chain regulators are compounds which have one or more, such as two, amino groups which are reactive during polyamide formation or one or more, such as two, carboxyl groups which are reactive in polyamide formation.
Im ersten Fall erhält man Fasern, bei denen die zur Herstellung des Polyamids des Kerns (I) eingesetzten Monomeren eine höhere Zahl an zur Bildung der Polymerkette eingesetzten Amin-Gruppen oder deren Äquivalente als zur Bildung der Polymerkette eingesetzte Carbonsäure-Gruppen oder deren Äquivalente aufweisen.In the first case one obtains fibers, in which those for the production of the polyamide of the core (I) used a higher monomer Number of amine groups used to form the polymer chain or their equivalents as used to form the polymer chain Carboxylic acid groups or their equivalents.
Im zweiten Fall erhält man Fasern, bei denen die zur Herstellung des Polyamids des Kerns (I) eingesetzten Monomeren eine höhere Zahl an zur Bildung der Polymerkette eingesetzten Carbonsäure-Gruppen oder deren Äquivalente als zur Bildung der Polymerkette eingesetzte Amin-Gruppen oder deren Äquivalente aufweisen. In the second case, one obtains fibers in which for the production of the polyamide of the core (I) used a higher monomer Number of carboxylic acid groups used to form the polymer chain or their equivalents than to form the polymer chain have used amine groups or their equivalents.
Als Kettenregler können vorteilhaft Monocarbonsäuren, wie Alkancarbonsäuren, beispielsweise Essigsäure, Proprionsäure, wie Benzol- oder Naphthalinmonocarbonsäure, beispielsweise Benzoesäure, Dicarbonsäuren, wie C4-C10-Alkandicarbonsäure, beispielsweise Adipinsäure, Azelainsäure, Sebacinsäure, Dodecandisäure, C5-C8-Cycloalkandicarbonsäuren, beispielsweise Cyclohexan-1.,4-dicarbonsäure, Benzol- oder Naphthalindicarbonsäure, beispielsweise Terephthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, C2 - bis C20 -, vorzugsweise C2 - bis C12 - Alkylamine, wie Cyclohexylamin, C6 - bis C20 -, vorzugsweise C6 - bis C10 - aromatische Monoamine, wie Anilin, oder C7 - bis C20 -, vorzugsweise C8 - bis C18 - arylaliphatische Monoamine, wie Benzylamin, Diamine, wie C4-C10-Alkandiamine, beispielsweise Hexamethylendiamin eingesetzt werden.Monocarboxylic acids, such as alkanecarboxylic acids, for example acetic acid, propionic acid, such as benzene- or naphthalene monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C 4 -C 10 -alkanedicarboxylic acid, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, C 5 -C 8 -cycloalkanedicarboxylic acids, may advantageously be used as chain regulators for example, cyclohexane-1, 4-dicarboxylic acid, benzene or naphthalenedicarboxylic acid, for example terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, C 2 - to C 20 -, preferably C 2 - to C 12 -alkylamines, such as cyclohexylamine, C 6 - to C 20 -, preferably C 6 - to C 10 - aromatic monoamines, such as aniline, or C 7 - to C 20 -, preferably C 8 - to C 18 - arylaliphatic monoamines, such as benzylamine, diamines, such as C 4 -C 10 alkanediamines, for example hexamethylenediamine be used.
Vorteilhaft kann man einen Kettenregler in Mengen von mindestens 0,01 Mol-%, vorzugsweise mindestens 0,05 Mol-%, insbesondere mindestens 0,2 Mol-%, bezogen auf 1 Mol Säureamidgruppen des Polyamids, einsetzen.Advantageously, one can use a chain regulator in amounts of at least 0.01 mol%, preferably at least 0.05 mol%, especially at least 0.2 mol%, based on 1 mol of acid amide groups of the polyamide, deploy.
Vorteilhaft kann man einen Kettenregler in Mengen von höchstens 1,0 Mol-%, vorzugsweise höchstens 0,6 Mol-%, insbesondere höchstens 0,5 Mol-%, bezogen auf 1 Mol Säureamidgruppen des Polyamids, einsetzen.Advantageously, one can use a chain regulator in amounts of at most 1.0 mol%, preferably at most 0.6 mol%, especially at most 0.5 mol%, based on 1 mol of acid amide groups of the polyamide, deploy.
In einer anderen bevorzugten Ausgestaltung wird die Polymerisation bzw. Polykondensation nach dem erfindungsgemäßen Verfahren in Gegenwart mindestens eines Pigments durchgeführt. Bevorzugte Pigmente sind Titandioxid, wobei Titandioxid vorzugsweise in der Anatas-Modifikation vorliegt, oder farbgebende Verbindungen anorganischer oder organischer Natur. Die Pigmente werden vorzugsweise in einer Menge von 0 bis 5 Gewichtsteile, insbesondere 0,02 bis 2 Gewichtsteile, jeweils bezogen auf 100 Gewichtsteile Polyamid, zugegeben. Die Pigmente können dem Reaktor mit den Ausgangsstoffen oder getrennt davon zugeführt werden.In another preferred embodiment, the polymerization or polycondensation by the process according to the invention in the presence of at least one pigment. preferred Pigments are titania, with titanium dioxide preferably in the Anatase modification, or inorganic coloring compounds or organic nature. The pigments are preferably in an amount of 0 to 5 parts by weight, especially 0.02 to 2 parts by weight, in each case based on 100 parts by weight of polyamide, added. The pigments can be added to the reactor with the starting materials or separately supplied therefrom.
Unter Polyolefinen werden Homopolymere, Copolymere, Mischungen und Pfropfungen von synthetischen langkettigen Polyolefinen verstanden, die durch Polymerisation aus olefinisch ungesättigten Verbindungen, wie Ethylen, Propylen, Styrol, Acrylsäure und deren Ester, Methacrylsäure und deren Ester, vorzugsweise Propylen, erhalten werden können.Polyolefins include homopolymers, copolymers, blends and grafts of synthetic long-chain polyolefins, by polymerization of olefinically unsaturated Compounds such as ethylene, propylene, styrene, acrylic acid and their Esters, methacrylic acid and their esters, preferably propylene can be.
Die Herstellung solcher Polyolefine kann nach an sich bekannter Weise erfolgen. The preparation of such polyolefins can be known per se Done way.
Erfindungsgemäß enthält die Faser einen den Kern (I) umgebenden Mantel (II), der auf einem Polyamid basierenden das ein an die Polymerkette chemisch gebundenes sterisch gehindertes Piperidin Derivat (III) enthält.According to the invention, the fiber contains a core (I) surrounding Mantle (II) based on a polyamide that is attached to the Polymer chain chemically bound sterically hindered piperidine Derivative (III) contains.
Unter Polyamiden werden Homopolymere, Copolymere, Mischungen und Pfropfungen von synthetischen langkettigen Polyamiden verstanden, die als wesentlichen Bestandteil wiederkehrend Amid-Gruppen in der Polymer-Hauptkette aufweisen. Beispiele solcher Polyamide sind Nylon 6 (Polycaprolactam), Nylon 6,6 (Polyhexamethylenadipamid), Nylon 4,6 (Polytetramethylenadipamid), Nylon 6,10 (Polyhexamethylensebacamid), Nylon 6,12 (Polyhexamethylendodecandisäureamid) Nylon 7 (Polyenantholactam), Nylon 11 (Polyundecanolactam), Nylon 12 (Polydodecanolactam). Diese Polyamide tragen bekanntermaßen den generischen Namen Nylon. Unter Polyamiden werden auch die sogenannten Aramide verstanden (aromatische Polyamide), wie Poly-metaphenylen-isophthalamid (NOMEX ® Faser, US-A-3,287,324) oder Poly-paraphenylen-terephthalamid (KEVLAR ® Faser, US-A-3,671,542).Polyamides are homopolymers, copolymers, mixtures and Understood grafts of synthetic long-chain polyamides, the recurrent amide groups in having the polymer backbone. Examples of such polyamides are nylon 6 (polycaprolactam), nylon 6,6 (polyhexamethylene adipamide), Nylon 4,6 (polytetramethylene adipamide), nylon 6,10 (polyhexamethylene sebacamide), Nylon 6,12 (polyhexamethylenedodecanedioic acid amide) Nylon 7 (polyeneantholactam), nylon 11 (polyundecanolactam), Nylon 12 (polydodecanolactam). Wear these polyamides known as the generic name nylon. Be under polyamides also understood the so-called aramids (aromatic polyamides), such as poly metaphenylene isophthalamide (NOMEX® fiber, US-A-3,287,324) or polyparaphenylene terephthalamide (KEVLAR® Fiber, US-A-3,671,542).
Die Herstellung von Polyamiden kann prinzipiell nach zwei Verfahren erfolgen.The preparation of polyamides can in principle by two methods respectively.
Bei der Polymerisation aus Dicarbonsäuren und Diaminen, wie auch bei der Polymerisation aus Aminosäuren oder deren Derivaten, wie Aminocarbonsäurenitrilen, Aminocarbonsäureamiden, Aminocarbonsäureestern oder Aminocarbonsäuresalzen, reagieren die Amino- und Carboxyl-Endgruppen der Ausgangsmonomere oder Ausgangsoligomere miteinander unter Bildung einer Amid-Gruppe und Wasser. Das Wasser kann anschließend von der Polymermasse entfernt werden. Bei der Polymerisation aus Carbonsäureamiden reagieren die Amino- und Amid-Endgruppen der Ausgangsmonomere oder Ausgangsoligomere miteinander unter Bildung einer Amid-Gruppe und Ammoniak. Der Ammoniak kann anschließend von der Polymermasse entfernt werden. Diese Polymerisationsreaktion bezeichnet man üblicherweise als Polykondensation.In the polymerization of dicarboxylic acids and diamines, as well in the polymerization of amino acids or their derivatives, such as Aminocarboxylic acid nitriles, aminocarboxylic acid amides, aminocarboxylic acid esters or aminocarboxylic acid salts, the amino and Carboxyl end groups of the starting monomers or starting oligomers with each other to form an amide group and water. The Water can then be removed from the polymer mass. In the polymerization of carboxylic acid amides, the amino and amide end groups of the starting monomers or starting oligomers with each other to form an amide group and ammonia. Of the Ammonia can then be removed from the polymer mass. This polymerization reaction is commonly referred to as Polycondensation.
Die Polymerisation aus Lactamen als Ausgangsmonomeren oder Ausgangsoligomeren bezeichnet man üblicherweise als Polyaddition.The polymerization of lactams as starting monomers or starting oligomers is usually referred to as polyaddition.
Solche Polyamide können nach an sich bekannten Verfahren, wie sie beispielsweise in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 oder in: Polymerization Processes, Interscience, New York, 1977, S. 424-467, insbesondere S. 444-446, beschrieben sind, erhalten werden aus Monomeren ausgewählt aus der Gruppe bestehend aus Lactamen, omega-Aminocarbonsäuren, omega-Aminocarbonsäurenitrilen, omega-Aminocarbonsäureamiden, omega-Aminocarbonsäuresalze, omega-Aminocarbonsäureester, äquimolaren Mischungen aus Diaminen und Dicarbonsäuren, Dicarbonsäure/Diamin-Salzen, Dinitrilen und Diaminen oder Gemischen solcher Monomere.Such polyamides can be prepared by methods known per se, such as for example in DE-A-14 95 198, DE-A-25 58 480, EP-A-129 196 or in: Polymerization Processes, Interscience, New York, 1977, Pp. 424-467, especially pp. 444-446 are selected from monomers selected from the group consisting of Lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylic acid salts, omega-aminocarboxylic acid esters, equimolar mixtures of Diamines and dicarboxylic acids, dicarboxylic acid / diamine salts, dinitriles and diamines or mixtures of such monomers.
mit einer C2 - bis C20 -, vorzugsweise C2 - bis C14 - aliphatischen Dicarbonsäure oder deren Mono- oder Dinitrile, wie Sebacinsäure, Dodecandisäure, Adipinsäure, Sebacinsäuredinitril, Decansäuredinitril oder Adipodinitril,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 2 to C 20 , preferably C 2 to C 12 , alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine,
with a C 2 - to C 20 -, preferably C 2 - to C 14 -aliphatic dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic dinitrile or adiponitrile,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C8 - bis C20 -, vorzugsweise C8 - bis C12 - aromatischen Dicarbonsäure oder deren Derivate, beispielsweise Chloride, wie 2,6-Naphthalindicarbonsäure, vorzugsweise Isophthalsäure oder Terephthalsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 2 to C 20 , preferably C 2 to C 12 , alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine,
with a C 8 - to C 20 -, preferably C 8 - to C 12 -aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C9 - bis C20 -, vorzugsweise C9 - bis C18 - arylaliphatischen Dicarbonsäure oder deren Derivate, beispielsweise Chloride, wie o-, m- oder p-Phenylendiessigsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 2 to C 20 , preferably C 2 to C 12 , alkyldiamine, such as tetramethylenediamine or, preferably, hexamethylenediamine,
with a C 9 - to C 20 -, preferably C 9 - to C 18 - arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C2 - bis C20 -, vorzugsweise C2 - bis C14 - aliphatischen Dicarbonsäure oder deren Mono- oder Dinitrile, wie Sebacinsäure, Dodecandisäure, Adipinsäure, Sebacinsäuredinitril, Decansäuredinitril oder Adipodinitril,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 6 - to C 20 -, preferably C 6 - to C 10 -aromatic diamine, such as m- or p-phenylenediamine,
with a C 2 - to C 20 -, preferably C 2 - to C 14 -aliphatic dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic dinitrile or adiponitrile,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C8 - bis C20 -, vorzugsweise C8 - bis C12 - aromatischen Dicarbonsäure oder deren Derivate, beispielsweise Chloride, wie 2,6-Naphthalindicarbonsäure, vorzugsweise Isophthalsäure oder Terephthalsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 6 - to C 20 - preferably C 6 - to C 10 -aromatic diamine, such as m- or p-phenylenediamine,
with a C 8 - to C 20 -, preferably C 8 - to C 12 -aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
mit einer C9 - bis C20 -, vorzugsweise C9 - bis C18 - arylaliphatischen Dicarbonsäure oder deren Derivate, beispielsweise Chloride, wie o-, m- oder p-Phenylendiessigsäure,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 6 - to C 20 - preferably C 6 - to C 10 -aromatic diamine, such as m- or p-phenylenediamine,
with a C 9 - to C 20 -, preferably C 9 - to C 18 - arylaliphatic dicarboxylic acid or derivatives thereof, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 7 - to C 20 -, preferably C 8 - to C 18 - arylaliphatic diamine, such as m- or p-xylylenediamine, having a C 2 - to C 20 -, preferably C 2 - to C 14 -aliphatic Dicarboxylic acid or its mono- or dinitriles, such as sebacic acid, dodecanedioic acid, adipic acid, sebaconitrile, decanoic dinitrile or adiponitrile,
and their dimers, trimers, tetramers, pentamers or hexamers,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 7 - to C 20 -, preferably C 8 - to C 18 - arylaliphatic diamine, such as m- or p-xylylenediamine, having a C 6 - to C 20 -, preferably C 6 - to C 10 -aromatic Dicarboxylic acid or its derivatives, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
sowie deren Dimere, Trimere, Tetramere, Pentamere oder Hexamere,Monomers or oligomers of a C 7 to C 20 , preferably C 8 to C 18 , arylaliphatic diamine, such as m- or p-xylylenediamine, having a C 9 to C 20 , preferably C 9 to C 18 , arylaliphatic diamine Dicarboxylic acid or its derivatives, for example chlorides, such as o-, m- or p-phenylenediacetic acid,
and their dimers, trimers, tetramers, pentamers or hexamers,
In einer bevorzugten Ausführungsform setzt man als Lactam Caprolactam, als Diamin Tetramethylendiamin, Hexamethylendiamin oder deren Gemische und als Dicarbonsäure Adipinsäure, Sebacinsäure, Dodecandisäure, Terephthalsäure, Isophthalsäure oder deren Gemische ein. Besonders bevorzugt ist als Lactam Caprolactam, als Diamin Hexamethylendiamin und als Dicarbonsäure Adipinsäure oder Terephthalsäure oder deren Gemische.In a preferred embodiment, the lactam used is caprolactam, as diamine tetramethylenediamine, hexamethylenediamine or their mixtures and as dicarboxylic acid adipic acid, sebacic acid, Dodecanedioic acid, terephthalic acid, isophthalic acid or mixtures thereof one. Particularly preferred as lactam caprolactam, as Diamine hexamethylenediamine and as dicarboxylic acid adipic acid or Terephthalic acid or mixtures thereof.
Besonders bevorzugt sind dabei solche Ausgangsmonomere oder Ausgangsoligomere, die bei der Polymerisation zu den Polyamiden Nylon 6, Nylon 6,6, Nylon 4,6, Nylon 6,10, Nylon 6,12, Nylon 7, Nylon 11, Nylon 12 oder den Aramiden Poly-metaphenylen-isophthalamid oder Poly-paraphenylen-terephthalamid, insbesondere zu Nylon 6 oder Nylon 66, führen.Particular preference is given to those starting monomers or starting oligomers, in the polymerization to the polyamides Nylon 6, Nylon 6,6, Nylon 4,6, Nylon 6,10, Nylon 6,12, Nylon 7, Nylon 11, nylon 12 or the aramid poly metaphenylene isophthalamide or poly-paraphenyleneterephthalamide, in particular to Nylon 6 or nylon 66, lead.
In einer bevorzugten Ausführungsform kann man bei der Herstellung der Polyamide mit einem oder mehreren Kettenreglern einsetzen. Als Kettenregler kommen vorteilhaft Verbindungen in Betracht, die eine oder mehrere, wie zwei, bei der Polyamidbildung reaktive Amino-Gruppen oder eine oder mehrere, wie zwei, bei der Polyamidbildung reaktive Carboxyl-Gruppen aufweisen.In a preferred embodiment, in the preparation use the polyamides with one or more chain regulators. As a chain controller advantageous compounds come into consideration, the one or more, such as two, reactive in polyamide formation Amino groups or one or more, such as two, in polyamide formation have reactive carboxyl groups.
Im ersten Fall erhält man Fasern, bei denen die zur Herstellung des Polyamids des Kerns (I) eingesetzten Monomeren eine höhere Zahl an zur Bildung der Polymerkette eingesetzten Amin-Gruppen oder deren Äquivalente als zur Bildung der Polymerkette eingesetzte Carbonsäure-Gruppen oder deren Äquivalente aufweisen.In the first case one obtains fibers, in which those for the production of the polyamide of the core (I) used a higher monomer Number of amine groups used to form the polymer chain or their equivalents as used to form the polymer chain Carboxylic acid groups or their equivalents.
Im zweiten Fall erhält man Fasern, bei denen die zur Herstellung des Polyamids des Kerns (I) eingesetzten Monomeren eine höhere Zahl an zur Bildung der Polymerkette eingesetzten Carbonsäure-Gruppen oder deren Äquivalente als zur Bildung der Polymerkette eingesetzte Amin-Gruppen oder deren Äquivalente aufweisen. In the second case, one obtains fibers in which for the production of the polyamide of the core (I) used a higher monomer Number of carboxylic acid groups used to form the polymer chain or their equivalents than to form the polymer chain have used amine groups or their equivalents.
Als Kettenregler können vorteilhaft Monocarbonsäuren, wie Alkancarbonsäuren, beispielsweise Essigsäure, Proprionsäure, wie Benzol- oder Naphthalinmonocarbonsäure, beispielsweise Benzoesäure, Dicarbonsäuren, wie C4-C10-Alkandicarbonsäure, beispielsweise Adipinsäure, Azelainsäure, Sebacinsäure, Dodecandisäure, C5-C8-Cycloalkandicarbonsäuren, beispielsweise Cyclohexan-1,4-dicarbonsäure, Benzol- oder Naphthalindicarbonsäure, beispielsweise Terephthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, C2 - bis C20 -, vorzugsweise C2 - bis C12 - Alkylamine, wie Cyclohexylamin, C6 - bis C20 -, vorzugsweise C6 - bis C10 - aromatische Monoamine, wie Anilin, oder C7 - bis C20 -, vorzugsweise C8 - bis C1B - arylaliphatische Monoamine, wie Benzylamin, Diamine, wie C4-C10-Alkandiamine, beispielsweise Hexamethylendiamin eingesetzt werden.Monocarboxylic acids, such as alkanecarboxylic acids, for example acetic acid, propionic acid, such as benzene- or naphthalene monocarboxylic acid, for example benzoic acid, dicarboxylic acids, such as C 4 -C 10 -alkanedicarboxylic acid, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, C 5 -C 8 -cycloalkanedicarboxylic acids, may advantageously be used as chain regulators For example, cyclohexane-1,4-dicarboxylic acid, benzene or naphthalenedicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, C 2 to C 20 -, preferably C 2 - to C 12 - alkylamines, such as cyclohexylamine, C 6 - to C 20 -, preferably C 6 - to C 10 - aromatic monoamines, such as aniline, or C 7 - to C 20 -, preferably C 8 - to C 1B - arylaliphatic monoamines, such as benzylamine, diamines, such as C 4 - C 10 -Alkandiamine, for example hexamethylenediamine can be used.
Solche Kettenregler können Substituenten tragen, wie Halogene, beispielsweise Fluor, Chlor oder Brom, Sulfonsäuregruppen oder deren Salze, wie Lithium-, Natrium-, Kalium-Salze, oder unsubstituiert sein.Such chain regulators may carry substituents, such as halogens, for example, fluorine, chlorine or bromine, sulfonic acid groups or their salts, such as lithium, sodium, potassium salts, or unsubstituted be.
Bevorzugt sind sulfonierte Dicarbonsäuren, insbesondere Sulfoisophthalsäure, sowie eines ihrer Salze, wie Alkalisalze, beispielsweise Lithium-, Natrium-, Kalium-Salze, vorzugsweise Lithium- oder Natrium-Salz, insbesondere Lithium-Salz.Preference is given to sulfonated dicarboxylic acids, in particular Sulfoisophthalic acid, and one of its salts, such as alkali metal salts, for example, lithium, sodium, potassium salts, preferably Lithium or sodium salt, especially lithium salt.
Vorteilhaft kann man einen Kettenregler in Mengen von mindestens 0,01 Mol-%, vorzugsweise mindestens 0,05 Mol-%, insbesondere mindestens 0,2 Mol-%, bezogen auf 1 Mol Säureamidgruppen des Polyamids, einsetzen.Advantageously, one can use a chain regulator in amounts of at least 0.01 mol%, preferably at least 0.05 mol%, especially at least 0.2 mol%, based on 1 mol of acid amide groups of the polyamide, deploy.
Vorteilhaft kann man einen Kettenregler in Mengen von höchstens 1,0 Mol-%, vorzugsweise höchstens 0,6 Mol-%, insbesondere höchstens 0,5 Mol-%, bezogen auf 1 Mol Säureamidgruppen des Polyamids, einsetzen.Advantageously, one can use a chain regulator in amounts of at most 1.0 mol%, preferably at most 0.6 mol%, especially at most 0.5 mol%, based on 1 mol of acid amide groups of the polyamide, deploy.
Erfindungsgemäß enthält Mantel (II) ein Polyamid, das ein an die Polymerkette chemisch gebundenes sterisch gehindertes Piperidin-Derivat (III) enthält.According to the invention, sheath (II) contains a polyamide which is an an Polymer chain chemically bonded sterically hindered piperidine derivative (III) contains.
Bevorzugt kommen als Verbindungen (III) solche der Formel wobei
- R1
- für eine funktionelle Gruppe steht, die zur Amidbildung
gegenüber der Polymerkette des Polyamids von Mantel (II)
fähig ist,
vorzugsweise eine Gruppe -(NH)R5, wobei R5 für Wasserstoff oder C1-C8-Alkyl steht, oder eine Carboxylgruppe oder ein Carboxylderivat oder eine Gruppe -(CH2)x(NH)R5, wobei X für 1 bis 6 steht und R5 für Wasserstoff oder C1-C8-Alkyl steht, oder eine Gruppe -(CH2)yCOOH, wobei Y für 1 bis 6 steht, oder ein -(CH2)yCOOH Säurederivat, wobei Y für 1 bis 6 steht, insbesondere für eine Gruppe -NH2 steht, - R2
- für eine Alkylgruppe steht, vorzugsweise eine C1-C4-Alkylgruppe,
wie Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl,
s-Butyl, s-Butyl,
insbesondere eine Methylgruppe, - R3
- für Wasserstoff, C1-C4-Alkyl oder O-R4 steht, wobei R4 für
Wasserstoff oder C1-C7 Alkyl steht,
insbesondere R3 für Wasserstoff steht,
- R 1
- is a functional group capable of amide formation with respect to the polymer chain of the polyamide of sheath (II),
preferably a group - (NH) R 5 , wherein R 5 is hydrogen or C 1 -C 8 alkyl, or a carboxyl group or a carboxyl derivative or a group - (CH 2 ) x (NH) R 5 , wherein X is 1 to 6 and R5 is hydrogen or C 1 -C 8 alkyl, or a group - (CH 2 ) y COOH, where Y is 1 to 6, or a - (CH 2 ) y COOH acid derivative, wherein Y is 1 to 6, in particular represents a group -NH 2 , - R 2
- is an alkyl group, preferably a C 1 -C 4 -alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, s-butyl,
especially a methyl group, - R 3
- is hydrogen, C 1 -C 4 -alkyl or OR 4 , where R 4 is hydrogen or C 1 -C 7 -alkyl,
in particular R 3 is hydrogen,
In solchen Verbindungen reagieren üblicherweise die tertiären, insbesondere sekundären Aminogruppen der Piperidin-Ringsysteme dabei wegen sterischer Hinderung nicht.In such compounds, the tertiary, especially secondary amino groups of the piperidine ring systems not because of steric hindrance.
Besonders bevorzugt als Verbindung (III) ist 4-Amino-2,2,6,6-Tetramethylpiperidin.Particularly preferred compound (III) is 4-amino-2,2,6,6-tetramethylpiperidine.
Vorteilhaft kann man Verbindung (III) in Mengen von mindestens 0,01 Mol-%, vorzugsweise mindestens 0,05 Mol-%, insbesondere mindestens 0,1 Mol-%, bezogen auf 1 Mol Säureamidgruppen des Polyamids, einsetzen. Advantageously, compound (III) in amounts of at least 0.01 mol%, preferably at least 0.05 mol%, especially at least 0.1 mol%, based on 1 mol of acid amide groups of the polyamide, deploy.
Vorteilhaft kann man Verbindung (II) in Mengen von höchstens 0,8 Mol-%, vorzugsweise höchstens 0,6 Mol-%, insbesondere höchstens 0,4 Mol-%, bezogen auf 1 Mol Säureamidgruppen des Polyamids, einsetzen.Advantageously, compound (II) can be used in amounts of at most 0.8 Mol%, preferably at most 0.6 mol%, in particular at most 0.4 mol%, based on 1 mol of acid amide groups of the polyamide, use.
In einer anderen bevorzugten Ausgestaltung wird die Polymerisation bzw. Polykondensation nach dem erfindungsgemäßen Verfahren in Gegenwart mindestens eines Pigments durchgeführt. Bevorzugte Pigmente sind Titandioxid, wobei Titandioxid vorzugsweise in der Anatas-Modifikation vorliegt, oder farbgebende Verbindungen anorganischer oder organischer Natur. Die Pigmente werden vorzugsweise in einer Menge von 0 bis 5 Gewichtsteile, insbesondere 0,02 bis 2 Gewichtsteile, jeweils bezogen auf 100 Gewichtsteile Polyamid, zugegeben. Die Pigmente können dem Reaktor mit den Ausgangsstoffen oder getrennt davon zugeführt werden.In another preferred embodiment, the polymerization or polycondensation by the process according to the invention in the presence of at least one pigment. preferred Pigments are titania, with titanium dioxide preferably in the Anatase modification, or inorganic coloring compounds or organic nature. The pigments are preferably in an amount of 0 to 5 parts by weight, especially 0.02 to 2 parts by weight, in each case based on 100 parts by weight of polyamide, added. The pigments can be added to the reactor with the starting materials or separately supplied therefrom.
Vorteilhaft als Mantel (II) einsetzbare Polyamide, die ein an die Polymerkette chemisch gebundenes sterisch gehindertes Piperidin-Derivat (III) enthalten, sind beispielsweise in WO 95/28443, WO 97/05189, WO 98/50610, WO 99/46323, WO 99/48949, EP-A-822 275, EP-A-843 696 und den beiden deutschen Anmeldungen 10030515.6 und 10030512.1 beschrieben.Advantageously as a coat (II) usable polyamides, the one to the Polymer chain chemically bonded sterically hindered piperidine derivative (III) are, for example, in WO 95/28443, WO 97/05189, WO 98/50610, WO 99/46323, WO 99/48949, EP-A-822 275, EP-A-843 696 and the two German applications 10030515.6 and 10030512.1 described.
Erfindungsgemäß sind Kern (I) und Mantel (II) chemisch unterschiedlich.According to the invention, core (I) and shell (II) are chemically different.
Vorteilhaft weisen Kern (I) und Mantel (II) einen unterschiedlichen Gehalt an an die Polymerkette chemisch gebundenem sterisch gehindertem Piperidin-Derivat (III) auf, wobei vorzugsweise dieser Gehalt in Kern (I) kleiner ist als in Mantel (II), insbesondere dieser Gehalt, molar gerechnet, in Kern (I) weniger als 50 % dieses Gehalts in Mantel (II) beträgt. In einer besonders bevorzugten Ausführungsform weist Kern (I) kein an die Polymerkette chemisch gebundenes sterisch gehindertes Piperidin-Derivat (III) auf.Advantageously, core (I) and shell (II) have a different one Content of sterically bound to the polymer chain hindered piperidine derivative (III), preferably this Content in core (I) is smaller than in shell (II), in particular this content, in molar terms, in core (I) less than 50% this content in coat (II) is. In a particularly preferred Embodiment does not have core (I) attached to the polymer chain chemically bound sterically hindered piperidine derivative (III) on.
Die Herstellung der Fasern kann in an sich bekannter Weise erfolgen, wie beispielsweise in US-A-3,803,453, US-A-5,445,884, US-A-5,447,794, US-A-5,888,651, EP-A-410 415, EP-A-056 667 beschrieben.The production of the fibers can take place in a manner known per se, for example, in US-A-3,803,453, US-A-5,445,884, US-A-5,447,794, US-A-5,888,651, EP-A-410,415, EP-A-056,667.
So kann man beispielsweise das Polymer für Kern (I) und das Polyamid für Mantel (II) getrennt herstellen, mittels einer Fördervorrichtung, wie eines Extruders, jeweils eine Schmelze der Polymere einem Spinnplattenpaket zuführen und dort die Faser spinnen, insbesondere durch Schnellspinnen bei Abzugsgeschwindigkeiten von mindestens 4000 m/min.So you can, for example, the polymer for core (I) and the polyamide for coat (II) produce separately, by means of a conveyor, like an extruder, each a melt of the polymers feed a spin pack package and spin the fiber there, in particular by quick spinning at take-off speeds of at least 4000 m / min.
Vorteilhaft kommen dabei solche Fasern in Betracht, bei denen Mantel (II) zu Kern (I) ein Gewichtsverhältnis im Bereich von 5:95 bis 80:20, vorzugsweise 5:95 bis 50:50 aufweist.Advantageous in this case are those fibers in which Coat (II) to core (I) a weight ratio in the range of 5:95 to 80:20, preferably 5:95 to 50:50.
Aus den erfindungsgemäßen Fasern können in an sich bekannter Weise Garne, Gewebe und Teppiche hergestellt werden, wie bereits eingangs beschrieben.From the fibers according to the invention can be known in per se The way yarns, fabrics and carpets are made, as before described at the beginning.
In den Beispielen wurden folgende Polyamide eingesetzt:
Aufgebaut aus den Monomeren 1 Gew.-% Lithiumsulfoisophthalat, 0,07 Gew.-% Hexamethylendiamin, 0,15 Gew.-% 4-Amino-2,2,6,6,-Tetramethylpiperidin, Rest Caprolactam
Aufgebaut aus den Monomeren 1 Gew.-% Lithiumsulfoisophthalat, 0,07 Gew.-% Hexamethylendiamin, 0,25 Gew.-% 4-Amino-2,2,6,6,-Tetramethylpiperidin, 0,3 Gew.-% Titandioxid, Rest Caprolactam
Aufgebaut aus den Monomeren 0,15 Gew.-% Propionsäure, Rest Caprolactam
Aufgebaut aus den Monomeren 0,15 Gew.-% Propionsäure, 0,3 Gew.-% Palamid Rot-Farbpigment, Rest Caprolactam
Built up from the monomers 1% by weight of lithium sulfoisophthalate, 0.07% by weight of hexamethylenediamine, 0.15% by weight of 4-amino-2,2,6,6-tetramethylpiperidine, the remainder caprolactam
Made up of the monomers 1% by weight of lithium sulfoisophthalate, 0.07% by weight of hexamethylenediamine, 0.25% by weight of 4-amino-2,2,6,6-tetramethylpiperidine, 0.3% by weight of titanium dioxide , Rest caprolactam
Built up from the monomers 0.15% by weight of propionic acid, the remainder caprolactam
Built up from the monomers 0.15% by weight of propionic acid, 0.3% by weight of palamide red color pigment, the remainder caprolactam
Aus den Polyamiden gemäß Tabelle 1 wurden Fasern mit einer Feinheit
von 2700 dtex und rundem Querschnitt hergestellt, bei einem
Gewichtsverhältnis von Kern (I) zu Mantel (II) von 70:30 gesponnen
und strecktexturiert unter Erhalt der aus der Tabelle ersichtlichen
Daten.
Aus der Tabelle ist ersichtlich, daß die erfindungsgemäßen Fasern eine bessere Kräuselung aufweisen als Fasern nach dem Stand der Technik, die nur aus dem Material von Mantel (II) bestehen (Vergleichsbeispiel 1) oder nur aus dem Material von Kern (I) bestehen (Vergleichsbeispiel 2).From the table it can be seen that the fibers according to the invention have a better crimping than fibers according to the prior Technique consisting only of the material of sheath (II) (Comparative Example 1) or consist only of the material of core (I) (Comparative Example 2).
Claims (16)
- A fiber containing a longitudinal core (I) of a polymer and a chemically different surrounding sheath (II), wherein said sheath (II) is based on a polyamide containing a sterically hindered piperidine derivative (III) attached to the polymer chain by chemical bonding.
- The fiber of claim 1, wherein the weight ratio of said sheath (II) to said core (I) is in the range from 5:95 to 80:20.
- The fiber of claim 1, wherein the weight ratio of said sheath (II) to said core (I) is in the range from 5:95 to 50:50.
- The fiber of any of claims 1 to 3, wherein said sheath (II) contains from 0.03 to 0.8 mol%, based on 1 mol of acid amide group of said polyamide in said sheath (II), of amine radical of the formula (III).
- The fiber of any of claims 1 to 4, wherein compound (III) is 4-amino-2,2,6,6-tetramethylpiperidine and it is attached to said polymer chain by an amide bond.
- The fiber of any of claims 1 to 5, wherein said sheath (II) is based on a polyamide obtainable from monomers selected from the group consisting of lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylate salts, omega-aminocarboxylate esters, equimolar mixtures of diamines and dicarboxylic acids, dicarboxylic acid/diamine salts, dinitriles and diamines or mixtures thereof.
- The fiber of any of claims 1 to 6, wherein said core (I) is based on a polyamide.
- The fiber of any of claims 1 to 7, wherein said core (I) is based on a polyamide obtainable from monomers selected from the group consisting of lactams, omega-aminocarboxylic acids, omega-aminocarbonitriles, omega-aminocarboxamides, omega-aminocarboxylate salts, omega-aminocarboxylate esters, equimolar mixtures of diamines and dicarboxylic acids, dicarboxylic acid/diamine salts, dinitriles and diamines or mixtures thereof.
- The fiber of any of claims 1 to 8, wherein the lactam used is caprolactam.
- The fiber of any of claims 1 to 9, wherein the diamine used is tetramethylenediamine, hexamethylenediamine or their mixture.
- The fiber of any of claims 1 to 10, wherein the dicarboxylic acid used is adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid or a mixture thereof.
- The fiber of any of claims 1 to 11, wherein said sheath (II) contains a sulfonated dicarboxylic acid, or a salt thereof, bonded to the polymer chain.
- The fiber of claim 12, wherein said sulfonated dicarboxylic acid is sulfoisophthalic acid.
- The fiber of any of claims 1 to 13, wherein said monomers used for preparing said polyamide of said sheath (II) have a higher number of amine groups, or their equivalents, used for forming said polymer chain than carboxylic acid groups, or their equivalents, used for forming said polymer chain.
- The fiber of any of claims 1 to 13, wherein said monomers used for preparing said polyamide of said sheath (II) have a higher number of carboxylic acid groups, or their equivalents, used for forming said polymer chain than amine groups, or their equivalents, used for forming said polymer chain.
- The use of fiber as claimed in any of claims 1 to 15 for producing yarn, fabric and carpet.
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DE10058291 | 2000-11-23 | ||
DE10058291A DE10058291A1 (en) | 2000-11-23 | 2000-11-23 | Multicomponent fiber |
PCT/EP2001/013576 WO2002042531A1 (en) | 2000-11-23 | 2001-11-22 | Multicomponent fibre |
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EP (1) | EP1339900B1 (en) |
JP (1) | JP2004532357A (en) |
KR (1) | KR20030062352A (en) |
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US4596742A (en) | 1985-04-22 | 1986-06-24 | Monsanto Company | Partially oriented nylon yarn and process |
US5168909A (en) * | 1991-04-08 | 1992-12-08 | Joyner Jr George R | Combination golf club head cover and hand warmer |
RU2167893C2 (en) * | 1994-04-15 | 2001-05-27 | Басф Аг | Inherently photo- and thermostabilized polyamide, method of its synthesis, threads obtained by high-speed forming and fabrics obtained from threads |
CA2214189C (en) * | 1997-01-10 | 2001-05-29 | Basf Corporation | Novel bicomponent fibers having core domain formed of regenerated polymeric materials and methods of making the same |
US6136433A (en) * | 1997-05-01 | 2000-10-24 | Basf Corporation | Spinning and stability of solution-dyed nylon fibers |
DE19812135A1 (en) | 1998-03-20 | 1999-09-23 | Basf Ag | Production of polyamide with improved wet fastness, useful for production of filaments, fibers, film, sheet materials and moldings |
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PL362423A1 (en) | 2004-11-02 |
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EP1339900A1 (en) | 2003-09-03 |
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