EP1116243A1 - Isolant pour fil electrique - Google Patents

Isolant pour fil electrique

Info

Publication number
EP1116243A1
EP1116243A1 EP99947633A EP99947633A EP1116243A1 EP 1116243 A1 EP1116243 A1 EP 1116243A1 EP 99947633 A EP99947633 A EP 99947633A EP 99947633 A EP99947633 A EP 99947633A EP 1116243 A1 EP1116243 A1 EP 1116243A1
Authority
EP
European Patent Office
Prior art keywords
layers
wire
layer
acrylate
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99947633A
Other languages
German (de)
English (en)
Other versions
EP1116243B1 (fr
Inventor
Giles Henry Rodway
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tyco Electronics UK Ltd
Original Assignee
Tyco Electronics UK Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tyco Electronics UK Ltd filed Critical Tyco Electronics UK Ltd
Publication of EP1116243A1 publication Critical patent/EP1116243A1/fr
Application granted granted Critical
Publication of EP1116243B1 publication Critical patent/EP1116243B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • H01B3/42—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 polyesters; polyethers; polyacetals
    • 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
    • H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—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 vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • 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

Definitions

  • This invention relates to insulation for electrical wire or cable (hereinafter "wire") in which a strong bond is achieved at an interface between a layer of polyolefm-based material and a layer of polyvinylidene fluoride-based material.
  • the invention is especially useful in multi-layer insulation of electrical wires, making it possible to achieve high- performance bonding between layers of such materials while retaining an acceptable balance in the complex relationships of other wire performance requirements, which are specialised and different from the criteria for other kinds of article such as mouldings or packaging films.
  • PJ Primary jacket
  • pro-rad crosslinking promoter
  • TMPTM trimethylolpropanetrimethacrylate
  • ASTM American Society for Testing and Materials
  • PVDF polyvinylidene fluoride
  • VDF vinylidene fluoride
  • HFP hexafluoropropy lene ;
  • HDPE high density polyethylene
  • EEA ethylene/ethyl acrylate
  • EMA ethylene/methyl acrylate
  • EVA ethylene/vinyl acetate
  • EA ethyl acrylate
  • MA methyl acrylate
  • VA vinyl acetate
  • Dual wall wire insulation comprising a polyolefin inner layer (core) and polyvinylidene fluoride (PVDF) outer layer (primary jacket or PJ) has been commercially available for over 30 years, and is available from several different manufacturers. These products all have negligible adhesion between the inner (polyolefin) and outer (PVDF) layers, which are consequently easily separable. It has been necessary to accept certain disadvantages arising from this lack of bonding, which limits the robustness of the construction. For example, the outer insulation layer can crack and peel off the inner layer if subjected to mechanical stress, exposure to certain fluids, contact with sharp objects, or impact.
  • Abrasion and flexural fatigue resistance of the insulation, as well as resistance to wrinkling on bending (which can cause difficulties in sealing the wire or inserting it into grommets or connectors) are also detrimentally affected by having two readily separable insulation layers. It has not been thought possible to bond layers of two such dissimilar classes of material as polyolefins and PVDFs on a wire at commercially acceptable cost and manufacturing efficiency. Moreover, available bonding techniques could unacceptably affect the wire performance characteristics.
  • the conventional approach to the bonding of polyolefins and PVDF is to employ a tie layer material (e.g. US patent 5,589,028), but these tend to be expensive, and when used on wire may compromise other properties, e.g. heat ageing, and add complexity to the manufacturing process in forming the extra layer. They may also be of limited effectiveness in terms of the bond strength developed.
  • the dissimilar insulation materials of a polyolefm-based core and a polyvinylidene fluoride-based PJ can be bonded together to a significant level of adhesion on an electrical wire or cable; that this bonding tends to reduce or eliminate the aforementioned robustness problems on a wire; and that this bonding can be achieved, contrary to expectation, without unacceptable effects on crack propagation resistance, cost, or on the general balance of wire performance characteristics.
  • the invention accordingly provides an electrical wire having insulation comprising: (i) at least a first layer of a polyolefin-based material comprising, of which at least 20% , preferably at least 40% , more preferably at least 60% or at least 80%, by weight (of the whole material composition) of a carbonyl-containing polymer (homopolymer or copolymer or terpolymer) having a non-aromatic backbone, of which polymer the or at least one constituent monomer is a carboxylic acid ester, preferably an acrylate or acetate, especially an alkyl acrylate (preferably methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate), the said monomer itself constituting at least 5%, preferably at least 9%, more preferably at least 15% by weight of the said co-, or ter- polymer when used, and the remainder of the said co-, or ter- polymer preferably being derived from olefinic monomer, preferably
  • an electrical wire having insulation comprising:
  • At least a first layer of a polyolefin-based formulation of which at least 20% , preferably at least 40% , more preferably at least 60% or very preferably at least 80% of the weight of the polymeric portion of the said formulation consists of a carbonyl- containing polymer (homopolymer or copolymer or terpolymer), of which polymer the or at least one constituent monomer is a carboxylic acid ester, preferably an acrylate or acetate, especially an alkyl acrylate (preferably methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate), the said monomer itself constituting at least 5% , preferably at least 9% , more preferably at least 15% by weight of the said co-, or ter- polymer when used, and the remainder or the majority of the remainder of the said co-, or ter- polymer preferably being derived from olefmic monomer, preferably ethylene; in contact with (ii)
  • the respective layers have been brought into contact with each other at a temperature above the melting or softening point of the polymeric material in at least one of the layers, thus tending to maximise the intimacy of their interfacial contact and so possibly encouraging the formation of adhesion-promoting interfacial cross-links in the subsequent cross-linking reaction.
  • the polvolefin-based layer (i) in addition to the polymeric portion of the formulation, for which the requirements are stipulated above, may contain whatever else is required in the way of additives such as anti-oxidants, pigments, fillers, flame retardants, etc, as known per se, to give the required mechanical, thermal, electrical etc. properties to the polymer.
  • the polyvinylidene fluoride-based layer (ii) also may contain other additives as known per se to give it required properties in addition to bonding.
  • the bond strength described in this application can be measured in terms of peel strength between bonded strips of the two materials in question.
  • a standard method which can be used for such a test is ASTM 1876-95. By this definition, a significant bond could be one for which the peel force exceeds 5N, and a strong bond one of peel force greater than ION.
  • a convenient method for gauging the bond strength between the said layers, (i) and (ii), when they have been fabricated onto a wire is to place a sample wire, of total length 60mm, into acetone (e.g. Fisher Scientific UK, AR certified grade acetone), to a depth of acetone equivalent to 70% of the length of sample wire, at 23 (+/- 3)°C, for a period of 1 hour.
  • acetone e.g. Fisher Scientific UK, AR certified grade acetone
  • Wires with negligible bonding of the insulation layers experience an extension of the PVDF PJ, along the axis of the wire, that is independent of any extension of the polyolefin core, and/or wrinkling of the PJ such that it delaminates from the core in places.
  • the above-mentioned extension of the PJ typically results in a PJ "tube" extending for 1mm or more beyond the cut end of the core in the sample wire, following the above test.
  • Wires with significantly bonded insulation layers experience an extension of the core and PJ, together, without separation, beyond the cut edge of the conductor, along the axis of the wire and/or wrinkling of the core and PJ layers together, without delamination. Any such wrinkling of the core and PJ together can be distinguished from wrinkling of the PJ only by examining a cross-section of the wrinkles under a microscope.
  • Methods of fabricating the wire may include any process which causes intimate contact between the above-mentioned layers (i) and (ii). Examples include coating of one material onto a pre-formed layer of the other, dual or multi-walled extrusion to form insulation layers respectively containing one or other of the aforementioned two classes of material.
  • the olefin-based material (i) is preferably the inner layer and the PVDF-based layer (ii) preferably the outer layer on the wire.
  • the layers made from the two different materials could be coextruded, tandem extruded, multipass extruded, or coated by other means.
  • Known wire insulation processes such as tube draw-down extrusion may be used, to form one or more of the layers, but pressure extrusion as known per se is preferred for optimum adhesion of the second and any subsequent insulation layers to be applied to a pre-formed underlying layer.
  • the insulation on the wire is exposed to a cross-linking reaction, which may involve chemical reagents such as peroxides, but preferably is effected by radiation, especially from a source of ionising radiation capable of causing the formation of free radicals and thus, cross-links, in the polymers, some of which should preferably be formed in the region of the interface between the two materials.
  • the radiation source could, for example, be a radio-isotope, or an X-ray source, or possibly a non-ionising radical-generating source, for example a UV source, but is preferably an electron beam, more preferably one providing a beam dose greater than 2 Mrads, preferably at least 5 Mrads, more preferably at least 10 Mrads, very preferably at least 15Mrads, into the material.
  • Additives preferably include a cross-linking promoter ("pro-rad") in the polyolefin-based material and/or in the PVDF-based material.
  • cross-linking promoter e.g., pro-rad
  • Known cross-linking materials may be used, preferably methacrylate/acrylate based ones, and, very preferably, those of the type trimethylolpropanetrimethacrylate (TMPTM), in the polyolefin material and/or in the PVDF-based material.
  • TMPTM trimethylolpropanetrimethacrylate
  • Pressing pressure 20-40 Tons over a 300mm by 300mm metal plate Cooling conditions: 2 minutes between water cooled, 300mm by 300mm, metal plates, at a pressure as above
  • suBs ⁇ r ⁇ iJTE SHEET (RULE 26)
  • the inner layer of insulation i.e. nearer to the wire conductor
  • This layer was pressure extruded onto the metallic conductor.
  • the outer layer of insulation consisted predominantly of a PVDF/HFP copolymer containing 10wt% HFP, which in this example contains a crosslinking promoter, and other known additives such as pigments, plasticisers, stabilisers, antioxidants and process aids in usual proportions totalling 7.5wt% ..
  • This outer layer was pressure extruded in a separate operation onto the pre-formed inner layer.
  • This coated wire product was then passed through an electron beam, and received a radiation dose of 20Mrads.
  • a wire was made as above, in which the crosslinking promoter in the inner layer was 4% TMPTM, and the outer layer of insulation was comprised solely of the PVDF/HFP copolymer containing 10wt% HFP.
  • This coated wire product was then passed through an electron beam, and received a radiation dose of 20 Mrads.
  • This wire was subjected to the acetone immersion test, confirming that the insulation layers were significantly bonded together.
  • a wire of the same construction as the second example was made by tandem pressure extrusion of the inner and outer insulation layers. This coated wire product was then passed through an electron beam, and received a radiation dose of 20 Mrads. This wire was subjected to the acetone immersion test, confirming that the insulation layers were significantly bonded together.
  • wire A A wire of the above construction and manufacturing process
  • wire B a market leading commercially available polyolefm/PVDF dual-walled wire
  • Equipment conventional type wire scrape abrader, wire size

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Inorganic Insulating Materials (AREA)
  • Resistance Heating (AREA)
  • Processes Specially Adapted For Manufacturing Cables (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Die Bonding (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Communication Cables (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un fil ou un câble électrique muni d'un isolant qui comprend ce qui suit: (i) au moins une première couche d'une formulation à base de polyoléfine dont au moins 20 %, de préférence au moins 40 %, si possible au moins 60 % et dans le meilleur des cas au moins 80 % du poids de la partie polymère de ladite formulation sont constitués d'un polymère carbonylé (homopolymère ou copolymère ou terpolymère), au moins un constituant monomère dudit polymère (ou son unique constituant) est un ester d'acide carboxylique, de préférence un acrylate ou un acétate, mieux un acrylate d'alkyle (de préférence, acrylate de méthyle, acrylate d'éthyle, acrylate de propyle ou acrylate de butyle), ledit monomère représentant au moins 5 %, de préférence au moins 9 %, si possible au moins 15 % du poids dudit co- ou ter- polymère, le reste ou la plus grande partie du reste dudit co- ou terpolymère ayant été de préférence dérivée d'un monomère oléfinique, de préférence de l'éthylène; ladite couche est en contact avec (ii) au moins une deuxième couche d'une autre formulation de matériau qui contient au moins 10 %, si possible au moins 50 %, dans le meilleur des cas au moins 90 % et dans l'idéal 100 % en poids de la deuxième couche de fluorure de polyvinylidine (PVDF), de préférence d'un copolymère à base de VDF avec un comonomère partiellement ou complètement fluoré, si possible d'un copolymère de VDF et de hexafluoropropylène (HFP); lesdites couches (i) et (ii), en contact l'une avec l'autre, ayant été soumises à la réaction de réticulation, de préférence par rayonnement, si possible par rayonnement ionisant suffisant soit pour empêcher le délaminage des deux couches lors d'un test d'immersion dans l'acétone pendant 1 heure à 23 °C soit pour porter la résistance au délaminage de la liaison collée à 5N au moins conformément au procédé -STM B1876-95 décrit ci-dessous, de préférence, pour augmenter la résistance du collage d'au moins 50 %, si possible d'au moins 100 %, voire d'au moins 500 % ou même de 1000 % en comparaison aux couches non réticulées.
EP99947633A 1998-09-17 1999-09-17 Isolant pour fil electrique Expired - Lifetime EP1116243B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9820214.6A GB9820214D0 (en) 1998-09-17 1998-09-17 Bonding polymer interface
GB9820214 1998-09-17
PCT/GB1999/003116 WO2000017889A1 (fr) 1998-09-17 1999-09-17 Isolant pour fil electrique

Publications (2)

Publication Number Publication Date
EP1116243A1 true EP1116243A1 (fr) 2001-07-18
EP1116243B1 EP1116243B1 (fr) 2006-03-22

Family

ID=10838985

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99947633A Expired - Lifetime EP1116243B1 (fr) 1998-09-17 1999-09-17 Isolant pour fil electrique

Country Status (22)

Country Link
EP (1) EP1116243B1 (fr)
JP (1) JP2002525819A (fr)
KR (1) KR100638181B1 (fr)
CN (1) CN1331160C (fr)
AT (1) ATE321345T1 (fr)
AU (1) AU766430B2 (fr)
BR (1) BR9913843A (fr)
CA (1) CA2340386C (fr)
CZ (1) CZ299046B6 (fr)
DE (1) DE69930532T2 (fr)
ES (1) ES2260937T3 (fr)
GB (1) GB9820214D0 (fr)
HU (1) HU226699B1 (fr)
ID (1) ID29877A (fr)
IL (2) IL141338A0 (fr)
NO (1) NO324458B1 (fr)
PL (1) PL192515B1 (fr)
RO (1) RO121928B1 (fr)
RU (1) RU2231147C2 (fr)
TR (1) TR200100761T2 (fr)
WO (1) WO2000017889A1 (fr)
ZA (1) ZA200101181B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2888389A1 (fr) * 2005-07-05 2007-01-12 Arkema Sa Structure multicouche isolante
WO2019224452A1 (fr) * 2018-05-22 2019-11-28 Arkema France Cables multicouches pour environnement offshore

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0006333D0 (en) 2000-03-16 2000-05-03 Raychem Ltd Electrical wire insulation
JP2002225204A (ja) * 2001-01-30 2002-08-14 Reitekku:Kk 改質フッ素樹脂被覆材およびその製造方法
FR2856404B1 (fr) * 2003-06-06 2008-08-08 Atofina Procede de greffage de polymere fluore et structures multicouches comprenant ce polymere greffe
US7241817B2 (en) 2003-06-06 2007-07-10 Arkema France Process for grafting a fluoropolymer and multilayer structures comprising this grafted polymer
WO2007006897A2 (fr) * 2005-07-05 2007-01-18 Arkema France Structure multicouche isolante
CN100370556C (zh) * 2005-12-01 2008-02-20 上海交通大学 不饱和羧酸盐改性的抗水树绝缘材料及制备方法
KR100716381B1 (ko) * 2006-02-15 2007-05-11 엘에스전선 주식회사 전선 피복용 절연재 제조용 조성물 및 이를 이용하여제조된 전선
CN101117393B (zh) * 2006-08-04 2011-03-16 上海尚聚化工科技有限公司 多层核壳结构的含氟聚合物颗粒及含有它的热塑性聚烯烃制品
US8007857B1 (en) * 2006-09-08 2011-08-30 Abbott Cardiovascular Systems Inc. Methods for controlling the release rate and improving the mechanical properties of a stent coating
CN102667967B (zh) * 2009-11-10 2014-04-16 大金工业株式会社 电线、电线管及其制造方法
GB2479371B (en) * 2010-04-07 2014-05-21 Tyco Electronics Ltd Uk Primary wire for marine and sub-sea cable
US9536635B2 (en) 2013-08-29 2017-01-03 Wire Holdings Llc Insulated wire construction for fire safety cable
CN106128627A (zh) * 2015-07-26 2016-11-16 常熟市谷雷特机械产品设计有限公司 一种电力用高压电缆
RU2606500C1 (ru) * 2015-09-17 2017-01-10 Акционерное общество "Лидер-Компаунд" Пероксидносшиваемая композиция для изоляции силовых кабелей

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Publication number Priority date Publication date Assignee Title
US3269862A (en) * 1964-10-22 1966-08-30 Raychem Corp Crosslinked polyvinylidene fluoride over a crosslinked polyolefin
US3650827A (en) * 1969-11-17 1972-03-21 Electronized Chem Corp Fep cables
US5206459A (en) * 1991-08-21 1993-04-27 Champlain Cable Corporation Conductive polymeric shielding materials and articles fabricated therefrom
US5589028A (en) * 1994-11-03 1996-12-31 Elf Atochem North America, Inc. Bonding method employing tie layers for adhering polyethylene to fluoropolymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0017889A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2888389A1 (fr) * 2005-07-05 2007-01-12 Arkema Sa Structure multicouche isolante
WO2019224452A1 (fr) * 2018-05-22 2019-11-28 Arkema France Cables multicouches pour environnement offshore
FR3081602A1 (fr) * 2018-05-22 2019-11-29 Arkema France Cables multicouches pour environnement offshore

Also Published As

Publication number Publication date
PL192515B1 (pl) 2006-10-31
CN1331160C (zh) 2007-08-08
KR20010079751A (ko) 2001-08-22
IL141338A (en) 2006-12-31
CZ2001482A3 (cs) 2001-07-11
WO2000017889A1 (fr) 2000-03-30
DE69930532T2 (de) 2007-03-08
CA2340386A1 (fr) 2000-03-30
ATE321345T1 (de) 2006-04-15
CZ299046B6 (cs) 2008-04-09
NO20011307D0 (no) 2001-03-15
PL346214A1 (en) 2002-01-28
RO121928B1 (ro) 2008-07-30
NO20011307L (no) 2001-03-15
AU766430B2 (en) 2003-10-16
DE69930532D1 (de) 2006-05-11
NO324458B1 (no) 2007-10-22
BR9913843A (pt) 2001-08-14
ZA200101181B (en) 2002-05-13
CA2340386C (fr) 2009-04-14
ID29877A (id) 2001-10-18
AU6101999A (en) 2000-04-10
HUP0103585A3 (en) 2002-04-29
JP2002525819A (ja) 2002-08-13
GB9820214D0 (en) 1998-11-11
KR100638181B1 (ko) 2006-10-26
ES2260937T3 (es) 2006-11-01
IL141338A0 (en) 2002-03-10
HU226699B1 (en) 2009-07-28
EP1116243B1 (fr) 2006-03-22
CN1318200A (zh) 2001-10-17
HUP0103585A2 (hu) 2002-01-28
TR200100761T2 (tr) 2001-09-21
RU2231147C2 (ru) 2004-06-20

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