EP0790335A1 - Fibres d'aramide résistant aux coupures, fils contenant ces fibres et leur utilisation - Google Patents

Fibres d'aramide résistant aux coupures, fils contenant ces fibres et leur utilisation Download PDF

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Publication number
EP0790335A1
EP0790335A1 EP97101675A EP97101675A EP0790335A1 EP 0790335 A1 EP0790335 A1 EP 0790335A1 EP 97101675 A EP97101675 A EP 97101675A EP 97101675 A EP97101675 A EP 97101675A EP 0790335 A1 EP0790335 A1 EP 0790335A1
Authority
EP
European Patent Office
Prior art keywords
phenylene
recurring structural
mol
formula
structural units
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.)
Granted
Application number
EP97101675A
Other languages
German (de)
English (en)
Other versions
EP0790335B1 (fr
Inventor
Richard Dr. Neuert
Jürgen Dr. Idzko
E. O. Oakley
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.)
Clemson University Research Foundation (CURF)
Original Assignee
Hoechst Trevira GmbH and Co KG
Clemson University Research Foundation (CURF)
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 Trevira GmbH and Co KG, Clemson University Research Foundation (CURF) filed Critical Hoechst Trevira GmbH and Co KG
Publication of EP0790335A1 publication Critical patent/EP0790335A1/fr
Application granted granted Critical
Publication of EP0790335B1 publication Critical patent/EP0790335B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/442—Cut or abrasion resistant yarns or threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • 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
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • 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 aramid fibers which have improved cut resistance.
  • fiber-forming polymers are usually mixed with solids, such as titanium dioxide or colloidal quartz, as matting agents.
  • solids such as titanium dioxide or colloidal quartz
  • matting agents for example for generating magnetic properties. Examples of this can be found in JP-A-55-098,909 or in JP-A-3-130,413.
  • the use of such matting agents in solution-spun aramid fibers has so far not been common.
  • Aromatic polyamides are known to be raw materials with high thermal and chemical stability and low flammability.
  • fibers and foils made from such raw materials have very good mechanical properties, such as high strength and high initial modulus (modulus of elasticity) and are well suited for technical areas of application - for example for reinforcing plastics or as filter materials.
  • threads or fibers can be produced from polyaramides with high strength and high initial modulus if the amide bonds on the aromatic cores are oriented coaxially or almost parallel to one another, thereby producing rigid, rod-shaped polymer molecules.
  • a typical polyamide of this type is, for example, poly (p-phenylene terephthalamide).
  • copolyamides In addition to aromatic polyamides of this type, which are difficult to produce and process because of their insolubility in polar organic solvents, copolyamides have been developed which have good solubility in the known amide solvents, which can also be spun well and whose filaments can be stretched by high Mark strength values and initial moduli. Examples of such aromatic copolyamides can be found in DE-PS-2,556,883, in DE-A-3,007,063, and in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860.
  • the polymers to be used in the fibers according to the invention are aramids which are composed to a substantial extent of para-aromatic monomers and which are soluble in polar aprotic organic solvents.
  • soluble aromatic polyamide is understood to mean an aromatic polyamide that has a solubility in N-methylpyrrolidone of at least 50 g / l at 25 ° C.
  • the polar aprotic organic solvent preferably contains at least one solvent of the amide type, such as, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, 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 for the process according to the invention are N-methyl-2-pyrrolidone, N, N-dimethylacetamide and a mixture of these compounds.
  • aromatic polyamides to be used according to the invention are compounds which are soluble in polar aprotic organic solvents, preferably with the formation of isotropic solutions, and which have at least two, in particular three, different recurring structural units which differ in the diamine units have the above definition.
  • radicals mean divalent aromatic radicals, the valence bonds of which are in para- or in a comparable coaxial or parallel position to one another, these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear.
  • heterocyclic-aromatic radicals these 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 linearly connected to one another via C-C bonds or via -CO-NH groups.
  • valence bonds which are in a coaxial or parallel position, are directed in opposite directions.
  • An example of coaxial, oppositely directed bonds are the biphenyl-4,4'-ene bonds.
  • An example of parallel, opposite bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene 1,8 bonds are parallel aligned.
  • Examples of preferred divalent aromatic radicals are mononuclear aromatic radicals with mutually para-free valences, in particular 1,4-phenylene or dinuclear fused aromatic radicals with parallel directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear aromatic residues linked via a CC bond with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.
  • radicals mean divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another, these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear.
  • heterocyclic-aromatic radicals these 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 -O-, -CH 2 -, -S-, -CO- or -SO 2 -.
  • Examples of preferred divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another are mononuclear aromatic radicals with free valences which are meta to one another, in particular 1,3-phenylene or dinuclear condensed aromatic radicals with bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a CC bond with bonds oriented at an angle to one another, in particular 3,4'-biphenylene.
  • Smaller proportions for example up to 5 mol% of the monomer units, based on the polymer, can be aliphatic or cycloaliphatic in nature, for example alkylene or cycloalkylene units.
  • Alkylene radicals are to be understood as meaning branched and in particular straight-chain alkylene, for example alkylene with two to four carbon atoms, in particular ethylene.
  • Cycloalkylene radicals are, for example, radicals having five to eight carbon atoms, in particular cyclohexylene.
  • substituents are alkyl, alkoxy or halogen.
  • Alkyl radicals are to be understood as meaning branched and in particular straight-chain alkyl, for example alkyl having one to six carbon atoms, in particular methyl.
  • Alkoxy radicals are to be understood as meaning branched and in particular straight-chain alkoxy, for example alkoxy with one to six carbon atoms, in particular methoxy.
  • radicals are halogen, it is, for example, fluorine, bromine or, in particular, chlorine.
  • Aromatic polyamides based on unsubstituted radicals are preferably used.
  • Terephthalic acid units are preferably used as the dicarboxylic acid unit in the aromatic polyamides containing the recurring structural units of the formulas I, II and optionally III.
  • Examples of preferred diamine combinations on which these preferred recurring structural units of the formulas III and IV or the formulas III and VI or the formulas III, IV and V or the formulas III, IV and VI are based are 1,4-phenylenediamine and 3,4 ' -Diaminodiphenyl ether; 1,4-phenylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dichloro-, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; as well as 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; as well as 1,4-phen
  • Aramides which are derived from such diamine combinations and which can preferably be used according to the present invention are described in part in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP- A-424,860.
  • aromatic polyamides to be used according to the invention are known per se.
  • the polycondensation and the production of fibers from the coaramides to be used according to the invention is carried out according to methods known per se, such as these e.g. have been described in the documents listed above.
  • the mixing in of the filler and the production of filler-containing fibers can be carried out, for example, by the process described in EP-A-662,534.
  • the aromatic copolyaramides to be used according to the invention must have a molecular weight which is sufficient for fiber production.
  • a sufficient molecular chain length of the copolyaramides to be used according to the invention is present, for example, if the viscosity of the polymer solution obtained in the polycondensation corresponds to an inherent viscosity of the polymer of more than 2.5 dl / g, preferably 2.5 to 7.0 dl / g .
  • ⁇ rel means the relative viscosity, c the concentration used in g / 100 ml.
  • the filler used in the fibers according to the invention very generally has a Mohs hardness of greater than or equal to 3, preferably greater than or equal to 5.
  • any materials can be used as fillers, ie semimetals or preferably metals or non-metals as well as alloys of these materials, provided that they have the hardness defined above.
  • Metals which are preferably used are, for example, aluminum, iron, nickel, stainless steel, copper, zinc, tantalum, titanium, tungsten or mixtures thereof.
  • Metal alloys with tungsten as an alloy component are particularly preferred which have a Mohs hardness of 6.5 to 7.5.
  • Non-metals which are preferably used are, for example, metal oxides, such as aluminum oxide; Metal carbides such as tungsten carbide; Metal nitrides, metal silicates, metal sulfates, metal phosphates, metal borides or mixtures thereof. Ceramic materials can also be used.
  • the proportion of the filler in the fiber according to the invention should in any case be selected so that the cut resistance is increased in comparison with the unmodified fiber, for example by at least more than 8% (measured according to the CPP test).
  • the remaining mechanical properties of the fibers such as tensile strength or modulus, are only insignificantly impaired by the use of the filler.
  • the tensile strength of a filled fiber with increased cut resistance drops to approximately 205 cN / tex, compared to the tensile strength of approximately 215 cN / tex of the unfilled fiber.
  • Typical amounts of filler are in the range of less than 25% by weight, based on the weight of the fiber, preferably in the range of 0.05 to 20 % By weight.
  • the particle shape of the filler used can be any; for example spherical or elliptical or irregular.
  • the filler is mixed in, for example, in the form of a powder.
  • the filler preferably has an average particle diameter of less than or equal to 20 ⁇ m, in particular from 0.05 to 5 ⁇ m.
  • fibers is to be understood in its broadest meaning within the scope of this invention; this includes, for example, staple fibers or, in particular, filaments of any titer, including monofilaments.
  • the fibers according to the invention are distinguished by excellent mechanical properties, such as high tear strengths and initial moduli and low elongation at break, and by the above-mentioned increased cut resistance.
  • the fibers according to the invention preferably have single filament titer greater than or equal to 0.6 dtex, in particular from 1 to 20 dtex.
  • the tensile strength of the fibers according to the invention is preferably 150 to 300 cN / tex.
  • the initial modulus, based on 100% elongation, of the fibers according to the invention is preferably 20 to 120 N / tex.
  • the cross-sectional shape of the fibers according to the invention can be any, for example triangular, tri-or multilobal or in particular elliptical or round.
  • the fibers according to the invention can be used for the production of protective clothing, anti-vandalism textiles and composite materials.
  • the use of the fibers for these purposes is also the subject of the present invention.
  • the fibers according to the invention are generally used in the form of yarns. This can be secondary spun yarns or preferably multifilament yarns. Typical yarn titers range from 50 to 9000 dtex.
  • Yarns containing the fibers of the invention are also an object of the present invention.
  • a preferred embodiment relates to blended yarns containing the fibers and fibers according to the invention made of inorganic materials, such as glass, boron, carbon, metals or ceramic materials. Mixing yarns of this type are characterized by a further increased cut resistance.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP97101675A 1996-02-15 1997-02-04 Fibres d'aramide résistant aux coupures, fils contenant ces fibres et leur utilisation Expired - Lifetime EP0790335B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19605511A DE19605511A1 (de) 1996-02-15 1996-02-15 Schnittresistente Aramidfasern, Garne enthaltend diese Aramidfasern und deren Verwendung
DE19605511 1996-02-15

Publications (2)

Publication Number Publication Date
EP0790335A1 true EP0790335A1 (fr) 1997-08-20
EP0790335B1 EP0790335B1 (fr) 2005-06-15

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EP97101675A Expired - Lifetime EP0790335B1 (fr) 1996-02-15 1997-02-04 Fibres d'aramide résistant aux coupures, fils contenant ces fibres et leur utilisation

Country Status (3)

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US (1) US5738940A (fr)
EP (1) EP0790335B1 (fr)
DE (2) DE19605511A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999017626A1 (fr) * 1997-10-08 1999-04-15 Hoechst Celanese Corporation Articles polymeres ayant une resistant aux coupures accrue
CN101611182B (zh) * 2006-12-15 2012-08-01 帝人高科技产品株式会社 含杂环芳族聚酰胺纤维及其制备方法以及由该纤维构成的布帛和经该纤维补强的纤维强化复合材料

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US6162538A (en) * 1992-11-24 2000-12-19 Clemson University Research Foundation Filled cut-resistant fibers
AU2652799A (en) * 1998-01-20 1999-08-02 Hna Holdings, Inc. Ballistic-resistant textile articles made from cut-resistant fibers
FR2789094B1 (fr) * 1999-02-03 2001-05-25 Speed France Fil de coupe ou fil de peche en matiere synthetique
DE60013977T2 (de) * 1999-07-29 2005-10-06 Sumitomo Chemical Co. Ltd. Hitzbeständiger blattformiger Katalysator und Verfahren zu seiner Herstellung
JP4831974B2 (ja) * 2005-01-27 2011-12-07 帝人テクノプロダクツ株式会社 防護衣料
US9334587B2 (en) 2005-02-11 2016-05-10 W. L. Gore & Associates, Inc. Fluoropolymer fiber composite bundle
US20060182962A1 (en) * 2005-02-11 2006-08-17 Bucher Richard A Fluoropolymer fiber composite bundle
WO2007004848A1 (fr) * 2005-07-06 2007-01-11 Kolon Industries, Inc Filament polyamide aromatique et procédé de fabrication idoine
US7559653B2 (en) * 2005-12-14 2009-07-14 Eastman Kodak Company Stereoscopic display apparatus using LCD panel
WO2008012925A1 (fr) * 2006-07-26 2008-01-31 Teijin Techno Products Limited Fibre à base de polyamide aromatique et son procédé de production et vêtement de protection utilisant ladite fibre à base de polyamide aromatique
JP7372004B2 (ja) 2017-04-03 2023-10-31 アビエント プロテクティブ マテリアルズ ビー． ブイ． 切断抵抗性である充填された長尺体
US11598027B2 (en) 2019-12-18 2023-03-07 Patrick Yarn Mills, Inc. Methods and systems for forming a composite yarn
KR102208801B1 (ko) * 2020-12-16 2021-01-28 김용건 고강력사 및 이를 이용한 장갑 제조방법

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US4004295A (en) 1975-12-30 1977-01-25 Byrnes Sr Robert M Protective glove constructed of flexible strands of metal wire and fiber yarn
JPS5598909A (en) 1979-01-24 1980-07-28 Takeshi Naito Fiber and sewn product
DE3007063A1 (de) 1979-02-26 1980-08-28 Teijin Ltd Aromatisches copolyamid und verfahren zu seiner herstellung
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EP0199090A2 (fr) 1985-03-23 1986-10-29 Hoechst Aktiengesellschaft Objets moulés en copolyamide aromatique et leur procédé de fabrication
EP0364892A2 (fr) 1988-10-18 1990-04-25 Hoechst Aktiengesellschaft Polyamides entièrement aromatiques, procédé pour leur préparation et objets moulés
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DE4411755A1 (de) * 1994-04-06 1995-10-12 Hoechst Ag Verfahren zur Herstellung von Fasern oder Filmen unter Verwendung spezieller Ausformlösungen, sowie die danach erhältlichen Fasern oder Filme
US5597649A (en) * 1995-11-16 1997-01-28 Hoechst Celanese Corp. Composite yarns having high cut resistance for severe service

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2328105A (en) 1940-12-28 1943-08-31 Louis J Strobino X-ray shield
DE2556883C2 (de) 1974-12-27 1981-11-26 Teijin Ltd., Osaka Aromatische Copolyamide und deren Verwendung zur Herstellung von Fasern, Fäden, Filmen und Folien
US4004295A (en) 1975-12-30 1977-01-25 Byrnes Sr Robert M Protective glove constructed of flexible strands of metal wire and fiber yarn
US4384449A (en) 1976-10-05 1983-05-24 Robert M. Byrnes, Sr. Protective gloves and the like and a yarn with flexible core wrapped with aramid fiber
US4470251A (en) 1978-03-30 1984-09-11 Bettcher Industries, Inc. Knittable yarn and safety apparel made therewith
JPS5598909A (en) 1979-01-24 1980-07-28 Takeshi Naito Fiber and sewn product
DE3007063A1 (de) 1979-02-26 1980-08-28 Teijin Ltd Aromatisches copolyamid und verfahren zu seiner herstellung
EP0199090A2 (fr) 1985-03-23 1986-10-29 Hoechst Aktiengesellschaft Objets moulés en copolyamide aromatique et leur procédé de fabrication
EP0364891A2 (fr) 1988-10-18 1990-04-25 Hoechst Aktiengesellschaft Polyamides entièrement aromatiques, procédé pour leur préparation et objets moulés
EP0364893A2 (fr) 1988-10-18 1990-04-25 Hoechst Aktiengesellschaft Polyamides entièrement aromatiques, procédé pour leur préparation et objets moulés
EP0364892A2 (fr) 1988-10-18 1990-04-25 Hoechst Aktiengesellschaft Polyamides entièrement aromatiques, procédé pour leur préparation et objets moulés
US5020161A (en) 1989-09-29 1991-06-04 E. I. Dupont De Nemours And Company Waterproof glove for protective coveralls
JPH03130413A (ja) 1989-10-17 1991-06-04 Teijin Ltd 芯鞘型複合磁性繊維及びそれを用いた磁性繊維集合体
EP0424860A2 (fr) 1989-10-25 1991-05-02 Hoechst Aktiengesellschaft Polyamides entièrement aromatiques, procédé de préparation et produits formés
EP0458343A1 (fr) 1990-05-25 1991-11-27 BETTCHER INDUSTRIES, INC. (a Delaware Corporation) Fil tricotable et vêtement de protection
EP0599231A1 (fr) 1992-11-24 1994-06-01 Hoechst Celanese Corporation Fibre chargée
US5296543A (en) * 1993-04-23 1994-03-22 E. I. Du Pont De Nemours And Company Aromatic polyamide compositions and fibers
EP0662534A1 (fr) 1994-01-06 1995-07-12 Hoechst Aktiengesellschaft Procédé pour la fabrication de structures façonnées à base de polyamides aromatiques et prémélange pour la fabrication de structures façonnées
WO1995031593A1 (fr) * 1994-05-16 1995-11-23 Hoechst Celanese Corporation Fibre pleine resistant aux coupures
WO1996041042A1 (fr) * 1995-06-07 1996-12-19 Hoechst Celanese Corporation Fibres thermoplastiques chargees resistantes a la coupure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999017626A1 (fr) * 1997-10-08 1999-04-15 Hoechst Celanese Corporation Articles polymeres ayant une resistant aux coupures accrue
US6080474A (en) * 1997-10-08 2000-06-27 Hoechst Celanese Corporation Polymeric articles having improved cut-resistance
CN101611182B (zh) * 2006-12-15 2012-08-01 帝人高科技产品株式会社 含杂环芳族聚酰胺纤维及其制备方法以及由该纤维构成的布帛和经该纤维补强的纤维强化复合材料

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EP0790335B1 (fr) 2005-06-15
US5738940A (en) 1998-04-14
DE59712341D1 (de) 2005-07-21
DE19605511A1 (de) 1997-08-21

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