EP1043733B1 - Cable autoextinguible à faible fumée et composition résistant aux flammes utilisée dans ce cable - Google Patents

Cable autoextinguible à faible fumée et composition résistant aux flammes utilisée dans ce cable Download PDF

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Publication number
EP1043733B1
EP1043733B1 EP20000201096 EP00201096A EP1043733B1 EP 1043733 B1 EP1043733 B1 EP 1043733B1 EP 20000201096 EP20000201096 EP 20000201096 EP 00201096 A EP00201096 A EP 00201096A EP 1043733 B1 EP1043733 B1 EP 1043733B1
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Prior art keywords
flame
retardant
weight
cable according
inorganic filler
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English (en)
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EP1043733A1 (fr
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Luca Castellani
Diego Tirelli
Franco Peruzzotti
Enrico Albizzati
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Prysmian SpA
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Pirelli and C SpA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame

Definitions

  • the present invention relates to cables, in particular electrical cables for low-voltage power transmission or for telecommunications, or alternatively for data transmission, as well as mixed power/telecommunications cables, which have self-extinguishing properties and produce a low level of fumes, and to flame-retardant compositions used therein.
  • Self-extinguishing cables are generally produced by extruding over the core of the cable a flame-retardant coating consisting of a polymer composition to which flame-retardant properties have been imparted by the addition of a suitable flame-retardant filler of inorganic type, generally a hydroxide, a hydrated oxide or a hydrated salt of a metal, in particular of magnesium or aluminium.
  • the polymer base generally consists of copolymers of ethylene and ethylenically unsaturated esters, in particular ethylene/vinyl acetate or ethylene/ethyl acrylate copolymers, optionally mixed with polyolefins (see for example patents US-4,673,620 and EP-530,940).
  • Patent application WO 96/23311 describes a low-voltage, high-current cable in which the inner sheath, the insulating coating and the outer sheath consist of the same black-coloured base material and the insulating layer contains a longitudinal coloured stripe for identification purposes. The use of this material for the various layers would not require the separation of the various components in a recycling process.
  • the base material can, depending on the maximum working temperature of the cable, be a polyethylene with a density of between 0.92 and 0.94 g/cm 3 and a Shore D hardness ⁇ 42, or a thermoplastic elastomer based on polypropylene, for example polypropylene modified with an ethylene/propylene copolymer or a polypropylene-based reactor mixture wherein the elastomeric phase content is greater than 25%.
  • the amount of flame-retardant filler required is high, generally greater than 30% by weight, usually more than 50% by weight, relative to the total weight of the flame-retardant coating.
  • Such a high level of inorganic filler leads to a deterioration in processability and in mechanical properties of the flame-retardant composition, in particular as regards elongation at break and stress at break.
  • the Applicant has found that, in order to obtain a self-extinguishing cable which satisfies the specifications required by the market, it is necessary to have available a polymer base which is capable of incorporating large amounts of flame-retardant filler and, at the same time, of maintaining good mechanical properties, in particular as regards elongation at break and stress at break.
  • the Applicant has now found that it is possible to produce self-extinguishing cables with high flame resistance and excellent mechanical properties by using as flame-retardant coating a mixture of a flame-retardant inorganic filler and a polymer base comprising a heterophase copolymer having an elastomeric phase based on ethylene copolymerized with an ⁇ -olefin and a thermoplastic phase based on propylene, wherein the elastomeric phase is at least 45% by weight relative to the total weight of the heterophase copolymer and this copolymer is substantially devoid of crystallinity deriving from polyethylene sequences.
  • the present invention thus relates to a cable comprising at least one conductor and at least one flame-retardant coating layer based on a polymer material and a flame-retardant inorganic filler, characterized in that the said polymer material comprises a heterophase copolymer having an elastomeric phase based on ethylene copolymerized with an ⁇ -olefin and a thermoplastic phase based on propylene, the said elastomeric phase in the said heterophase copolymer being at least 45% by weight relative to the total weight of the heterophase copolymer, the said heterophase copolymer being substantially devoid of crystallinity deriving from polyethylene sequences.
  • the said polymer material comprises a heterophase copolymer having an elastomeric phase based on ethylene copolymerized with an ⁇ -olefin and a thermoplastic phase based on propylene, the said elastomeric phase in the said heterophase copolymer being at least 45% by weight
  • the cable has an electrically insulating inner layer and the flame-retardant coating is placed outside the said insulating inner layer.
  • the flame-retardant coating is placed directly on the conductor.
  • the present invention relates to a flame-retardant composition based on a polymer material and a flame-retardant inorganic filler, characterized in that the said polymer material comprises a heterophase copolymer having an elastomeric phase based on ethylene copolymerized with an ⁇ -olefin and a thermoplastic phase based on propylene, the said elastomeric phase in the said heterophase copolymer being at least 45% by weight relative to the total weight of the heterophase copolymer, the said heterophase copolymer being substantially devoid of crystallinity deriving from polyethylene sequences.
  • the said polymer material comprises a heterophase copolymer having an elastomeric phase based on ethylene copolymerized with an ⁇ -olefin and a thermoplastic phase based on propylene, the said elastomeric phase in the said heterophase copolymer being at least 45% by weight relative to the total weight of the heterophase copolymer,
  • the use of a heterophase copolymer as described above as a base polymer material makes it possible to obtain self-extinguishing cables which have a flame-retardant coating with an elongation at break (E.B.) value, measured according to CEI standard 20-34 ⁇ 5.1, of at least 100%, preferably of at least 150%, and a stress at break (S.B.) value, measured according to CEI standard 20-34 ⁇ 5.1, of at least 6 MPa, preferably of at least 9 MPa.
  • E.B. elongation at break
  • S.B. stress at break
  • heterophase copolymer having an elastomeric phase based on ethylene copolymerized with an ⁇ -olefin and a thermoplastic phase based on propylene means a thermoplastic elastomer obtained by sequential copolymerization of: (a) propylene, optionally containing small amounts of at least one olefin comonomer selected from ethylene and ⁇ -olefins other than propylene; and then of: (b) a mixture of ethylene with an ⁇ -olefin, in particular propylene and, optionally, with small amounts of a diene.
  • This class of products is also commonly referred to as "thermoplastic reactor elastomers”.
  • heterophase copolymer substantially devoid of crystallinity deriving from polyethylene sequences means that the heterophase copolymer, subjected to differential scanning calorimetry (DSC) analysis, shows no appreciable melting peaks attributable to a crystalline polyethylene phase, i.e. to (CH 2 ) n sequences of the crystalline type.
  • DSC differential scanning calorimetry
  • the substantial absence of crystallinity due to polyethylene sequences can be ascertained by extracting the elastomeric (amorphous) phase using suitable organic solvents (for example refluxing xylene at 135°C for 20 min.) and analysing the residue formed by the crystalline phase, for example by X-ray defractometry.
  • suitable organic solvents for example refluxing xylene at 135°C for 20 min.
  • analysing the residue formed by the crystalline phase for example by X-ray defractometry.
  • the amount of elastomeric phase present in the heterophase copolymer can be determined according to known techniques, for example by extracting the elastomeric (amorphous) phase with a suitable organic solvent (in particular refluxing xylene at 135°C for 20 min.): the amount of elastomeric phase is calculated as the difference between the initial weight of the sample and the weight of the dried residue.
  • a suitable organic solvent in particular refluxing xylene at 135°C for 20 min.
  • the ⁇ -olefin can be selected, for example, from: propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene and the like.
  • the preparation of the heterophase copolymers according to the present invention is usually carried out by copolymerization of the corresponding monomers in the presence of Ziegler-Natta catalysts based on halogenated titanium compounds supported on magnesium chloride. Details regarding the preparation of these copolymers are given, for example, in EP-A-0,400,333, EP-A-0,373,660 and US-A-5,286,564.
  • the thermoplastic phase of the heterophase copolymer mainly produced during the above mentioned step (a) of the process, consists of a propylene homopolymer or a crystalline copolymer of propylene with an olefin comonomer selected from ethylene and ⁇ -olefins other than propylene.
  • the olefin comonomer is preferably ethylene.
  • the amount of olefin comonomer is preferably less than 10 mol% relative to the total number of moles of the thermoplastic phase.
  • the elastomeric phase of the heterophase copolymer is at least 45% by weight, preferably at least 55% by weight, and even more preferably at least 60% by weight, relative to the total weight of the heterophase copolymer, and consists of an elastomeric copolymer of ethylene with an ⁇ -olefin, and optionally with a diene.
  • the said ⁇ -olefin is preferably propylene.
  • the diene optionally present as comonomer generally contains from 4 to 20 carbon atoms and is preferably selected from: linear, conjugated or non-conjugated diolefins, for example 1,3-butadiene, 1,4-hexadiene, 1,6-octadiene and the like; monocyclic or polycyclic dienes, for example 1,4-cyclohexadiene, 5-ethylidene-2-norbomene, 5-methylene-2-norbornene and the like.
  • the composition of the elastomeric phase is generally as follows: from 15 to 85 mol% of ethylene, from 15 to 85 mol% of ⁇ -olefin, from 0 to 5 mol% of a diene.
  • the elastomeric phase consists of an elastomeric copolymer of ethylene and propylene which is rich in propylene units, in particular having the following composition: from 15 to 50% by weight, more preferably from 20 to 40% by weight, of ethylene, and from 50 to 85% by weight, more preferably from 60 to 80% by weight, of propylene, relative to the weight of the elastomeric phase.
  • the amount of propylene units in the elastomeric phase can be determined by extracting the elastomeric (amorphous) phase using a suitable organic solvent (for example refluxing xylene at 135°C for 20 min.), followed by analysing the dried extract according to known techniques, for example by infrared (IR) spectroscopy.
  • a suitable organic solvent for example refluxing xylene at 135°C for 20 min.
  • Heterophase copolymers with structural properties and related physicochemical properties according to the present invention can be found on the market among the large class of so-called "polypropylene reactor mixtures" sold, for example, by Montell under the brand name Hifax®.
  • Flame-retardant inorganic fillers which can generally be used are hydroxides, hydrated oxides, salts or hydrated salts of metals, in particular of calcium, aluminium or magnesium, such as, for example: magnesium hydroxide, aluminium hydroxide, alumina trihydrate, magnesium carbonate hydrate, magnesium carbonate, magnesium calcium carbonate hydrate, magnesium calcium carbonate, or mixtures thereof.
  • magnesium hydroxide, aluminium hydroxide and alumina trihydrate Al 2 O 3 ⁇ 3H 2 O
  • mixtures thereof are particularly preferred.
  • the above mentioned metal hydroxides, in particular the magnesium and aluminium hydroxides, are preferably used in the form of particles with sizes which can range between 0.1 and 100 ⁇ m, preferably between 0.5 and 10 ⁇ m.
  • natural magnesium hydroxide indicates the magnesium hydroxide obtained by milling minerals based on magnesium hydroxide, such as brucite and the like.
  • Brucite is found in nature as such, or, more frequently, in combination with other minerals, such as calcite, aragonite, talc or magnesite, usually in stratified form between silicate deposits, such as, for example, in serpentine, in chlorite or in schists.
  • Brucite can be milled, according to known techniques, under wet or dry conditions, preferably in the presence of milling coadjuvants, such as polyglycols or the like.
  • the specific surface area of the milled product generally ranges from 5 to 20 m 2 /g, preferably from 6 to 15 m 2 /g.
  • the magnesium hydroxide thus obtained can subsequently be classified, for example by sieving, in order to obtain an average particle diameter ranging from 1 to 15 ⁇ m, preferably from 1. 5 to 5 ⁇ m, and a particle size distribution such that the particles with a diameter of less than 1.5 ⁇ m form not more than 10% of the total, and the particles with a diameter of greater than 20 ⁇ m form not more than 10% of the total.
  • Natural magnesium hydroxide generally contains various impurities deriving from salts, oxides and/or hydroxides of other metals, such as Fe, Mn, Ca, Si, V, etc.
  • the amount and nature of the impurities present can vary as a function of the origin of the starting material.
  • the degree of purity is generally between 80 and 98% by weight.
  • the content of impurities of water-soluble ionic type can be determined indirectly by measuring the electrical conductivity of the aqueous extract obtained by placing the magnesium hydroxide in contact with a suitable amount of water for a predetermined time and at a predetermined temperature according to ISO method 787. According to this method, the electrical conductivity of the aqueous extract obtained from natural magnesium hydroxide is generally between 100 and 500 ⁇ S/cm, preferably between 120 and 350 ⁇ S/cm.
  • the amount of flame-retardant inorganic filler to be used in the compositions of the present invention is predetermined so as to obtain a cable which is capable of passing the usual flame resistance tests, for example those according to IEC standard 332-1 and IEC 332.3 A, B and C.
  • This amount is generally between 10 and 90% by weight, preferably between 30 and 80% by weight, and even more preferably between 50 and 70% by weight, relative to the total weight of the flame-retardant composition.
  • the flame-retardant fillers can be used advantageously in the form of coated particles.
  • Coating materials preferably used are saturated or unsaturated fatty acids containing from 8 to 24 carbon atoms, and metal salts thereof, such as, for example: oleic acid, palmitic acid, stearic acid, isostearic acid, lauric acid; magnesium or zinc stearate or oleate; and the like.
  • a coupling agent selected, for example, from: saturated silane compounds or silane compounds containing at least one ethylenic unsaturation; epoxides containing an ethylenic unsaturation; organic titanates; mono- or dicarboxylic acids containing at least one ethylenic unsaturation, or derivatives thereof such as, for example, anhydrides or esters, can be added to the mixture in order to enhance the compatibility between the inorganic filler and the polymer material.
  • silane compounds are: ⁇ -propyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, methyltriethoxysilane, methyltris(2-methoxyethoxy)silane, dimethyldiethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, octyltriethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane and the like, or mixtures thereof.
  • epoxides containing an ethylenic unsaturation are: glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, maleic acid glycidyl ester, vinyl glycidyl ether, allyl glycidyl ether and the like, or mixtures thereof.
  • An example of a suitable organic titanate is tetra-n-butyl titanate.
  • Mono- or dicarboxylic acids containing at least one ethylenic unsaturation, or derivatives thereof, which can be used as coupling agents are, for example: maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, acrylic acid, methacrylic acid and the like, and the anhydrides or esters derived therefrom, or mixtures thereof.
  • Maleic anhydride is particularly preferred.
  • the coupling agents can be used as such or pregrafted onto a polyolefin, for example polyethylene or copolymers of ethylene with an ⁇ -olefin, by means of a radical reaction (see, for example, patent EP-0,530,940).
  • the amount of grafted coupling agent is generally between 0.05 and 5 parts by weight, preferably from 0.1 to 2 parts by weight, relative to 100 parts by weight of polyolefin.
  • Polyolefins grafted with maleic anhydride are available as commercial products identified, for example, by the brand names Fusabond®, (Du Pont), Orevac® (Elf Atochem), Exxelor® (Exxon Chemical), Yparex® (DSM), etc.
  • the coupling agents of carboxylic or epoxy type mentioned above for example maleic anhydride
  • silanes containing an ethylenic unsaturation for example vinyltrimethoxysilane
  • a radical initiator so as to graft the compatibilizing agent directly onto the polymer material.
  • Initiators which can be used are, for example, organic peroxides such as tert-butyl perbenzoate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide and the like. This technique is described, for example, in patent US-4,317,765 and in Japanese patent application JP/62-58774.
  • the amount of coupling agent to be added to the mixture can vary mainly as a function of the type of coupling agent used and the amount of flame-retardant filler added, and is generally between 0.01 and 10%, preferably between 0.02 and 5%, and even more preferably between 0.05 and 2%, by weight relative to the total weight of the base polymer mixture.
  • antioxidants examples include: polymerized trimethyldihydroquinoline, 4,4'-thiobis(3-methyl-6-tert-butyl)phenol; pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like, or mixtures thereof.
  • Processing coadjuvants usually added to the polymer material are, for example, calcium stearate, zinc stearate, stearic acid, paraffin wax, silicone rubbers and the like, or mixtures thereof.
  • fillers which can be used are, for example: glass particles, glass fibres, calcined kaolin, talc and the like, or mixtures thereof.
  • the flame-retardant compositions according to the present invention are preferably used in non-crosslinked form, in order to obtain a coating with thermoplastic and thus recyclable properties.
  • the flame-retardant compositions according to the present invention can be prepared by mixing the polymer component, the filler and the additives according to techniques known in the art.
  • the mixing can be carried out, for example, using an internal mixer of the type with tangential rotors (Banbury) or with interpenetrating rotors, or alternatively in continuous mixers such as Ko-Kneader (Buss) or corotating or counter-rotating twin-screw mixers.
  • the flame-retardant composition can thus be used to coat the conductor directly, or to produce an outer self-extinguishing sheath on the conductor which has been precoated with an insulating layer.
  • the coating step is generally carried out by means of extrusion. When two layers are present, the extrusion can be carried out in two separate steps, extruding the inner layer onto the conductor in a first run and the outer layer onto this inner layer in a second run.
  • the coating process can advantageously be carried out in a single run, for example by means of a "tandem" method, wherein two separate extruders arranged in series are used, or alternatively by co-extrusion using a single extrusion head.
  • low voltage generally means a voltage of less than 5 kV, preferably less than 2 kV and even more preferably less than 1 kV.
  • the cable in Figure 1 comprises a metal conductor (1), and inner layer (2) which acts as an electrical insulator, and an outer layer (3) which acts as a protective sheath with flame-retardant properties according to the present invention.
  • the inner layer (2) can consist of a crosslinked or non-crosslinked polymer composition, preferably devoid of halogens, with electrical insulating properties, which is known in the art, selected, for example, from: polyolefins (homopolymers or copolymers of different olefins), olefin/ethylenically unsaturated ester copolymers, polyesters, polyethers, polyether/polyester copolymers and mixtures thereof.
  • polyolefins homopolymers or copolymers of different olefins
  • olefin/ethylenically unsaturated ester copolymers polyesters
  • polyethers polyether/polyester copolymers and mixtures thereof.
  • polyethylene in particular linear low-density PE (LLDPE); polypropylene (PP); propylene/ethylene thermoplastic copolymers; ethylene-propylene rubbers (EPR) or ethylene-propylene-diene rubbers (EPDM); natural rubbers; butyl rubbers; ethylene/vinyl acetate (EVA) copolymers; ethylene/methyl acrylate (EMA) copolymers; ethylene/ethyl acrylate (EEA) copolymers; ethylene/butyl acrylate (EBA) copolymers; ethylene/ ⁇ -olefin copolymers and the like.
  • PE polyethylene
  • LLDPE linear low-density PE
  • PP polypropylene
  • EPR ethylene-propylene rubbers
  • EPDM ethylene-propylene-diene rubbers
  • EVA ethylene/vinyl acetate copolymers
  • EMA ethylene/methyl acrylate
  • EAA ethylene/ethyl acrylate
  • the cable in Fig. 2 comprises a conductor (1) coated directly with a flame-retardant sheath (3) according to the present invention, without interposing the insulating layer (2).
  • the conductor (1) is metallic, the self-extinguishing coating (3) also acts as electrical insulation.
  • a thin polymer layer having an anti-abrasive function, to which a suitable pigment is optionally added in order to produce a coloration for identification purposes, can then be added externally.
  • Figs. 1 and 2 show only two possible types of cable according to the present invention. It is clear that suitable modifications known in the art can be made to these embodiments, without thereby departing from the scope of the present invention.
  • telecommunications cables or data transmission cables, or alternatively mixed power/telecommunications cables can be produced using the flame-retardant compositions according to the present invention.
  • the present description is mainly directed to self-extinguishing cables, the flame-retardant compositions according to the invention can be used to impart self-extinguishing properties to other articles, in particular electrical junction or termination devices.
  • Table 1 gives a number of properties of some heterophase copolymers used according to the present invention (Cop. 1 and Cop. 2) and for comparative purposes (Cop. 3 and Cop. 4).
  • melt flow index was measured at 230°C and 21.6 N according to ASTM standard D 1238/L.
  • the heat of fusion deriving from polypropylene sequences (PP enthalpy) and the heat of fusion deriving from polyethylene sequences (PE enthalpy) was measured using DSC instrumentation from Mettler (second melting value) with a scanning speed of 10°C/min. (instrument head: DSC 30 type; microprocessor: PC 11 type; software: Mettler Graphware TA72AT.1).
  • DSC curves of the four heterophase copolymers in Table 1 are given in Figures 3-6.
  • the DSC curve for Cop. 2 shows a single melting peak associated with the polypropylene phase centred at about 145°C, with a very pronounced "tail" which extends below 130°C and which can be attributed to the presence of a polypropylene phase with low crystallinity presumably consisting of short sequences of propylene units interrupted by ethylene units.
  • the percentage of elastomeric phase was determined by extraction with refluxing xylene at 135°C for 20 min., calculated as the difference between the initial weight of the sample and the weight of the dried residue.
  • the propylene content of the elastomeric phase was determined by IR spectroscopic analysis of the polymer extracted as described above and dried by evaporation of the solvent. The propylene content is determined, by means of suitable calibration curves, as the ratio between the intensity of the bands at 4377 and 4255 cm -1 .
  • the heterophase copolymers in Table 1 were used to prepare the flame-retardant compositions reported in Table 2, using a 1.6 litre Banbury mixer with a volumetric packing ratio of about 75%.
  • 1 mm plates were prepared with the compositions thus obtained by compression moulding at 190-195°C and 200 bar after preheating for 5 min. at the same temperature.
  • Small cables were then prepared by extruding identical compositions of Table 2 onto a single red copper wire with a cross-section of 1.5 mm 2 , so as to obtain a 0.7 mm thick flame-retardant layer.
  • the plates and small cables thus prepared were subjected to mechanical tensile strength tests (E.B. and S.B.) according to CEI standard 20-34, paragraph 5.1.
  • the pulling speed of the jaws was 250 mm/min.
  • the cables were also subjected to the flame resistance test according to IEC standard 332-1, which consists in subjecting a sample 60 cm long, placed vertically, to the direct action of a Bunsen burner flame applied for 1 min at an inclination of 45° relative to the sample. All the cable samples passed the test.

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  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Claims (16)

  1. Câble comprenant au moins un conducteur (1) et au moins une couche de revêtement (3) résistant à l'inflammation, à base d'une matière polymère et d'une charge minérale ignifugeante, caractérisé en ce que ladite matière polymère comprend un copolymère hétérophase ayant une phase élastomère à base d'éthylène copolymérisé avec une α-oléfine et une phase thermoplastique à base de propylène, ladite phase élastomère dudit copolymère hétérophase représentant au moins 45 % en poids du poids total du copolymère hétérophase, ledit copolymère hétérophase étant pratiquement dénué de cristallinité provenant de séquences polyéthylène.
  2. Câble selon la revendication 1, dans lequel une couche interne électriquement isolante est présente et la couche de revêtement résistant à l'inflammation est placée à l'extérieur de ladite couche interne isolante.
  3. Câble selon la revendication 1, dont le revêtement résistant à l'inflammation est placé directement sur le conducteur.
  4. Câble selon l'une quelconque des revendications précédentes, pour lequel ledit copolymère hétérophase est un copolymère ayant une chaleur de fusion correspondant aux pics présents à une température inférieure à 130 °C et attribuables à des séquences polyéthylène, inférieure à 3 J/g.
  5. Câble selon la revendication 4, pour lequel ledit copolymère hétérophase est un copolymère ayant une chaleur de fusion correspondant aux pics présents à une température inférieure à 130 °C et attribuables à des séquences polyéthylène, qui est pratiquement égale à zéro.
  6. Câble selon l'une quelconque des revendications 1 à 5, pour lequel ladite phase élastomère est constituée d'un copolymère élastomère comprenant 15 à 50 % en poids d'éthylène et 50 à 85 % en poids de propylène, ces pourcentages étant rapportés au poids de la phase élastomère.
  7. Câble selon la revendication 6, pour lequel ladite phase élastomère est constituée d'un copolymère élastomère comprenant 20 à 40 % en poids d'éthylène et 60 à 80 % en poids de propylène, ces pourcentages étant rapportés au poids de la phase élastomère.
  8. Câble selon l'une quelconque des revendications précédentes, pour lequel la charge minérale ignifugeante est choisie parmi des hydroxydes, des oxydes hydratés, des sels métalliques ou sels métalliques hydratés, et leurs mélanges.
  9. Câble selon la revendication 8, pour lequel la charge minérale ignifugeante est choisie parmi l'hydroxyde de magnésium, le trihydrate d'alumine et leurs mélanges.
  10. Câble selon la revendication 9, pour lequel la charge minérale ignifugeante est de l'hydroxyde de magnésium naturel.
  11. Câble selon l'une quelconque des revendications précédentes, dans lequel la charge minérale ignifugeante est présente en une proportion comprise entre 10 % et 90 % en poids par rapport au poids total de la couche résistant à l'inflammation.
  12. Câble selon la revendication 11, dans lequel la charge minérale ignifugeante est présente en une proportion comprise entre 30 et 80 % en poids par rapport au poids total de la couche résistant à l'inflammation.
  13. Câble selon la revendication 12, dans lequel la charge minérale ignifugeante est présente en une proportion comprise entre 50 % et 70 % en poids par rapport au poids total de la couche résistant à l'inflammation.
  14. Composition résistant à l'inflammation, à base d'une matière polymère et d'une charge minérale ignifugeante, caractérisée en ce que ladite matière polymère comprend un copolymère hétérophase ayant une phase élastomère à base d'éthylène copolymérisé avec une α-oléfine et une phase thermoplastique à base de propylène, ladite phase élastomère dudit copolymère hétérophase représentant au moins 45 % en poids du poids total du copolymère hétérophase, ledit copolymère hétérophase étant pratiquement dénué de cristallinité provenant de séquences polyéthylène.
  15. Composition selon la revendication 14, pour laquelle le copolymère hétérophase est un copolymère tel que défini dans l'une quelconque des revendications 4 à 7.
  16. Composition selon la revendication 14 ou 15, pour laquelle la charge minérale ignifugeante est une charge telle que définie dans l'une quelconque des revendications 8 à 13.
EP20000201096 1999-04-03 2000-03-27 Cable autoextinguible à faible fumée et composition résistant aux flammes utilisée dans ce cable Revoked EP1043733B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20000201096 EP1043733B1 (fr) 1999-04-03 2000-03-27 Cable autoextinguible à faible fumée et composition résistant aux flammes utilisée dans ce cable

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP99201109 1999-04-03
EP99201109 1999-04-03
EP20000201096 EP1043733B1 (fr) 1999-04-03 2000-03-27 Cable autoextinguible à faible fumée et composition résistant aux flammes utilisée dans ce cable

Publications (2)

Publication Number Publication Date
EP1043733A1 EP1043733A1 (fr) 2000-10-11
EP1043733B1 true EP1043733B1 (fr) 2004-08-25

Family

ID=8240080

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20000201096 Revoked EP1043733B1 (fr) 1999-04-03 2000-03-27 Cable autoextinguible à faible fumée et composition résistant aux flammes utilisée dans ce cable

Country Status (10)

Country Link
EP (1) EP1043733B1 (fr)
JP (1) JP2000322948A (fr)
AR (1) AR023931A1 (fr)
AT (1) ATE274746T1 (fr)
AU (1) AU777541B2 (fr)
BR (1) BR0001533B1 (fr)
CA (1) CA2303656C (fr)
DE (1) DE60013196T2 (fr)
ES (1) ES2226701T3 (fr)
NZ (1) NZ503676A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11042000B2 (en) 2015-05-28 2021-06-22 Prysmian S.P.A. Optical cable for terrestrial networks

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313377A (ja) * 2002-04-26 2003-11-06 Yazaki Corp 難燃性ポリプロピレン系樹脂組成物及び自動車用絶縁電線
DE10236288A1 (de) * 2002-08-08 2004-02-26 Nexans Elektrisches Kabel
US7125924B2 (en) 2002-09-17 2006-10-24 Basell Poliolefine Italia S.P.A. Highly filled soft polyolefin compositions
ATE370193T1 (de) * 2002-09-17 2007-09-15 Basell Poliolefine Srl Hochgefüllte weiche polyolefinzusammensetzungen
US7518064B2 (en) 2003-07-30 2009-04-14 Sumitomo Electric Industries, Ltd. Halogen free flame retardant cable
EP1745493B1 (fr) * 2004-05-05 2017-12-27 Union Carbide Chemicals & Plastics Technology LLC Cable ignifuge pour vide technique
JP4330603B2 (ja) 2006-07-18 2009-09-16 株式会社オートネットワーク技術研究所 絶縁電線およびワイヤーハーネス
GB2441158A (en) * 2006-08-22 2008-02-27 Tyco Electronics Ltd Uk Zero-halogen wire or cable insulation
JP4197187B2 (ja) * 2006-12-12 2008-12-17 株式会社オートネットワーク技術研究所 難燃性樹脂組成物ならびにこれを用いた絶縁電線およびワイヤーハーネス
KR100997825B1 (ko) * 2008-08-27 2010-12-01 엘에스전선 주식회사 분산성과 기계적 물성이 개선된 난연성 폴리프로필렌 절연 수지 조성물 및 이를 이용한 절연 전선
WO2012152803A1 (fr) 2011-05-11 2012-11-15 Basell Poliolefine Italia S.R.L. Compositions de polyoléfine souples hautement chargées
EP2660287A1 (fr) 2012-05-04 2013-11-06 Basell Poliolefine Italia S.r.l. Compositions de polyoléfine souple hautement chargées
BR112013028699B1 (pt) 2011-05-11 2021-03-16 Basell Poliolefine Italia S.R.L composições de poliolefina e de poliolefina enchida bem como artigos, folhas ou películas para cobertura e enchimento interno para cabos industriais ou embainhamento de cabos compreendendo as referidas composições
ES2715702T3 (es) * 2015-01-27 2019-06-05 Borealis Ag Composición de polipropileno retardante de las llamas
WO2019002917A1 (fr) 2017-06-29 2019-01-03 Prysmian S.P.A. Câble électrique ignifuge, à faible fumée et résistant au froid

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3047269C2 (de) * 1980-12-16 1983-08-04 AEG-Telefunken Kabelwerke AG, Rheydt, 4050 Mönchengladbach "Thermoplastische Polymermischung"
DE3150798C2 (de) * 1981-12-22 1989-11-23 AEG-Telefunken Kabelwerke AG, Rheydt, 4050 Mönchengladbach Thermoplastische, halogenfreie flammwidrige Polymermischung
DE3228119A1 (de) * 1982-07-28 1984-02-02 AEG-Telefunken Kabelwerke AG, Rheydt, 4050 Mönchengladbach Halogenfreies, flammwidriges kabel mit funktionserhalt im brandfall fuer eine bestimmte zeit
JPS60133042A (ja) * 1983-12-20 1985-07-16 Nippon Petrochem Co Ltd 電気絶縁用樹脂組成物
GB2190384A (en) * 1986-05-12 1987-11-18 Exxon Chemical Patents Inc Halogen free flame retardant compositions
IE873315L (en) * 1986-12-31 1988-06-30 Flork Michel Filled elastomer blends
US4910359A (en) * 1988-10-31 1990-03-20 American Telephone And Telegraph Company, At&T Technologies, Inc. Universal cordage for transmitting communications signals
JPH03231944A (ja) * 1990-02-07 1991-10-15 Nippon Petrochem Co Ltd 難燃性樹脂組成物
CA2038626A1 (fr) * 1990-03-22 1991-09-23 Behrooz A. Khorramian Cable a gaine de matiere plastique sans halogene
GB9023188D0 (en) * 1990-10-24 1990-12-05 Bicc Plc Polymer compositions
US5162609A (en) * 1991-07-31 1992-11-10 At&T Bell Laboratories Fire-resistant cable for transmitting high frequency signals
CN1152471A (zh) * 1995-11-10 1997-06-25 阿尔卡塔尔-阿尔斯托姆通用电气公司 具备高度抗火焰蔓延性的组合物
JP3765511B2 (ja) * 1997-02-14 2006-04-12 三井金属鉱業株式会社 難燃性ケーブル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11042000B2 (en) 2015-05-28 2021-06-22 Prysmian S.P.A. Optical cable for terrestrial networks

Also Published As

Publication number Publication date
DE60013196D1 (de) 2004-09-30
ATE274746T1 (de) 2004-09-15
CA2303656C (fr) 2008-06-10
NZ503676A (en) 2001-09-28
AR023931A1 (es) 2002-09-04
BR0001533B1 (pt) 2011-05-17
AU777541B2 (en) 2004-10-21
AU2519700A (en) 2000-10-05
JP2000322948A (ja) 2000-11-24
DE60013196T2 (de) 2005-08-11
ES2226701T3 (es) 2005-04-01
EP1043733A1 (fr) 2000-10-11
BR0001533A (pt) 2001-10-09
CA2303656A1 (fr) 2000-10-03

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