EP0091547B2 - Fibre polyoléfinique à chaîne allongée revêtue - Google Patents

Fibre polyoléfinique à chaîne allongée revêtue Download PDF

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Publication number
EP0091547B2
EP0091547B2 EP19830101727 EP83101727A EP0091547B2 EP 0091547 B2 EP0091547 B2 EP 0091547B2 EP 19830101727 EP19830101727 EP 19830101727 EP 83101727 A EP83101727 A EP 83101727A EP 0091547 B2 EP0091547 B2 EP 0091547B2
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EP
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Prior art keywords
fiber
dtex
den
coated
fibers
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EP19830101727
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German (de)
English (en)
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EP0091547B1 (fr
EP0091547A1 (fr
Inventor
Gary Allan Harpell
Sheldon Kavesh
Igor Palley
Dusan Ciril Prevorsek
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Allied Corp
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Allied Corp
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated

Definitions

  • Extended chain polyethylene and extended chain polypropylene fibers of extremely high tenacity and modulus values are known materials, having been described by various publications of Professor Pennings and co-workers, Smith and Lemstra, and in certain copending commonly assigned patent applications of Kavesh et al
  • These mechanical properties are due, at least in part, to the high degree of crystallinity and orientation imparted to the fiber by the production processes, which include either drawing an ultrahigh molecular weight polyolefin from a supersaturated solution or spinning a hot solution of the ultrahigh molecular weight polyolefin through a dye to form a gel fiber.
  • Subsequent processing, including especially a stretching step impart a high crystallinity and orientation to the polylolefin.
  • Asecond disadvantageous property of the extended chain polyolefin fibers is that their crystallinity causes these fibers to have poor adhesion to most matrix materials. This tends to limit the usefulness of these fibers in composite structures.
  • Polyolefin fibers coated with polymers are known. See, e.g., DE-A-2,029,754.
  • coated fibers may be used alone under appropriate conditions of temperature and pressures to produce simple composite structures, which single composite structures are the subject of an application "Composite containing polyolefin fiber and polymer matrix" (EP-A-89,502, published September 28, 1983) commonly assigned.
  • the present invention includes a polyolefin fiber coated with a polymer characterized in that the polyolefin fiber comprises:
  • the present invention further includes a composite structure comprising a network of the above-described coated fibers in a matrix which is not a material with ethylene or propylene crystallinity.
  • the coated fiber of the present invention (which forms a part of the composite structure of the present invention) includes an extended chain polyolefin fiber, which may be ultrahigh molecular weight polyethylene or ultrahigh molecular weight polypropylene.
  • Suitable polyethylene fibers are made of polyethylene having a weight average molecular weight at least 500,000, preferably at least 1 million and more preferably between about 2 million and about 5 million.
  • the fiber may be grown by solution techniques, is described in more detail in U.S. Application Serial No.
  • polyolefin fiber may also be produced by processes involving the spinning of polyolefin solutions to form a gel structure upon cooling, and especially in such a process as described in EP-A-64,167 (corresponding to U.S. Application Serial No. 259,266, of Kavesh, et al, filed April 30, 1981, a continuation-in-part, thereof, U.S.S.N.
  • the polyethylene fibers used have tenacity values of at least 14.5 g/den (13.1 g/dtex), preferably at least about 20 g/den (18 g/dtex), more preferably at least about 25 or 30 g/den (22.5 or 27 g/dtex) and most preferably at least about 40 g/den (36 g/dtex).
  • the preferred tensile modulus values for the polyethylene fibers are at least 300 g/den (270 g/dtex), preferably at least about 500 g/den (450 g/dtex), more preferably at least 750 or 1,000 g/den (675.1 or 900.1 g/dtex) and most preferably at least about 1,500 g/den (1350 g/dtex).
  • the tenacity and modulus values are directly related and rise together in a relatively linear fashion for most of the processes used, but it is contemplated that for certain applications fibers selected for particularly high tenacities, without regard to modulus, or with particularly high modulus, without regard to tenacity, such as are produced by melt spinning, may be used.
  • the elongation value is particularly important.
  • coated fibers and composites used in ballistic applications as described in greater detail in an application of the same inventors as the present application, entitled "Ballistic Article Containing Polyolefin Fiber", now US-A-4,403,012 and commonly assigned, both tenacity and modulus values are extremely important.
  • the melting point of the polyolefin fiber is not a particularly critical value in the present invention, but the melting point is generally above about 138°C (e.g. 145-155°C) for polyethylene fibers and above about 168°C (e.g. 170-173°C) for polypropylene fibers.
  • Other properties which are not critical but may have importance for particular applications, include work to break values (as measured by ANSI/ASTM D-2256), creep values (as measured, for example, under 10% of breaking load for 50 days at room temperature), elongation to break, elongation at yield, UV stability, oxidative stability, thermal stability and hydrolytic stability. It is expected that most, if not all, of these other properties obtained by the polyolefin fiber will correspond to similar, linearly dependent or enhanced values for the coated polyolefin fiber.
  • the polyethylene fiber used in the present invention may be either a monofilament or a multifilament, with multifilaments of from 2-500 or more strands being contemplated, and with arrangements varying from totally parallel filaments, to wound filaments, to braided and twisted strands also being contemplated. In the case of multifilaments of other than parallel arrangement, it is contemplated that the winding or other rearrangement of the filament may occur before, during or after application of the coating.
  • coated fibers of the present invention may either be extremely long fibers (referred to sometimes as being of substantially indefinite length), of relatively short pieces, or even of extremely short pieces as, for example, in resins reinforced by short fibers (e.g., bulk molding compounds or sheet molding compounds).
  • extended chain polypropylene fibers may be used with generally the same geometries, molecular weights, fiber-forming processes and filament structure as the extended chain polyethylene fibers.
  • the major difference resides in the properties of the fiber, with polypropylene fibers of tenacity at least 8 g/den (7.2 g/dtex), and preferably at least about 15 g/den (13.5 g/dtex), and of tensile modulus at least about .160 g/den (144 g/dtex), preferably at least about 200 g/den (180 g/dtex), being suitable.
  • the extended chain polypropylene fibers will have a main melting point significantly higher than the corresponding polyethylene fibers, although the melting point is not a critical feature of the polypropylene fiber.
  • Representative main melting points for extended chain polypropylene fibers are from about 168 to about 180°C, or typically between about 168 and about 173°C, preferably at least about 170°C.
  • Suitable coating materials for the coated fibers of the present invention include polyethylene of various forms, polypropylene of various forms, ethylene copolymers of various forms having at least 10% ethylene crystallinity, propylene copolymers of various forms having at least 10% propylene crystallinity and various ethylene-propylene copolymers.
  • Polyethylene coatings may be either low density (having, for example, about 0.90-0.94 specific gravity), high density (having, for example, about 0.94-0.98 specific gravity), with various amounts of branching, linearity, relatively minor comonomers as found in materials generally labeled as "polyethylene", molecular weights, melt viscosities, and other values.
  • Suitable polypropylene coatings include isotactic, atactic and syndiotactic polypropylene. The atactic or amorphous polypropylene is generally less preferred, however, compared to the two crystalline forms.
  • Suitable ethylene copolymer coatings include copolymers of ethylene with one or more other olefinically unsaturated monomers from several broad classes.
  • suitable propylene copolymers include copolymers of propylene with one or more olefinically unsaturated monomers from several broad classes: 1-monoolefins, olefins containing one terminal polymerizable double bond and one or more internal double bond or bonds.
  • the ethylene or propylene content of the copolymers is preferably higher than that minimum necessary to achieve about 10 volume percent ethylene or propylene crystallinity.
  • the ethylene or propylene crystallinity be at least about 25 volume percent, more preferably at least about 50 volume percent, and most preferably at least about 70 volume percent.
  • the proportion of coating compared to fiber may vary over a wide range depending upon the application for which the coated fibers are to be used.
  • a general broad range is from 0.1 to 200% coating, by weight of fiber.
  • a preferred coating amount is between about 10 and about 50%, by weight of fiber.
  • the same or lower proportion of coating may be used when the coated fiber is to be used to form a simple composite in which the coating is fused into a continuous matrix.
  • Higher amounts of coating may be preferred for other applications such as composites containing other fibers (e.g glass fibers) and/or fillers, in which coating amounts of 50-200%, 75-150% and 75-100% are preferred, more preferred and most preferred.
  • the coating may be applied to the fiber in a variety of ways.
  • One method is to apply the neat resin of the coating material to the stretched high modulus fibers either as a liquid, a sticky solid or particles in suspension or as a fluidized bed.
  • the coating may be applied as a solution or emulsion in a suitable solvent which does not adversely affect the properties of the fiber at the temperature of application.
  • any solvent capable of dissolving or dispersing the coating polymer may be used, preferred groups of solvents include paraffin oils, aromatic solvents or hydrocarbon solvents, with illustrative specific solvents including paraffin oil, xylene, toluene and octane.
  • the techniques used to dissolve or disperse the coating polymers in the solvents will be those conventionally used for the coating of similar polymeric materials on a variety of substrates.
  • the fiber may then be stretched at elevated temperatures to produce the coated fibers.
  • the extruded gel fiber may be passed through a solution of the appropriate coating polymer (solvent may be paraffin oil, aromatic or aliphatic solvent) under conditions to attain the desired coating. Crystallization of the high molecularweight polyethylene in the gel fiber may or may not have taken place before the fiber passes into the cooling solution. Alternatively, the fiber may be extruded into a fluidized bed of the appropriate polymeric powder.
  • fillers such as carbon black, calcium carbonate, silica or barium ferrite may also be incorporated to attain desired physical properties, e.g. incorporation of carbon black to obtain UV, protection and/or enhanced electrical conductivity.
  • the coating may be applied to a precursor material of the final fiber.
  • the desired and preferred tenacity, modulus and other properties of the fiber should be judged by continuing the manipulative process on the fiber precursor in a manner corresponding to that employed in the coated fiber precursor.
  • the coating is applied to the xerogel fiber described in EP-A-64,167 and the corresponding U.S. Applications of Kavesh et al, and the coated xerogel fiber is then stretched under defined temperature and stretch ratio conditions, then the fiber tenacity and fiber modulus values would be measured on uncoated xerogel fiberwhich is similarly stretched.
  • coated fibers of the present invention may be further processed for use in a variety of applications such as preparation of composites using coated fibers alone, weaving, felts, fabrics and non-woven and knitted articles.
  • coated fibers of the present invention may be used to form the complex composite structures of the present invention.
  • Such complex composites contain the coated fibers (either monofilament or multifilament) described above, formed into a network of conventional type, such as completely parallel fibers, layers of parallel fibers located between layers in a variety of ways, randomly oriented lengths of fibers (including felts) and other arrangements.
  • the complex composites include a matrix different from the coating material which may be a thermosetting polymeric material, a thermoplastic polymeric material, an elastomeric polymeric material or even various non-polymeric materials.
  • Suitable matrices include thermoset polymers such as epoxies, unsaturated polyesters, polyurethanes, polyfunctional allyl polymers (e.g. diallyl phthalate), urea-formaldehyde polymers, phenol-formaldehyde polymers and vinyl ester resins; thermoplastic matrices such as poly-1-butene, polystyrene, styrene copolymers, polyvinyl chloride and ABS resin (it will be appreciated that polyethylene, polypropylene, ethylene copolymers and propylene copolymers, as matrices, are covered in EP-A-89,502; elastomers matrices such as polybutadiene, butadiene copolymers, thermoplastic elastomers (e.g.
  • Such complex composite structures have special utility in ballistic applications, boat hulls, motorcycle helmets, road surfacing, building constructions, films, hoses and belts.
  • Composite structures may be prepared using chopped coated fiber of this invention alone (simple composites) or together with other thermoplastics and thermoset matrices (called complex composites and described more fully herein).
  • other materials may be present in the complex composite, including lubricants, fillers, adhesion agents, other fiber materials (e.g. aramids, boron fibers, glass fibers, glass microballoons, graphite fibers and mineral fibers such as mica, woolastonite and asbestos) in various regular or irregular geometric arrangements.
  • the coating should be selected for good adhesion with the matrix material.
  • adhesion can be improved by using ethylene copolymers of propylene copolymers having comonomers with similar ionic character, aromatic character or other properties of the matrix.
  • relatively ionic monomers such acrylic acid, vinyl acetate or methacrylic acid will, in general, improve the adhesion of the coated fiber to the epoxy matrix compared to the adhesion of the corresponding uncoated fiber with the same epoxy matrix.
  • some preferred comonomers in the coating include acrylic acid, 1,4-hexadiene, vinyl alcohol and unreacted free radically polymerizable monomers (e.g. acrylates).
  • preferred coatings include hydroxyl-containing polyethylene copolymers such as ethylene-vinyl alcohol copolymers.
  • hydroxyl-containing polyethylene copolymers such as ethylene-vinyl alcohol copolymers.
  • suitable thermoplastic matrices and corresponding representative preferred comonomers for the coating material are indicated in Table 1 below.
  • the properties of these complex composites will generally include various advantageous properties derived from the coated fiber, and especially for the extended chain polyolefin fiber component of the coated fiber, including especially tenacity and modulus, but in some instances also including dimensional stability, low water absorption and chemical stability.
  • the complex composites may also have advantageous properties derived from the matrix material including, for example, high heat distortion temperature, appropriate flexibility or stiffness and abrasion resistance.
  • the coating component generally does not contribute substantially to the mechanical or other properties of the composite except insofar as it improves the inherent properties of the extended chain polyolefin as described above in connection with the novel coated fiber, e.g. by improving the transverse strength of a multifilament fiber.
  • the proportion of coated fiber(orforthat matter, extended chain polyolefin fiber) in the composite is not critical, but may have preferred values for various applications.
  • the coated fibers and complex composite structures of the present invention may be formed into a variety of articles.
  • vests may be made containing either knitted or woven or non-woven fabric of the present coated fiber, relatively rigid portions of the composite of the present invention, or a combination of these.
  • Helmets may be fabricated employing the complex composites of the present invention using a thermosetting matrix.
  • Shielding for helicopters, tanks and other articles where ballistic-resistance articles are desired may also be formed out of either the coated fiber or complex composite of the present invention, with the matrix material especially being selected based upon the desired physical properties of the shielding material.
  • Such articles are described in more detail in US-A-4,403,012 entitled "Ballistic Article Containing Polyolefin Fiber", of the present inventors, commonly assigned.
  • complex composites of the present invention may be formed into a variety of conventional geometric arrangements.
  • the polyethylene/ethylene copolymer coatings may be crosslinked by crosslinking techniques known in the art such as the use of. peroxides, sulfur or radiation cure systems, or may be reacted with polyfunctional acid chlorides or isocyanates in order to obtain a crosslinked coating on the high modulus fibers.
  • the filaments were stretched in a one meter long tube at 145°C at a feed roll speed of 25 cm/min to a stretch ratio of 19:1 to produce a 625 den (562.6 dtex) yarn having a tenacity of 19 g/den (17.1 g/dtex), a modulus of 732 g/den (659 g/dtex) and an elongation to break of 4.4%. These fibers were used in Example 2.
  • a similar fiber preparation (but as a monofilament) involved dissolving the same polymer to a 5 weight % solution at 200°C and extruding through a single two millimeter diameter die to produce a gel fiber at 598 cm/min.
  • the extracted and dried fiber was stretched in the one meter long tube at 130°C at a stretch ratio of 19:1 to produce a 65 den (58.5 dtex) fiber having a tenacity of 14.5 g/den (13.1 g/dtex), a modulus of 366 g/den (329 g/dtex) and an ultimate elongation of 6%.
  • This monofilament fiber was used in Example 3.
  • a similar multifilament fiber employed an 181V polyethylene dissolved to 6 weight % in paraffin oil at 220°C. Extruding the solution through a 16 hole die (with 0.76 mm hole diameters) produced gel fiber at 3.08 m/min. The wet gel fiber was stretched at 100°C to a stretch ratio of 11: 1, extracted and dried.
  • the 198 den (178.2 dtex) yarn produced had a tenacity of 25 g/den (22.5 g/dtex), a modulus of 971 g/den (874 g/dtex) and an elongation of 4.5% and was used in Example 4.
  • a high molecular weight linear polyethylene (intrinsic viscosity of 17.5 in decalin at 135°C) was dissolved in paraffin oil at 220°C to produce a 6 weight % solution. This solution was extruded through a sixteen-hole die (hole diameter 1 mm) at the rate of 3.2 m/min. The oil was extracted from the fiber with trichlorotrifluoroethane and then the fiber was subsequently dried.
  • the fiber increased in weight by 19.5%.
  • the coated fiber was stretched to a stretch ratio of 20:1 in a 100 cm long tube heated to 140°C, using a feed roll speed of 25 cm/min to produce a single filament of 208 den (187.2 dtex).
  • Tensile testing of the coated fiber showed a tensile strength of 19.9 g/den (17.9 g/dtex) and a modulus of 728 g/den (655.3 g/dtex).
  • Uncoated fiber was stretched in an identical manner to produce a multifilament yarn. Tensile testing of this uncoated fiber showed a tensile strength (tenacity) of 18.9 g/den (17 g/dtex) and a modulus of 637 g/den (573.4 g/dtex).
  • the coated fiber has a higher tensile strength and modulus in spite of the fact that 20% of the fiber weight consists of low density polyethylene coating.
  • the coated fiber was then tied around a small post, making five knots (each knot drawn down on the previous knot). Examination under an optical microscope indicated that no fibrillation occurred, a result particularly significance for suture applications.
  • Single 13 den (11.7 dtex) ECPE filaments having a modulus of 732 g/den (658.9 g/dtex) and a tensile strength of 19 g/den (17.1 g/dtex) were dipped into a solution of ethylene-acrylic acid copolymer (Dow EAA-455, containing 0.932 milliequivalents acrylic acid/g polymer) in toluene under conditions shown in Table 1.
  • the fiber was removed, allowed to dry in air and then subsequently embedded in an epoxy resin, Devkon 5 minute epoxy manufactured by Devkon Corporation, to a depth of 5 mm.
  • the resin was cured at room temperature for one hour, and then heated in an air-circulating oven for 30 minutes at 100°C.
  • An extended chain polyethylene fiber of 14.5 g/den ( 13.1 g/dtex) tenacity and 366 g/den (329.4 g/dtex) modulus prepared by stretching a xerogel at a 19:1 stretch ratio at 130°C was cut into approximately 40 cm pieces. Some of the pieces were tied into knots and thereupon fibrillated extensively, with examination under an optical microscope at 50x magnification showing microfibrillae approximately 8-9 ⁇ m in diameter.
  • An extended claim polyethylene fiber of 25 g/den (22.5 g/dtex) tenacity and 971 g/den (874 g/dtex) modulus was coated in one of two treatment regimes with various polymers in xylene solution (at 60 or 120 g/I concentration). The first regime was to dip the fiber in the solution for two minutes and then dry. The second regime was to dip for 30 seconds, dry in air for three minutes and then (for four repetitions) dip for two seconds and dry for three minutes. All of the coated fibers were then placed in a rectangular parallelopiped mold of an epoxy resin (the same resin as Example 2) which was then cured at 25°C for 24 hours.
  • an epoxy resin the same resin as Example 2
  • the fiber passed through a trichlorotrifluoroethane and then dried, giving a fiber weight of 8.06 g. This fiber was then stretched in a 100°C tube at 140°C, using a feedroll speed of 25 cm/min.
  • the resultant fiber had a denier of 234 (210.6 g/dtex), tenacity of 20.2 g/den (18.2 g/dtex), modulus of 696 g/den (626.5 g/dtex) and ultimate elongation of 3.9%.
  • Adhesion to epoxy matrix was determined in the same manner as in Example 4. Force required to pull fiber out of the matrix was 1.33 N (0.30 Ib) and shear stress was 2340 kPa (340 ib/in).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Claims (10)

1. Une fibre polyoléfinique revêtue d'un polymère caractérisée en ce que la fibre polyoléfinique revêtue comprend :
(a) une fibre monofilament ou multifilament de polyéthylène ou de polypropylène de poids moléculaire pondéral moyen d'au moins 500.000, ayant, dans le cas du polyéthylène, une ténacité d'au moins 14,5 g/den (13,1 g/tex) et un module d'élasticité en traction d'au moins 300 g/den (270 g/dtex) et, dans le cas du polypropylène, une ténacité d'au moins 8 g/den (7,2 g/dtex) et un module d'élasticité en traction d'au moins 160 g/den (144 g/dtex), et
(b) un revêtement sur le monofilament et sur au moins une portion des filaments du multifilament contenant un polymère ayant au moins 10 % en volume d'éthylène ou la cristallinité du propylène, ledit revêtement étant présent en quantité comprise entre 0,1% et 200% en poids de la fibre.
2. La fibre polyoléfinique revêtue de la revendication 1 dans laquelle ladite fibre est un multifilament de polyéthylène.
3. La fibre polyoléfinique revêtue de la revendication 1 ou 2 dans laquelle ledit polyéthylène a un poids moléculaire pondéral moyen d'au moins 1.000.000.
4. La fibre polyoléfinique revêtue de la revendication 1 ou 2 ou 3 dans laquelle ledit polyéthylène a une ténacité d'au moins 30 g/den (27 g/dtex) et un module d'élasticité en traction d'au moins 1000 g/den (900,1 g/dtex).
5. La fibre polyoléfinique revêtue de la revendication 1 ou 2 ou 3 ou 4 dans laquelle ledit revêtement est du polyéthylène.
6. La fibre revêtue de la revendication 1 ou 2 ou 3 ou 4 dans laquelle ledit revêtement est un copolymère de l'éthylène.
7. La fibre polyoléfinique revêtue de la revendication 6 dans laquelle ledit copolymère de l'éthylène a au moins 25% en volume de la cristallinité de l'éthylene.
8. Un composite comprenant un réseau de la fibre polyoléfinigue revêtue de l'une quelconque des revendications précédentes et une matrice différente du matériau de revêtement.
9. Le composite de la revendication 8 dans lequel ladite matrice est un polymère thermodurcissable.
10. Un composite comprenant un réseau de la fibre revêtue de l'une quelconque des revendications 1 à 7 et une matrice époxy.
EP19830101727 1982-03-19 1983-02-23 Fibre polyoléfinique à chaîne allongée revêtue Expired - Lifetime EP0091547B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35997682A 1982-03-19 1982-03-19
US359976 1994-12-20

Publications (3)

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EP0091547A1 EP0091547A1 (fr) 1983-10-19
EP0091547B1 EP0091547B1 (fr) 1986-08-06
EP0091547B2 true EP0091547B2 (fr) 1993-02-24

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EP19830101727 Expired - Lifetime EP0091547B2 (fr) 1982-03-19 1983-02-23 Fibre polyoléfinique à chaîne allongée revêtue

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EP (1) EP0091547B2 (fr)
JP (1) JP2604347B2 (fr)
CA (1) CA1198862A (fr)
DE (1) DE3365055D1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60162869A (ja) * 1984-01-31 1985-08-24 東洋紡績株式会社 高強力防水布
US4663101A (en) * 1985-01-11 1987-05-05 Allied Corporation Shaped polyethylene articles of intermediate molecular weight and high modulus
JPH06102847B2 (ja) * 1985-05-31 1994-12-14 三井石油化学工業株式会社 プラスチツクワイヤ−及びその製造方法
JPS61282417A (ja) * 1985-06-05 1986-12-12 Toray Ind Inc ポリエチレンマルチフイラメントヤ−ン
EP0205960B1 (fr) * 1985-06-17 1990-10-24 AlliedSignal Inc. Fibre de polyoléfine à haute ténacité, à faible retrait, à module très élevé et à très bas fluage et ayant une bonne rétention de résistance à haute température ainsi que sa méthode de fabrication
GB9200583D0 (en) * 1992-01-13 1992-03-11 Hutton Geoffrey H Improvements in or relating to a moisture sensor
US6168855B1 (en) 1997-12-01 2001-01-02 Polyeitan Composites Ltd. Polyolefin composites for printed circuit board and antenna base material
US5972484A (en) * 1997-12-01 1999-10-26 Polyeitan Composites Ltd. Ultrahigh molecular weight polyethylene composite for printed circuit board and antenna base material
JP2001303467A (ja) * 2000-04-28 2001-10-31 Yotsuami:Kk 擬似モノフィラメント
DE102005051550A1 (de) * 2005-10-27 2007-05-03 Fibertex A/S Superhydrophobe Beschichtung eines Polymervlieses, insbesondere eines Polypropylenvlieses
WO2011154383A1 (fr) * 2010-06-08 2011-12-15 Dsm Ip Assets B.V. Corde en hmpe protégée
EA030165B1 (ru) * 2012-03-20 2018-06-29 ДСМ АйПи АССЕТС Б.В. Гель-формованное волокно, способ его получения и изделие
US10132006B2 (en) * 2012-07-27 2018-11-20 Honeywell International Inc. UHMWPE fiber and method to produce
KR20150096412A (ko) * 2012-12-20 2015-08-24 디에스엠 아이피 어셋츠 비.브이. 폴리올레핀 얀 및 제조 방법
WO2017060469A1 (fr) 2015-10-09 2017-04-13 Dsm Ip Assets B.V. Feuille composite à base de fibres haute performance
US20190040556A1 (en) * 2015-10-09 2019-02-07 Dsm Ip Assets B.V. Composite lengthy body
CN110709545B (zh) 2017-04-03 2022-06-24 帝斯曼知识产权资产管理有限公司 耐切割的经填充的伸长体
EP3606983A1 (fr) 2017-04-03 2020-02-12 DSM IP Assets B.V. Feuille hybride à fibres haute performance
WO2018184821A1 (fr) 2017-04-06 2018-10-11 Dsm Ip Assets B.V. Feuille composite à base de fibres haute performance

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1124464B (de) * 1958-04-21 1962-03-01 Ruhrchemie Ag Verfahren zur Impraegnierung von Textilien mit in Loesungsmittel geloestem Polyaethylen
DE1097403B (de) * 1958-04-25 1961-01-19 Ruhrchemie Ag Verfahren zur Impraegnierung von Textilfasern oder Textilien mit Polyaethylen und bzw. oder Polypropylen
DE1150650B (de) * 1958-10-07 1963-06-27 Ruhrchemie Ag Verfahren zur wasser- und schmutzabweisenden Ausruestung von Textilien mit Niederdruckpolyolefinen
NL281307A (fr) * 1962-07-04
NL6501260A (fr) * 1964-02-13 1965-08-16
GB1299725A (en) * 1969-06-17 1972-12-13 Dunlop Co Ltd Improvements relating to the bonding of polyalkenes to elastomers
JPS4975819A (fr) * 1972-11-29 1974-07-22
NL177840C (nl) * 1979-02-08 1989-10-16 Stamicarbon Werkwijze voor het vervaardigen van een polyetheendraad.

Also Published As

Publication number Publication date
EP0091547B1 (fr) 1986-08-06
CA1198862A (fr) 1986-01-07
JPS58169521A (ja) 1983-10-06
DE3365055D1 (en) 1986-09-11
JP2604347B2 (ja) 1997-04-30
EP0091547A1 (fr) 1983-10-19

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