AU2009315516A1 - Fireproof electric cable - Google Patents

Fireproof electric cable Download PDF

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Publication number
AU2009315516A1
AU2009315516A1 AU2009315516A AU2009315516A AU2009315516A1 AU 2009315516 A1 AU2009315516 A1 AU 2009315516A1 AU 2009315516 A AU2009315516 A AU 2009315516A AU 2009315516 A AU2009315516 A AU 2009315516A AU 2009315516 A1 AU2009315516 A1 AU 2009315516A1
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Australia
Prior art keywords
layer
composition
cable according
insulated electrical
cable
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AU2009315516A
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AU2009315516B2 (en
Inventor
Alain Clertant
Yannick Goutille
Nicolas Rousselet
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Nexans SA
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Nexans SA
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/307Other macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00Layered products having a non-planar shape
    • B32B1/08Tubular products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/44Insulators 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
    • H01B3/441Insulators 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/46Insulators 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 silicones
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/17Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29Protection against damage caused by extremes of temperature or by flame
    • H01B7/295Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202Conductive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/732Dimensional properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
  • Organic Insulating Materials (AREA)

Description

WO 2010/055247 PCT/FR2009/052135 Fireproof electric cable The present invention relates to an electric cable comprising an assembly of insulated electrical 5 conductors, and also to a process for manufacturing said cable. The invention applies typically, but not exclusively, to the field of fireproof safety cables, especially halogen-free safety cables, capable of 10 functioning for a given period of time under fire conditions, without, however, propagating the fire or generating a lot of fumes. These safety cables are in particular power transmission cables or low-frequency transmission cables, such as control or signaling cables. 15 one of the major challenges of the cable industry is the improvement of the behavior and performance of cables under extreme thermal conditions, especially those encountered in a fire. For essentially safety reasons, it is in fact desirable to maximize the capacities of the 20 cable to retard the propagation of flames, on the one hand, and to withstand fire, on the other hand, in order to ensure continuity of functioning. Significant slowing-down of the progress of flames will gain valuable time for evacuating the premises 25 and/or for implementing appropriate extinction means. In the event of a fire, the cable must be able to withstand the fire in order to function for as long as possible and to limit its degradation. A safety cable must also not be hazardous to its environment, i.e. it must not give off 30 toxic and/or opaque fumes when it is subjected to extreme thermal conditions. Document EP 0 942 439 discloses a halogen-free fireproof safety electric cable comprising an assembly of insulated electrical conductors, said assembly being 35 surrounded by an outer sheath. Each insulated electrical WO 2010/055247 PCT/FR2009/052135 2 conductor is formed from an electrical conductor surrounded by an insulating layer obtained from a composition comprising a polymer material and at least one ceramic-forming filler, said insulating layer thus 5 being capable of being converted at least superficially into the ceramic state at high temperatures corresponding to fire conditions. The polymer material of this single insulating layer is chosen from a polysiloxane and an ethylene copolymer, or a mixture thereof. 10 However, it has been found that this safety cable of the prior art, although having good fireproof properties, is mechanically fragile. More particularly, the insulated electrical conductors are sensitive to the various mechanical constraints to which these cables are 15 typically subjected during their manufacture, transportation, handling, installation or connection. The aim of the present invention is to overcome the drawbacks of the techniques of the prior art by especially proposing an electric cable that is easy to 20 handle, which limits the risks of mechanical degradation of the insulated electrical conductors of which it is composed, while at the same time maintaining excellent fireproofing properties that satisfy standard NF C 32-070 CR1. 25 One subject of the present invention is an electric cable comprising: - an assembly of insulated electrical conductors, each insulated electrical conductor comprising an electrical conductor surrounded with an insulating layer 30 that is capable of being converted at least superficially into the ceramic state at high temperatures corresponding to fire conditions, and - an outer sheath surrounding the assembly of insulated electrical conductors, empty spaces being 35 provided between said sheath and the assembly of WO 2010/055247 PCT/FR2009/052135 3 insulated electrical conductors, characterized in that said insulating layer comprises a first crosslinked layer surrounding the electrical conductor, and a second crosslinked layer 5 surrounding said first layer, the first layer being obtained from a first composition comprising a polyorganosiloxane-based polymer matrix, and the second layer being obtained from a second composition comprising a polyolefin-based polymer matrix. 10 In the text hereinbelow: - the term "polyorganosiloxane-based polymer matrix" denotes a polymer matrix comprising only one or more polymers predominantly formed from polyorganosiloxane, and 15 - the term "polyolefin-based polymer matrix" denotes a polymer matrix comprising only one or more polymers formed predominantly from polyolefin. By virtue of the invention, the second layer, known 20 as the outer layer, based on polyolefin mechanically protects the first layer, known as the inner layer, based on polyorganosiloxane. This property allows the insulating layer of each insulated electrical conductor to improve the mechanical properties of the cable, 25 especially the hardness, the abrasion strength and the tear strength of the insulated electrical conductors of which it is composed, to facilitate the installation of said cable, and to make the cable more robust during its manufacture, irrespective of whether there is good or 30 poor adhesion between the first layer and the second layer of the insulating layer. Furthermore, the safety electric cable comprising the insulating layer according to the invention satisfies standard NF C 32-070 CR1. The electrical conductors are 35 thus protected against fire, or in other words, the WO 2010/055247 PCT/FR2009/052135 4 electric cable affords high-quality fire behavior in terms, at least, of ash cohesion. The invention as thus defined also has the advantage of being economical since it makes it possible 5 to significantly reduce the amount of polyorganosiloxane in the insulating layer of the insulated electrical conductors, while at the same time having very good fireproofing properties. The polyorganosiloxane, or polyorganosiloxane 10 polymer, according to the present invention contains not more than 4% and preferably from 0.01% to 3% by weight of vinyl groups. When these polyorganosiloxane polymers have viscosities at 25 0 C of between 50 000 and 1 000 000 mPa.s, they are known as oils, but their 15 viscosity may be higher than 1 000 000 mPa.s and they are then known as gums. In the compositions according to the present invention, the polyorganosiloxane polymers may be oils or gums or mixtures. 20 According to one particular example, the poly organosiloxane contains not more than 4% by weight of vinyl groups and has a viscosity of at least 1 000 000 mPa.s at 250C and preferably a viscosity of about 20 000 000 mPa.s at 250C. 25 These polyorganosiloxanes are linear polymers, whose diorganopolysiloxane chain is formed essentially from units of formula R 2 SiO. This chain is blocked at each end with a unit of formula R 3 Sio.
5 and/or a radical of formula OR'. In these 30 formulae: - the symbols R, which may be identical or different, represent monovalent hydrocarbon-based radicals such as alkyl radicals, for example methyl, ethyl, propyl, octyl, octadecyl, etc., aryl radicals, for 35 example phenyl, tolyl, xylyl, etc., aralkyl radicals such WO 2010/055247 PCT/FR2009/052135 5 as benzyl, phenylethyl, etc., cycloalkyl and cycloalkenyl radicals such as cyclohexyl, cycloheptyl, cyclohexenyl, etc. radicals, alkenyl radicals, for example vinyl, allyl, etc. radicals, alkaryl radicals, cyanoalkyl 5 radicals such as a cyanoethyl radical etc., haloalkyl, haloalkenyl and haloaryl radicals such as chloromethyl, 3,3, 3-trifluoropropyl, chlorophenyl, dibromophenyl, trifluoromethylphenyl radicals, - the symbol R' represents a hydrogen atom, an 10 alkyl radical containing from 1 to 4 carbon atoms or a $-methoxyethyl radical. Preferably, at least 60% of the groups R represent methyl radicals. The presence, along the diorganopolysiloxane chain, 15 of small amounts of units other than R 2 SiO, for example units of formula RSiOi.
5 and/or SiO 2 , is, however, not excluded in a proportion of not more than 2%, these percentages expressing the number of T and/or Q units per 100 silicon atoms. The trifunctional units, of symbol T, 20 make it possible to obtain three-dimensional networks. The tetrafunctional units, of symbol Q, lead to three dimensional products whose structure is similar to that of silicates. As concrete examples of units of formulae R 2 SiO and 25 R 3 SiOo.
5 that may be mentioned are those of formulae:
(CH
3 ) 2 SiO, CH 3
(CH
2 =CH) SiO, CH 3
(C
6
H
5 ) SiO, (C 6
H
5 ) 2 SiO,
CH
3
(C
2
H
5 ) SiO, (CH 3
CH
2
CH
2 ) CH 3 SiO, CH 3 (n. C 3
H
7 ) SiO, (CH 3 ) 3 SiOo.
5 ,
(CH
3
)
2
(CH
2 =CH)SiOo.
5 , CH 3
(C
6
H
5
)
2 SiOo.
5 , CH 3
(C
6
H
5 ) (CH 2 =CH)SiOo.s As concrete examples of units of radicals of 30 formula OR' that may be mentioned are those of formulae: OH, -OCH 3 , -OC 2
H
5 , -O-n.C 3 H, -O-iso.C 3
H
7 , -O-n.C 4
H
9 ,
-OCH
2
CH
2
OCH
3 . These oils and gums are sold by silicone manufacturers or may be manufactured by working according 35 to already-known techniques.
WO 2010/055247 PCT/FR2009/052135 6 The polyolefin of the second composition according to the invention may be chosen from ethylene homopolymers and copolymers, or a mixture thereof. As a preferred example of ethylene homopolymers, 5 mention may be made of low-density polyethylene (LDPE). The ethylene copolymers may advantageously be chosen from ethylene/octene copolymers (PEO), ethylene/vinyl acetate copolymers (EVA), ethylene/butyl acrylate copolymers (EBA), ethylene/methyl acrylate 10 copolymers (EMA) and ethylene/ethyl acrylate copolymers (EEA), ethylene/propylene/rubber copolymers (EPR) and ethylene/propylene/diene/monomer copolymers (EPDM), or a mixture thereof. As a preferred example of ethylene copolymers, 15 mention may be made of ethylene/vinyl acetate copolymers (EVA). In one preferred embodiment, the first composition also comprises at least one filler that forms ceramic under the effect of the high temperatures of a fire. 20 In another preferred embodiment, the second composition also comprises at least one flame-retardant mineral filler and/or at least one ceramic-forming filler. The ceramic-forming filler, or ceramizable filler, 25 mentioned in the present description may comprise at least one mineral filler of the meltable ceramic filler and/or refractory filler type, and preferably at least one meltable ceramic filler and at least one refractory filler, so that the first layer affords sufficient 30 insulation when the organic part of the insulating layer, more particularly the second layer, has disappeared as a result of combustion. More particularly, the meltable ceramic filler has a melting point below a high temperature T, and the 35 refractory filler has a melting point above said WO 2010/055247 PCT/FR2009/052135 7 temperature T. This temperature T is advantageously at least 750 0 C and may be up to 11000C. The meltable ceramic filler may be at least one mineral filler chosen from boron oxides (e.g. B 2 0 3 ) , 5 anhydrous zinc borates (e.g. 2ZnO 3B 2 0 3 ) or hydrated zinc borates (e.g. 4ZnO B 2 0 3
H
2 0 or 2ZnO 3B 2 0 3 3.5H 2 0) and anhydrous boron phosphates (e.g. BPO 4 ) or hydrated boron phosphates, or a precursor thereof. This meltable ceramic filler typically has a 10 melting point below 500 0 C and gives rise to a glass when the temperature exceeds 5000C. The refractory filler may be at least one mineral filler chosen from magnesium oxides (e.g. MgO), calcium oxides (e.g. CaO), silicon oxides (e.g. Sio 2 or quartz), 15 aluminum oxides or aluminas (e.g. A1 2 0 3 ), chromium oxides (e.g. Cr 2 0 3 ), zirconium oxides (e.g. ZrO 2 ) and phyllosilicates such as, for example, montmorillonites, sepiolites, illites, attapulgites, talcs, kaolins or micas (e.g. mica muscovite 6 Si0 2 -3 A1 2 0 3
-K
2 0-2H 2 0), or a 20 mixture thereof. The flame-retardant mineral filler mentioned in the present description may be a hydrated flame-retardant mineral filler, chosen especially from metal hydroxides, for instance magnesium hydroxide or aluminum 25 trihydroxide. According to the present invention, the empty spaces promote the total combustion of the outer sheath subjected to fire, due to the presence of oxygen in these spaces, and the conversion of this sheath into residual 30 ash that detaches from the insulating layer of the electrical conductors. As a result, the empty spaces do not comprise, for example, any filling polymer material (or polymeric filler) between the assembly of insulated electrical conductors and the outer sheath. This outer 35 sheath is typically known as the tubing sheath or tubular WO 2010/055247 PCT/FR2009/052135 8 sheath. Preferably, the empty spaces of the electric cable occupy at least 10% of the cross section of said cable. In addition, according to a further characteristic, 5 the electric cable according to the invention is free of metallic shield, for instance a metallic strip or a composite strip placed along said cable between the assembly of insulated electrical conductors and the outer sheath. The term "composite strip" means a strip composed 10 of layers of metal and of polymer. Said metallic strip or said metallic layers of the composite strip may be made, for example, of copper or of aluminum. This type of metallic shield limits, or even cancels out, the benefit of said empty spaces and thus 15 significantly disrupts the process of ceramization of the ash of the insulating layers, leading to non-conformity of the fire resistance tests. In one particular embodiment, the outer sheath comprises a polyolefin-based matrix and at least one 20 hydrated flame-retardant mineral filler chosen especially from metal hydroxides, for instance magnesium hydroxide or aluminum trihydroxide. This sheath can thus burn completely locally and be converted into residual ash under the effect of the high 25 temperatures of a fire, without, however, being a fire propagator. The flame-retardant fillers used act mainly via a physical route by decomposing endothermically, which has the consequence of lowering the temperature of the material and limiting the propagation of flames along 30 the cable. In order to provide an HFFR cable "Halogen-Free Flame Retardant cable", the electric cable according to the invention does not comprise any halogenated compounds. These halogenated compounds may be of any 35 nature, for instance fluoropolymers or chloropolymers, WO 2010/055247 PCT/FR2009/052135 9 for instance polyvinyl chloride (PVC), halogenated plasticizers, halogenated mineral fillers, etc. In one particular embodiment in accordance with the invention, the thickness of the first layer is from 5 0.10 mm to 1.50 mm and the thickness of the second layer is from 0.05 mm to 1.50 mm, especially when the cross section of the electrical conductor is from 1.5 mm 2 to 4 mm 2 According to a first variant of this embodiment, 10 when the cross section of the electrical conductor is 1.5 mm 2 , the thickness of the first layer is preferably from 0.30 mm to 0.80 mm and more preferentially 0.45 mm. In this case, the thickness of the second layer is itself preferably from 0.10 mm to 0.50 mm, and more 15 preferentially 0.35 mm. According to a second variant of this embodiment, when the cross section of the electrical conductor is 2.5 mm2, the thickness of the first layer is preferably 0.30 mm to 0.90 mm, and more preferentially 0.50 mm. In 20 this case, the thickness of the second layer is, itself, preferably from 0.10 mm to 0.60 mm, and more preferentially 0.40 mm. According to a third variant of this embodiment, when the cross section of the electrical conductor is 25 4 mm 2 , the thickness of the first layer is preferably 0.35 mm to 1 mm, and more preferentially 0.55 mm. In this case, the thickness of the second layer is, itself, preferably from 0.10 mm to 0.70 mm, and more preferentially 0.45 mm. 30 Another subject according to the invention is a process for manufacturing an electric cable as described above in accordance with the invention, characterized in that it comprises the steps consisting in: i. forming the insulating layer of the insulated 35 electrical conductor by extrusion and WO 2010/055247 PCT/FR2009/052135 10 crosslinking of the first composition and of the second composition around an electrical conductor, ii. assembling at least two insulated electrical 5 conductors as obtained in step i, and iii.extruding an outer sheath in a tubing manner around the assembled insulated electrical conductors of step ii. According to this manufacturing process, the first 10 and second compositions are, on the one hand, extruded, and, on the other hand, crosslinked via standard techniques that are well known to those skilled in the art so as to obtain an extruded and crosslinked insulating layer. 15 According to a first variant of the process for manufacturing an electric cable, step i may consist in: i.1 extruding around an electrical conductor the first composition using a first extruder and the second composition using a second extruder, 20 the first and second extruders comprising the same extrusion head, to form at the extruder outlet the insulating layer of the insulated electrical conductor, i.2 crosslinking the extruded insulating layer of 25 step i.1, steps ii and iii of the process as described above remaining unchanged. Step i.1 of extrusion is referred to as coextrusion. According to a second variant of the process for 30 manufacturing an electric cable, step i may consist in: i.1 extruding using a first extruder the first composition and crosslinking at least partially the extruded first composition, i.2 extruding using a second extruder the second 35 composition, to form the insulating layer of WO 2010/055247 PCT/FR2009/052135 11 the insulated electrical conductor, and crosslinking the extruded insulating layer, steps ii and iii of the process as described above remaining unchanged. 5 Other characteristics and advantages of the present invention will emerge in the light of the examples that follow and of the attached figure, said examples and figure being given as illustrations and are in no way limiting. 10 Figure 1 is a schematic view in cross section of an electric cable according to the invention. For reasons of clarity, the same elements have been denoted with identical references in this figure. Similarly, only the elements that are essential for the 15 understanding of the invention have been schematically represented, and are not drawn to scale. The electric cable shown in Figure 1 comprises three electrical conductors 1, a first insulating layer 2a (inner layer) around. each electrical 20 conductor 1, a second insulating layer 2b (outer layer) around each insulating first layer 2a, and an outer sheath 3 surrounding the assembly of the three insulated electrical conductors, the insulated electrical conductors having a substantially circular cross section. 25 This outer sheath 3 creates empty spaces 4 between itself and the assembly of insulated electrical conductors it surrounds. This outer sheath 3 is said to be tubing since it leaves the insulated electrical conductors free inside said sheath. 30 The inner layer 2a is made from a first composition comprising a polyorganosiloxane-based polymer matrix, and the outer layer 2b is made from a second composition comprising a polyolefin-based polymer matrix, these two compositions being extruded and crosslinked. 35 The outer sheath 3 is itself made from a flame- WO 2010/055247 PCT/FR2009/052135 12 retardant composition comprising a polyolefin-based polymer matrix. Examples Process for manufacturing an electric cable 5 First, the following compositions are prepared: - composition Col based on polyorganosiloxanes and comprising ceramic-forming fillers, - composition C02 based on EVA and comprising flame retardant fillers, and 10 - composition C03 being a 50/50 mixture of composition Col and of composition C02, compositions Col to C03 also comprising a crosslinking agent of organic peroxide type. To do this, compositions C01 to C03 are mixed, for 15 example in an internal mixer. The mixing temperature of composition C01 is such that it allows the polyorganosiloxane to be softened while at the same time avoiding initiating the decomposition of the organic peroxide. By way of example, the mixing temperature is 20 between 30 0 C and 50 0 C. The mixing temperature of compositions C02 and C03 is, itself, such that it allows the polyolefin to melt (molten state), while at the same time avoiding initiating the decomposition of the organic peroxide. By way of example, the maximum mixing 25 temperature is 115 0 C. Compositions C01 to C03 are then extruded (step i) and deposited around an electrical copper wire 1.78 mm in diameter (2.5 mm 2 circular section of the copper) so as to obtain the following layers: 30 - an insulating layer C1 (monolayer) from composition C01, - an insulating layer C12 (monolayer) from composition C02, - an insulating layer C13 (monolayer) from 35 composition C03, and WO 2010/055247 PCT/FR2009/052135 13 - an insulating layer C14 (bilayer) comprising a first layer C14-1, of identical composition to composition C01, deposited around the electrical wire, and a second layer C14-2, of identical 5 composition to composition C02, deposited around the first layer C14-1. The insulating layers CI1 to C14 all have an identical thickness equal to 0.9 mm. More particularly, compositions C01 and C02 are 10 extruded on said electrical wire, respectively, using two extruders comprising the same extrusion head, composition C02 (outer layer) covering composition C0l (inner layer). This is then referred to as coextrusion of compositions C01 and C02. The insulating layer C14 is 15 thus formed from the inner layer 0.5 mm thick and the outer layer 0.4 mm thick. Next, the insulating layers CIl to C14 are rapidly immersed in a salt bath at 240 0 C so as to crosslink the monolayers CI1 to C13 and the two layers of the 20 insulating layer C14 (step ii), under the action of decomposition of peroxide. The insulated electrical wires thus obtained, noted as insulated wires F1 to F4, have a diameter of about 3.58 mm. 25 In an additional step (step iii), the respective insulated electrical wires F1 to F4 are then assembled in threes using an assembler, the assembling process being well known to those skilled in the art. Finally, a flame-retardant composition comprising a 30 polyolefin-based polymer matrix is extruded in a tubing manner around each group of three assembled electrical conducting wires F1 to F4, to form an outer sheath. The electric cables thus obtained are noted cables CEl to CE4. 35 Tensile strength property WO 2010/055247 PCT/FR2009/052135 14 The tensile strength mechanical properties are determined according to standard NF EN 60811-1-1. To do this, tubular specimens are prepared from the insulating layers of the insulated wires F1 to F4. The 5 specimens thus prepared, the surface area of which is measured precisely, are then tested on a tensile strength test bed with a traction speed of 250 mm/minute. The tensile strength is thus the maximum tensile stress withstood by the specimen during the tensile test 10 up to the point of failure. The results of these tests are collated in Table 1 below. Abrasion resistance property The abrasion resistance mechanical property is 15 determined according to standard EN 50305 part 5.2. To do this, samples corresponding to portions 75 cm long of the insulated wires F1 to F4 are placed in an abrasion test device as described in said standard. Each sample undergoes four tests. Each test is 20 terminated when the cutting edge of said device reaches the conducting core of said insulating wires. The abrasion resistance measurement corresponds to the mean value of the number of cycles performed in the four tests. 25 The results of these tests are collated in Table 1 below. Compression strength property The compression strength mechanical property is determined according to standard EN 50305 part 5.6. 30 To do this, a tensile testing machine functioning in compression mode is used, which is equipped with a device for recording the force required to drive a needle cutting edge onto the insulating layers of insulated wires Fl to F4. A low-voltage detection circuit, designed 35 to stop the machine when the edge crosses the insulating WO 2010/055247 PCT/FR2009/052135 15 envelope, is introduced into the installation. The force applied to the cutting edge that drives it onto the insulating envelope is increased at a constant rate until there is contact with the conducting 5 core. Four tests are performed on the sample, and the force corresponding to the electrical contact is recorded. The results of these tests are collated in Table 1 10 below. Fire resistance properties Standard NF C 32-070 CR1 concerns the duration of functioning of electric cables burning under defined conditions. The fire resistance is the consequence of the 15 production of ash, which must have a certain cohesion making it possible to maintain sufficient insulation for the functioning of the electrical cables. In this test, samples of the electric cables CEl to CE4 are placed in an oven whose temperature reaches 9200C 20 in 50 minutes, and this temperature is then maintained for 15 minutes. During this test, said samples fed with a nominal voltage of 500 V are subjected to regular impacts (every 30 seconds). The test is satisfactory if the sample of cable does not show any electrical failure 25 (breakdown or short circuit) after 65 minutes. The results of these tests are collated in Table 2 below. Insulated wire F1 F2 F3 F4 Tensile 6-8 18 8-10 12 strength (MPa)__________ Abrasion resistance 6-7 / 7-8 210-280 (cycles) Compression 16-17 / 30-40 59-60 WO 2010/055247 PCT/FR2009/052135 16 resistance (N) Table 1 Electric CE1 CE2 CE3 CE4 cable Pass Fail Fail Pass CR1 (> 65 minutes) (< 30 minutes) (< 40 minutes) (> 65 minutes) Table 2 5 The insulated electrical wire F4 that constitutes the electric cable CE4 significantly shows mechanical properties, such as the tensile strength, the abrasion resistance and the compression strength, greater than the electrical wire Fl constituting the electric cable CEl. 10 In addition, the electric cable CE4 satisfies the fire resistance standard NF C 32-070 CR1, which is not the case for the electric cables CE2 and CE3. Finally, the amount of polyorganosiloxane is reduced by about half between the insulating layer C14 in 15 accordance with the invention and the insulating layer CIl, for an identical total thickness of the insulating layer.

Claims (11)

1. Electric cable comprising: - an assembly of insulated electrical conductors, each 5 insulated electrical conductor comprising an electrical conductor (1) surrounded with an insulating layer that is capable of being converted at least superficially into the ceramic state at high temperatures corresponding to fire conditions, and 10 - an outer sheath (3) surrounding the assembly of insulated electrical conductors, empty spaces (4) being provided between said sheath (3) and the assembly of insulated electrical conductors, characterized in that said insulating layer comprises a 15 first crosslinked layer (2a) surrounding the electrical conductor (1), and a second crosslinked layer (2b) surrounding said first layer, the first layer (2a) being obtained from a first composition comprising a polyorganosiloxane-based polymer matrix, and the second 20 layer (2b) being obtained from a second composition comprising a polyolefin-based polymer matrix.
2. Cable according to claim 1, characterized in that the first composition also comprises at least one ceramic-forming filler. 25
3. Cable according to claim 1, characterized in that the second composition also comprises at least one flame-retardant mineral filler and/or at least one ceramic-forming filler.
4. Cable according to any one of the preceding 30 claims, characterized in that the outer sheath (3) comprises a polyolefin-based polymer matrix and at least one hydrated flame-retardant mineral filler.
5. Cable according to any one of the preceding claims, characterized in that said empty spaces (4) 35 occupy at least 10% of the cross section of said cable. WO 2010/055247 PCT/FR2009/052135 18
6. Cable according to any one of the preceding claims, characterized in that it does not comprise any halogenated compounds.
7. Cable according to any one of the preceding 5 claims, characterized in that the thickness of the first layer (2a) is from 0.10 mm to 1.50 mm, and the thickness of the second layer (2b) is from 0.05 mm to 1.50 mm
8. Cable according to claim 7, characterized in that the cross section of the electrical conductor (1) is 10 1.5 mm 2 to 4 mm2
9. Cable according to any one of the preceding claims, characterized in that the first layer (2a) and the second layer (2b) are extruded layers.
10. Cable according to any one of the preceding 15 claims, characterized in that the outer sheath (3) is a tubular sheath.
11. Process for manufacturing an electric cable as defined in claims 1 to 10, characterized in that it comprises the steps consisting in: 20 i. forming the insulating layer of the insulated electrical conductor by extrusion and crosslinking of the first composition and of the second composition around an electrical conductor, 25 ii. assembling at least two insulated electrical conductors as obtained in step i, and iii.extruding an outer sheath in a tubing manner around the assembled insulated electrical conductors of step ii. 30
AU2009315516A 2008-11-13 2009-11-04 Fireproof electric cable Ceased AU2009315516B2 (en)

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FR0857667 2008-11-13
FR0857667A FR2938368B1 (en) 2008-11-13 2008-11-13 FIRE RESISTANT ELECTRICAL CABLE
PCT/FR2009/052135 WO2010055247A1 (en) 2008-11-13 2009-11-04 Fireproof electric cable

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CN103886999A (en) * 2014-03-26 2014-06-25 申环电缆科技有限公司 Power cable for firefighting safety
NL1041590B1 (en) * 2015-11-23 2017-06-26 Beele Eng Bv A multi-layered structure of at least a polymer base-layer and paint-based protective layer or a paste-based protective layer.
CN106057347A (en) * 2016-08-15 2016-10-26 江苏亨通线缆科技有限公司 Long-distance network video transmission fireproof cable and communication system
CN106531302A (en) * 2016-12-29 2017-03-22 河南金水电缆集团有限公司 Firewall cable with rated voltage of 450/750V and below
CN111292890B (en) * 2020-02-18 2022-02-01 四川金力电缆集团有限公司 Fireproof cable and production process thereof
CN112701528A (en) * 2020-12-21 2021-04-23 欧耐特线缆集团有限公司 Fireproof high-voltage photovoltaic cable
CN112992411B (en) * 2021-01-16 2022-07-12 江西江缆科技有限公司 Flexible mineral insulation fireproof cable and preparation method thereof

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US3900681A (en) * 1973-08-22 1975-08-19 Gen Electric Insulated electrical conductor
FR2573910B1 (en) * 1984-11-29 1987-06-19 Habia Cable FLEXIBLE FIRE RESISTANT INSULATION COATING FOR ELECTRICAL CONDUITS, WIRES AND CABLES
DE4437596A1 (en) * 1994-10-20 1996-04-25 Daetwyler Ag Flame-resistant composition for the production of electrical cables with insulation and / or functional integrity
FR2776119B1 (en) * 1998-03-12 2000-06-23 Alsthom Cge Alcatel SECURITY CABLE, RESISTANT TO FIRE AND WITHOUT HALOGEN

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EP2346931B1 (en) 2018-08-29
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AU2009315516B2 (en) 2015-03-19
EP2346931A1 (en) 2011-07-27

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