EP0647731B1 - Fibres d'aramide à haute tenacité et à titre élevé, leur procédé de préparation et leur application - Google Patents

Fibres d'aramide à haute tenacité et à titre élevé, leur procédé de préparation et leur application Download PDF

Info

Publication number
EP0647731B1
EP0647731B1 EP94115184A EP94115184A EP0647731B1 EP 0647731 B1 EP0647731 B1 EP 0647731B1 EP 94115184 A EP94115184 A EP 94115184A EP 94115184 A EP94115184 A EP 94115184A EP 0647731 B1 EP0647731 B1 EP 0647731B1
Authority
EP
European Patent Office
Prior art keywords
fibers
tex
phenylene
linear density
aromatic
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
Application number
EP94115184A
Other languages
German (de)
English (en)
Other versions
EP0647731A1 (fr
Inventor
Holger Dr. Jung
Jutta Cardinal
Werner Dr. Bruckner
Richard Dr. Neuert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Invista Technologies SARL Switzerland
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0647731A1 publication Critical patent/EP0647731A1/fr
Application granted granted Critical
Publication of EP0647731B1 publication Critical patent/EP0647731B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
    • 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
    • Y10T428/2904—Staple length fiber
    • 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
    • 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
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2938—Coating on discrete and individual rods, strands or filaments
    • 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
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • the present invention relates to fibers containing selected aromatic Polyamides with high strength and high titers, process for their Production, and their use, in particular for the production of fiber reinforced composites.
  • Aromatic polyamides - also called aramids - are known fiber-forming ones Materials with high chemical resistance. Aramid fibers stand out above all due to good mechanical properties such as high strength and modulus.
  • High titer aramid fibers are already known.
  • aramid fibers with titers of more than 1.7 tex Further coarse titer fibers made from aramids are known from WO-A-92 / 12,279.
  • WO-A-92 / 12,018 describes reinforced composites containing such Fibers and from WO-A-92 / 12,285 is a method for plasma treatment of coarse titre aramid monofilaments. All of these publications describe fibers made from aramids, which are spun from anisotropic solutions become.
  • a typical representative of such aramids is poly (p-phenylene terephthalamide).
  • Aramids of this type can only be elaborate Spinning conditions, for example from solutions of aramid in concentrated sulfuric acid.
  • the present invention relates to fibers with a strength of more than 80 cN / tex and a single filament titer of more than 8 dtex and a titer uniformity a coefficient of variation (cV value) between 1.0 and 6% containing as fiber-forming material a soluble in organic solvents and from isotropic spinning solutions spinnable aromatic polyamide.
  • fiber is in its broadest scope within the scope of this invention To understand meaning, if it concerns coarse titer fibers; to count, for example, continuous fibers (filaments), such as mono- or Multifilaments, or staple fibers, preferably with staple lengths from 0.5 to 50 mm, or pulp.
  • continuous fibers such as mono- or Multifilaments
  • staple fibers preferably with staple lengths from 0.5 to 50 mm, or pulp.
  • the single filament titer of the fibers according to the invention is preferably 8 to 50 dtex, especially 10 to 30 dtex.
  • the strength of the fibers according to the invention is preferably 130 to 260 cN / tex, preferably 150 to 205 cN / tex.
  • the fibers according to the invention have a low elongation at break, for example an elongation at break of less than 10%, preferably an elongation at break of 4 to 5%.
  • the elastic modulus of the fibers according to the invention is usually high, that The initial modulus is, for example, more than 30 N / tex, preferably 30 to 80 N / tex, based on 100% elongation.
  • the single-filament titer has the fibers of the invention have a high uniformity.
  • the Thread uniformity or the titre uniformity of multifilament yarns or of monofilaments by the so-called USTER value expressed (DIN 53 817).
  • Fiber associations are used to determine this value or monofilaments passed through a measuring element, which the Mass fluctuations of the fiber structure or the monofilament in one converts proportional electrical signal.
  • the cV value for a round cross-section is 1.0 % (device-specific).
  • the fibers of the invention have cV values between 1.0 and 6.0% on (measured with the help of the ®USTER tester 2-C from the company Zellweger-Uster AG, Uster, Switzerland), in particular cV values from 1.8 to 5.0%.
  • the cross-sectional shape of the individual filaments of the fibers according to the invention can be arbitrary, for example triangular, tri- or multilobal or in particular elliptical or round. Hollow fibers can also be produced.
  • aramids for use in the production of the fibers according to the invention all aramides soluble in organic solvents can be used, as long as they form isotropic solutions.
  • Soluble aromatic polyamide is within the scope of this invention to understand aromatic polyamide that has a solubility at 25 ° C in N-methylpyrrolidone of at least 50 g / l.
  • Aromatic polyamide forming isotropic solutions is within the scope of this Invention to understand a polymer that at 25 ° C in an organic Solvent or a mixture of such solvents isotropic solutions trains.
  • aromatic polyamides which are polar aprotic Solvents are soluble and the formation of isotropic solutions at least two, especially three different ones in the diamond units have distinctive recurring structural units.
  • the aramide is preferably a polymer which has the recurring structural units of the formulas I, II and, if appropriate, III -OC-Ar 1 -CO-NH-Ar 2 -NH- -OC-Ar 1 -CO-NH-Ar 3 -NH- -OC-Ar 1 -CO-NH-Ar 4 -NH- wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 independently of one another represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in the meta position or in a parallel, coaxial or angled position comparable to these positions to each other, and Ar 2 , Ar 3 and optionally Ar 4 each have different meanings within the scope of the given definitions, and the respective monomer units on which the polymer is based are selected such that an aromatic polyamide which forms soluble and isotropic solutions in organic solvents is obtained.
  • Any residues mean divalent aromatic residues whose Valence bonds are in para- or comparable coaxial or parallel Position to each other, so it is single or multi-core aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be single or multi-core.
  • heterocyclic aromatic Residues have in particular one or two oxygen, nitrogen or Sulfur atoms in the aromatic nucleus.
  • Polynuclear aromatic radicals can be condensed with one another or via C-C bonds or linearly connected to one another via -CO-NH groups.
  • valence bonds that are in coaxial or parallel to each other Stand are directed in opposite directions.
  • An example of coaxial, oppositely directed bonds are the biphenyl-4,4'-ylene bonds.
  • An example of parallel, oppositely directed bonds are the Naphthylene 1,5 or 2,6 bonds, while the naphthylene 1,8 bonds are rectified in parallel.
  • Examples of preferred divalent aromatic radicals, their valence bonds in a para- or comparable coaxial or parallel position to each other are mononuclear aromatic residues with para to each other free valences, especially 1,4-phenylene or dinuclear fused aromatic residues with parallel, oppositely directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear via a C-C Binding linked aromatic residues with coaxial, opposite directed bonds, especially 4,4'-biphenyls.
  • Any residues mean divalent aromatic residues whose Valence bonds are in meta or comparable angled positions to each other, it is single or multi-core aromatic hydrocarbon radicals or heterocyclic-aromatic radicals, which can be single or multi-core.
  • heterocyclic aromatic Residues have in particular one or two oxygen, nitrogen or Sulfur atoms in the aromatic nucleus.
  • Polynuclear aromatic radicals can be condensed with one another or connected to one another via CC bonds or via bridging groups, such as, for example, -O-, -CH 2 -, -S-, -CO- or -SO 2 -.
  • Lower proportions, for example up to 5 mol% of the monomer units, based on the polymer, can be aliphatic or cycloaliphatic in nature be, for example alkylene or cycloalkylene units.
  • Alkylene radicals include branched and in particular straight-chain alkylene understand, for example alkylene with two to four carbon atoms, especially ethylene.
  • Cycloalkylene radicals include, for example, radicals with five to eight To understand carbon atoms, especially cyclohexylene.
  • substituents are alkyl, alkoxy or halogen.
  • Alkyl radicals include branched and in particular straight-chain alkyl understand, for example alkyl with one to six carbon atoms, in particular Methyl.
  • Alkoxy radicals include branched and in particular straight-chain alkoxy understand, for example alkoxy with one to six carbon atoms, especially methoxy.
  • radicals are halogen, these are, for example Fluorine, bromine or especially chlorine.
  • Aromatic polyamides based on unsubstituted are preferred Leftovers.
  • Examples of preferred diamine combinations that preferred this recurring structural units of the formulas I, II, and III are based 1,4-phenylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dichloro-, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,3'-dichloro-, 3,3'-dimethyl- or 3,3'-dimethoxybenzidine; as well as 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 3,3'-dichloro-, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; such as 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 4,4'-diaminobenzanilide; such as 1,4-phenylenediamine, 1,4-
  • Aramides which are derived from such diamine combinations and which are preferably used according to the present invention are in the EP-A-199,090, EP-A-364,891, EP-A-394,892, EP-A-394,893 and EP-A-424,860.
  • aromatic polyamides to be used according to the invention are in themselves known and can be produced by methods known per se.
  • Aromatic polyamides are preferably used which have the recurring structural units of the formulas I, II and optionally III defined above, in which Ar 1 represents a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in one of these positions comparable parallel or coaxial position to each other, Ar 2 represents a divalent mono- or polynuclear aromatic radical, the free valences of which are in the p-position or in a parallel or coaxial position with respect to one another, Ar 3 represents a radical of formula IV -Ar 5 -X-Ar 6 - in which Ar 5 and Ar 6 independently of one another represent a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position comparable to this position, or in which Ar 6 additionally contains a divalent mono- or represents polynuclear aromatic radical, the free valences of which are in the meta position or in an angled position comparable to one another, X is
  • aramids of this type are polymers in which Ar 1 is 1,4-phenylene, Ar 2 is 1,4-phenylene or a divalent radical of 4,4'-diaminobenzanilide, Ar 5 and Ar 6 are 1,4-phenylene, X is -O-, -CH 2 - or -O-1,4-phenylene-O- and Ar 4 is a divalent radical of 3,4-diaminodiphenyl ether, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine or of 3,3'-dimethoxybenzidine.
  • the polycondensation to be spun aromatic polyamides according to the invention is generally carried out as solution polymerization.
  • the Organic solvents preferably contain at least one solvent of the amide type, e.g. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, Tetramethyl urea, N-methyl-2-piperidone, N, N'-dimethylethylene urea, N, N, N ', N'-tetramethyl maleic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N'-dimethylpropionic acid amide, N, N-dimethylisobutylamide, N-methylformamide, N, N'-dimethylpropyleneurea.
  • the preferred organic solvents N-methyl-2-pyrrolidone, N, N-dimethylacetamide and a mixture of these Links.
  • the amide solvent is not only used as a solvent for the aromatic monomeric compounds and the aromatic obtained therefrom Copolyamide but also as an acid acceptor for a hydrogen halide used, e.g. for hydrogen chloride, which is a byproduct of Copolymerization of the aromatic monomeric compounds is formed.
  • a solubility enhancer to use additive, for example a metal halide of one of the metals Group I or II of the periodic system, which the Polycondensation mixture before, during or after the polycondensation is added.
  • alkali metal halides such as lithium chloride
  • alkaline earth metal halides such as calcium chloride
  • the polycondensation temperatures are in solution polymerization usually between -20 ° C and + 120 ° C, preferably between + 10 ° C and + 100 ° C. Particularly good results are obtained at reaction temperatures achieved between + 10 ° C and + 80 ° C.
  • the sum of the concentrations of the aromatic monomeric compounds in The polycondensation mixture solution can be made considering the desired Degree of polycondensation, the desired viscosity of the Polycondensation mixture, the type of aromatic used monomeric compounds, the type of solvent used and the desired polycondensation temperature can be set.
  • the cheapest The sum of the concentrations can be based on a series of preliminary tests be determined for the course of the polycondensation.
  • Polycondensation reactions are preferably carried out so that after Completion of the reaction 2 to 15, preferably 3 to 12 wt .-% Polycondensate is present in the solution. Particularly good results are found at Concentrations of 4 to 6 wt .-% achieved.
  • the molecular weight of the polymer increases in the course of the polycondensation and thus also the viscosity of the reaction mixture.
  • a sufficient molecular chain length is reached when the viscosity of the the polycondensation polymer solution obtained has an inherent viscosity of Polymers of more than 3.0 dl / g, preferably more than 5.0 dl / g, in particular Corresponds to 4.5 to 8.0 dl / g.
  • the polycondensation in the usual way by adding monofunctional compounds, e.g. Acetyl chloride can be stopped.
  • the resulting salt-like solution can then be added to the amide solvent bound hydrogen chloride neutralized by adding basic substances become.
  • Suitable for this are, for example, lithium hydroxide, calcium hydroxide, but especially calcium oxide.
  • Polyamide can be separated from the polycondensation mixture by a separation process are deposited, for example by precipitation.
  • the solution for molding the copolyamide is that obtained aromatic polyamide then in a suitable organic solvent solved, this method as a dissolution process for the preparation of Spinning solution is called.
  • the solvent of the amide type as a solvent used, especially the solvents mentioned above from Amide type, or a mixture of two or more of the compounds mentioned.
  • the spinning solution may contain an additive to promote solubility, wherein at least one metal halide of a metal of groups I and II of Periodic table can be used, for example lithium chloride, Calcium chloride or magnesium bromide, in one concentration between 0.2 and 10%, preferably between 0.5 and 5%, based on the Total weight of the spinning solution.
  • the additive to promote solubility promotes the stability of the spinning solution at elevated temperature.
  • the spinning of the spinning solution into the fibers according to the invention can be carried out any suitable dry process, wet process or dry-wet process respectively.
  • the Spinning solution extruded through a spinneret into a coagulating liquid.
  • the coagulation fluid is out Water or from an aqueous, a polar organic solvent containing solution.
  • the polar organic solvent can be selected from the same amide solvents that are commonly used for dissolving the aromatic polyamide can be used.
  • the same solvent used as in the molding solution is included.
  • the coagulation liquid is preferably at a Temperature between 0 ° C and the boiling point of the coagulation liquid used at atmospheric pressure.
  • the polar organic solvent is in the coagulation liquid preferably in a concentration between 70% by weight and less, in particular less than 50% by weight.
  • the Spinning solution through a spinning head with one or more spinning openings extruded, the filamentary streams of the spinning solution in one of the above specified coagulation liquids are solidified (wet process) or in an atmosphere that promotes evaporation (dry process).
  • a the so-called variant is also suitable "Dry Nozzle Wet Spinning Process" as e.g. in US-A-3,414,645 is described.
  • a usual horizontal or Vertical wet spinning machine, a dry jet wet spinning machine, or one Spinning machine can be used in which the material flow under tension after done below.
  • the size of the nozzle bores of the spinneret should be chosen so that produces a filament of the desired titer. Usually you bet Spinnerets with nozzle hole diameters from 0.1 to 1.0 mm. This Spinnerets can have individual nozzle holes (production of monofilaments) or also have several nozzle holes (production of multifilaments).
  • the Coagulation preferably using a coagulation liquid Additive to promote coagulation, taking part in this coagulation another coagulation step follows, in the course of which the coagulating Filaments of aromatic polyamide are introduced into a water bath, which is kept at a temperature between 0 and 100 ° C.
  • the additional coagulation step serves to complete the Coagulation by removing the solvent. Also be Additives for promoting coagulation, if such substances are used, washed out of the coagulated filaments.
  • aromatic polyamide using conventional spinning processes and devices can be easily processed into filaments without a dangerous or harmful solvent, e.g. concentrated Sulfuric acid.
  • those made from the copolyamide of the invention Filaments a dense internal structure.
  • the filaments produced according to the invention are usually one Subjected to stretching, by which not only the mechanical Properties such as tensile strength and modulus of elasticity but also the thermal properties, e.g. the thermal Stability of the fibers produced in this way.
  • Filaments are usually stretched for high mechanical strength and to achieve a high modulus of elasticity.
  • the aspect ratio is usually about 1: 6 to 1:20.
  • the stretching temperature is usually between 250 and 500 ° C, preferably between 300 and 480 ° C.
  • the stretching can be done in a single step, in two steps or in several Steps are carried out, for heating a hot plate or cylindrical heater can be used.
  • the drawn filaments of a further heat treatment with the same or subjected to higher temperatures to promote their crystalline structure.
  • the fibers of the invention are characterized by high tensile strengths and Initial moduli and low elongation at break.
  • Step c) may involve evaporation of the solvent Apply increased temperature act, so that a lower solvent Shaped structure is created that is sufficient for further processing has mechanical stability and freedom from tack (dry molding process).
  • Step c) is preferably an introduction of the primary shaped structure in a bath containing a coagulation liquid so that the organic solvent from said primary shaped structure is removed and the desired shaped structure by coagulation of the Primary structure arises, which is sufficient for further processing has mechanical stability (wet molding process).
  • It can be introduced by direct extrusion into a coagulation liquid take place or by extruding into a coagulation liquid Passing through an air gap of a predetermined length.
  • the fibers of the invention which have excellent mechanical and possess thermal properties and are characterized by high stretchability can be used industrially in a wide variety of ways, for example as reinforcement materials, for example for reinforcement of car tires and other rubber articles and especially for the Reinforcement of hydraulically setting materials, as heat-resistant Insulation materials, for the production of filter fabrics and as insulation materials.
  • An aromatic polyamide based on terephthalic acid dichloride, 25 mol% para-phenylenediamine, 50 mol% 3,3'-dimethylbenzidine and 25 mol% 1,4-bis (4-aminophenoxy) benzene is by solution polycondensation in NMP prepared so that the solution has an inherent viscosity of about 6 dl / g having.
  • the polymer solution obtained is directly through a 10 hole nozzle spun the wet spinning process.
  • the nozzle hole diameters are 150 to 300 ⁇ m.
  • the filaments are contained in an aqueous precipitation bath 35% by weight of NMP precipitated at 80 ° C and then in two water baths and washed in a washing machine at 80 ° C.
  • the single filament titer of the filaments obtained is 10 dtex.
  • the filaments have the following mechanical properties: fineness-related strength: 133 cN / tex Starting module: 66 N / tex, Elongation at break: 2.1%
  • the filament has the following mechanical properties: fineness-related strength: 203 cN / tex Starting module: 51 N / tex, Elongation at break: 4.1%

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyamides (AREA)
  • Woven Fabrics (AREA)

Claims (14)

  1. Fibres ayant une ténacité de plus de 80 cN/tex et un titre de filament individuel de plus de 8 dtex, et une uniformité de titre correspondant à un coefficient de variation (c.v.) compris entre 1,0 et 6,0 %, contenant en tant que matériau formant des fibres un polyamide aromatique soluble dans des solvants organiques et apte à être filé à partir de solutions de filage isotropes.
  2. Fibres selon la revendication 1, caractérisées en ce que leur titre de filament individuel va de 8 à 50 dtex.
  3. Fibres selon la revendication 2, caractérisées en ce que leur titre de filament individuel va de 10 à 30 dtex.
  4. Fibres selon la revendication 1, caractérisées en ce que leur ténacité va de 130 à 260 cN/tex.
  5. Fibres selon la revendication 4, caractérisées en ce que leur ténacité va de 150 à 205 cN/tex.
  6. Fibres selon la revendication 1, caractérisées en ce que leur ténacité est supérieure à 150 cN/tex et leur allongement à la rupture est de 4 à 5 %.
  7. Fibres selon la revendication 1, caractérisées en ce que leur module d'élasticité, sur la base d'un allongement de 100 %, va de 30 à 80 N/tex.
  8. Fibres selon la revendication 1, caractérisées en ce qu'il s'agit de monofilaments ou de multifilaments qui présentent unr uniformité de titre exprimé par un coefficient de variation (c.v.) compris entre 1,8 et 5,0 %.
  9. Fibres selon la revendication 1, caractérisées en ce que le polyamide aromatique consiste en un polymère qui comporte les motifs structuraux répétitifs de formules I, Il et éventuellement III -OC-Ar1-CO-NH-Ar2-NH- -OC-Ar1-CO-NH-Ar3-NH- -OC-Ar1-CO-NH-Ar4-NH- dans lesquelles Ar1, Ar2, Ar3 et Ar4 représentent, indépendamment les uns des autres, un radical aromatique divalent mono- ou polynucléaire, dont les valences libres se trouvent l'une par rapport à l'autre en position para ou en position méta ou en une position parallèle, coaxiale ou angulaire, comparable à ces positions, et
    Ar2, Ar3 et éventuellement Ar4 adoptent dans chaque cas particulier des significations différentes rentrant dans le cadre des définitions données, et les composants monomères respectifs à la base du polymère étant choisis de manière qu'il en résulte un polyamide aromatique soluble dans des solvants organiques et formant des solutions isotropes.
  10. Fibres selon la revendication 9, caractérisées en ce que Ar1 représente un radical aromatique divalent mono- ou polynucléaire dont les valences libres se trouvent l'une par rapport à l'autre en position para ou en une position parallèle ou caoaxiale comparable à cette position,
    Ar2 représente un radical aromatique divalent mono- ou polynucléaire dont les valences libres se trouvent l'une par rapport à l'autre en position p ou en une position parallèle ou coaxiale comparable à cette position,
    Ar3 représente un radical de formule IV -Ar5-X-Ar6- dans laquelle Ar5 et Ar6 représentent, indépendamment l'un de l'autre, un radical aromatique divalent mono- ou polynucléaire dont les valences libres se trouvent l'une par rapport à l'autre en position para ou en une position parallèle ou coaxiale comparable à cette position, ou dans laquelle Ar1 représente en outre un radical aromatique divalent mono- ou polynucléaire dont les valences libres se trouvent l'une par rapport à l'autre en position méta ou en une position angulaire comparable à cette position,
    X est un groupe de formule -O-, -S-, -SO2-, -O-phénylène-O- ou alkylène, et
    Ar4 adopte l'une des significations définies pour Ar2 ou
    Ar3 mais est différent du radical Ar2 ou Ar3 d'une molécule, choisi dans chaque cas.
  11. Fibres selon la revendication 10, caractérisées en ce que Ar1 est le groupe 1,4-phénylène, Ar2 est le groupe 1,4-phénylène ou un reste divalent du 4,4'-diaminobenzanilide, Ar5 et Ar6 représentent le groupe 1,4-phénylène, X est -O-, -CH2- ou le groupe -O-1,4-phénylène-O- et Ar4 est un reste divalent de l'éther 3,4'-diaminodiphénylique, de la 3,3'-dichlorobenzidine, de la 3,3'-diméthylbenzidine ou de la 3,3'-diméthoxybenzidine.
  12. Procédé pour la fabrication des fibres selon la revendication 1, comprenant les étapes suivantes:
    a) préparation d'une solution de filage isotrope contenant un solvant organique et au moins un polyamide aromatique soluble dans des solvants organiques,
    b) extrusion de la solution de filage par une filière, qui comporte des orifices en nombre et forme préétablis, de manière qu'il en résulte une fibre au titre désiré de filament individuel,
    c) élimination du solvant organique, d'une façon connue en soi, de manière à obtenir des filaments plus pauvres en solvant ou exempts de solvant qui présentent une absence de pégosité et une stabilité mécanique suffisantes pour la mise en oeuvre ultérieure, et
    d) étirage des filaments obtenus, d'une façon connue en soi.
  13. Procédé selon la revendication 12, caractérisé en ce que, dans l'étape c), on introduit la structure moulée primaire formée à l'étape b) dans un bain contenant un liquide de coagulation, de sorte que le solvant organique est éliminé de ladite structure moulée primaire et on obtient par coagulation de la structure primaire la structure moulée recherchée, qui présente une stabilité mécanique suffisante pour la mise en oeuvre ultérieure.
  14. Utilisation des fibres selon la revendication 1, en tant que matériaux de renforcement, en tant que matériaux d'isolation résistants à la chaleur, pour la fabrication de tissus filtrants et en tant que matériaux d'étanchéité.
EP94115184A 1993-10-06 1994-09-27 Fibres d'aramide à haute tenacité et à titre élevé, leur procédé de préparation et leur application Expired - Lifetime EP0647731B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4334004A DE4334004A1 (de) 1993-10-06 1993-10-06 Aramidfasern hoher Festigkeit und hohen Titers, Verfahren zu deren Herstellung sowie deren Verwendung
DE4334004 1993-10-06

Publications (2)

Publication Number Publication Date
EP0647731A1 EP0647731A1 (fr) 1995-04-12
EP0647731B1 true EP0647731B1 (fr) 1999-02-17

Family

ID=6499501

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94115184A Expired - Lifetime EP0647731B1 (fr) 1993-10-06 1994-09-27 Fibres d'aramide à haute tenacité et à titre élevé, leur procédé de préparation et leur application

Country Status (6)

Country Link
US (1) US5698324A (fr)
EP (1) EP0647731B1 (fr)
JP (1) JPH07150413A (fr)
AT (1) ATE176806T1 (fr)
DE (2) DE4334004A1 (fr)
ES (1) ES2128480T3 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5965260A (en) * 1991-09-12 1999-10-12 Kansai Research Institute (Kri) Highly oriented polymer fiber and method for making the same
FR2773178B1 (fr) * 1997-12-29 2000-04-21 Nylstar Sa Fils textiles multifilamentaires a section creuse - procede de fabrication de ces fils, et surfaces textiles obtenues avec ces fils
US6383623B1 (en) 1999-08-06 2002-05-07 Tex Tech Industries Inc. High performance insulations
DE102004010861A1 (de) * 2004-03-05 2005-09-22 Veritas Ag Flexibler Schlauch, insbesondere Ladeluftschlauch
JP4563926B2 (ja) * 2005-12-01 2010-10-20 帝人テクノプロダクツ株式会社 芳香族コポリアミド繊維
JP4563925B2 (ja) * 2005-12-01 2010-10-20 帝人テクノプロダクツ株式会社 芳香族コポリアミド繊維の製造方法
RU2452799C2 (ru) * 2006-12-15 2012-06-10 Тейдзин Текно Продактс Лимитед Ароматическое полиамидное волокно на основе гетероциклсодержащего ароматического полиамида, способ его изготовления, ткань, образованная волокном, и армированный волокном композитный материал
DE102007043946A1 (de) * 2007-09-14 2009-03-19 Bayerisches Zentrum für Angewandte Energieforschung e.V. Faserverbünde und deren Verwendung in Vakuumisolationssystemen
US20090075080A1 (en) * 2007-09-19 2009-03-19 General Electric Company Coated fiber and method for making the coated fiber
DE102008004347A1 (de) 2008-01-15 2009-04-23 Hoffmann & Krippner Gmbh Vorrichtung zur Erfassung des Orts einer Zusammendrückstelle
US8137809B2 (en) * 2008-04-11 2012-03-20 Dsm Ip Assets B.V. Ultra high molecular weight polyethylene multifilament yarns, and process for producing thereof
DE102014108343A1 (de) * 2014-06-13 2015-12-17 J.H. Ziegler Gmbh Verbundwerkstoffflusshilfevliesstoff

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4034138A (en) * 1973-12-28 1977-07-05 Hitco Aromatic polyamide fibers coated with a polyurethane
US4162346A (en) * 1976-09-23 1979-07-24 Celanese Corporation High performance wholly aromatic polyamide fibers
JPS5734125A (en) * 1980-08-07 1982-02-24 Teijin Ltd Fully aromatic polyamide fiber and film and their production
JPS589619A (ja) * 1981-07-06 1983-01-20 富士機工株式会社 椎茸原木等の加工台
DE3369353D1 (en) * 1982-11-02 1987-02-26 Akzo Nv Adhesive-coated multifilament yarn of an aromatic polyamide and a method for the manufacture thereof
EP0199090B1 (fr) * 1985-03-23 1990-10-03 Hoechst Aktiengesellschaft Objets moulés en copolyamide aromatique et leur procédé de fabrication
NL8601159A (nl) * 1986-05-06 1987-12-01 Akzo Nv Vezels en garens uit een mengsel van aromatische polyamiden.
US4835223A (en) * 1987-11-02 1989-05-30 Akzo N.V. Fibres and yarns from a blend of aromatic polyamides
DE69027108T2 (de) * 1989-06-28 1996-10-17 Michelin Recherche Et Technique, Fribourg Aramidemonofilament und verfahren zur herstellung
AT396535B (de) * 1990-06-13 1993-10-25 Semcotec Handel Nachrichtenübertragungssystem, insbesondere telefonsystem
EP0561886B1 (fr) * 1990-12-12 1995-11-02 Du Pont Canada Inc. Copolyamides d'acides terephtalique
FR2671110B1 (fr) * 1990-12-27 1993-04-09 Michelin Rech Tech Monofilament aramide ayant une peau faiblement structuree - procede pour obtenir ce monofilament.
FR2671113B1 (fr) * 1990-12-27 1994-05-20 Michelin Et Cie Traitement par plasma d'un monofilament aramide et monofilament ainsi obtenu.
FR2671030A1 (fr) * 1990-12-27 1992-07-03 Michelin Rech Tech Assemblages de renfort avec monofilaments en polymeres organiques.
JPH05163610A (ja) * 1991-12-18 1993-06-29 Teijin Ltd 芳香族ポリアミド偏平繊維
ATE153087T1 (de) * 1992-01-15 1997-05-15 Hoechst Ag Bondiertes fadenbündel, verfahren zu dessen herstellung und daraus erhältliche textile flächengebilde
SK383792A3 (en) * 1992-01-27 1995-02-08 Hoechst Ag Aromatic copolyamides, method of their preparation and use
CZ134893A3 (en) * 1992-07-08 1994-02-16 Hoechst Ag Aromatic copolyamides, process of their preparation and objects made therefrom
US5334693A (en) * 1993-05-21 1994-08-02 E. I. Du Pont De Nemours And Company Aramid composition

Also Published As

Publication number Publication date
JPH07150413A (ja) 1995-06-13
ES2128480T3 (es) 1999-05-16
US5698324A (en) 1997-12-16
ATE176806T1 (de) 1999-03-15
EP0647731A1 (fr) 1995-04-12
DE4334004A1 (de) 1995-04-13
DE59407824D1 (de) 1999-03-25

Similar Documents

Publication Publication Date Title
US5646234A (en) Production of fibers or films using specific forming solutions and the fibers of films obtainable thereby
EP0456306B1 (fr) Procédé pour la fabrication de fibres de polykétone
EP0678539A2 (fr) Copolyamides aromatiques, leur procédé de préparation, objets moulés et leur fabrication
DE60125870T2 (de) Verfahren zur herstellung einer meta-vollaromatischen polyamidfaser
DE3007063C2 (de) Faser- oder filmbildendes aromatisches Copolyamid, Verfahren zu seiner Herstellung und dessen Verwendung
DE2556883A1 (de) Aromatische copolyamide, hieraus gefertigte formgegenstaende und verfahren zu deren herstellung
EP0647731B1 (fr) Fibres d'aramide à haute tenacité et à titre élevé, leur procédé de préparation et leur application
EP0364892A2 (fr) Polyamides entièrement aromatiques, procédé pour leur préparation et objets moulés
EP0424860A2 (fr) Polyamides entièrement aromatiques, procédé de préparation et produits formés
EP0364893A2 (fr) Polyamides entièrement aromatiques, procédé pour leur préparation et objets moulés
US5662852A (en) Mass-colored formed structures based on aromatic polyamides, mass-colored fiber, and premix for producing mass-colored formed structures
EP0396020A2 (fr) Matériaux fibreux d'alliages homogènes de polyamides aromatiques et poly-N-vinyl-Pyrrolidone, leur procédé de fabrication et application
KR0127875B1 (ko) 가수분해 안정성이 향상된 섬유
EP0553755B1 (fr) Fibres d'un copolyamide aromatique et leur utilisation
EP0567998A1 (fr) Procédé de préparation de méta-aramides filables
EP0445673B1 (fr) Copolyamides aromatiques, leur procédé de préparation et articles moulés à partir de ceux-ci
EP0553756B1 (fr) Copolyamides aromatiques, procédé pour leur préparation et articles moulés à partir de ceux-ci
EP0852246A2 (fr) Compositions contenant un polyamide aromatique et un fullerène, objets moulés à partir de celles-ci
EP0522418B1 (fr) Copolyamides aromatiques, leur procédé de préparation, et articles formis à partir de ceux-ci
EP0578164A2 (fr) Copolyamides aromatiques, procédé pour leur préparation et objects moulés
DE4004652A1 (de) Vollaromatische polyamide, verfahren zu ihrer herstellung und daraus geformte gebilde
EP0499230B1 (fr) Copolyamides aromatiques, procédé pour leur préparation et articles moulés à partir de ceux-ci
DE4411757A1 (de) Aromatische Copolyamide, Verfahren zu deren Herstellung, geformte Gebilde und deren Herstellung
DE4421885A1 (de) Aromatische Copolyamide, Verfahren zu deren Herstellung, geformte Gebilde und deren Herstellung
DE3605394A1 (de) Geformte gebilde aus aromtischen copolyamiden und verfahren zu ihrer herstellung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19951012

17Q First examination report despatched

Effective date: 19970502

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IE IT LI LU NL PT SE

REF Corresponds to:

Ref document number: 176806

Country of ref document: AT

Date of ref document: 19990315

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 59407824

Country of ref document: DE

Date of ref document: 19990325

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2128480

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19990428

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 19990617

Year of fee payment: 6

Ref country code: IE

Payment date: 19990617

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19990618

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19990625

Year of fee payment: 6

Ref country code: NL

Payment date: 19990625

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990627

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19990701

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19990705

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19990719

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19990720

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19990723

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19990909

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: HOECHST AKTIENGESELLSCHAFT TRANSFER- ARTEVA TECHNO

NLS Nl: assignments of ep-patents

Owner name: ARTEVA TECHNOLOGIES S.A.R.L.

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000927

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000927

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000927

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000928

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000930

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000930

BECA Be: change of holder's address

Free format text: 20000126 *ARTEVA TECHNOLOGIES S.A.R.L.:TALSTRASSE 80, 8001 ZURICH

BERE Be: lapsed

Owner name: ARTEVA TECHNOLOGIES S.A.R.L.

Effective date: 20000930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010401

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20000927

EUG Se: european patent has lapsed

Ref document number: 94115184.7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010531

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20010401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20010331

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20011011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050927