EP0103487B1 - Elektrische Isolierung - Google Patents

Elektrische Isolierung Download PDF

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Publication number
EP0103487B1
EP0103487B1 EP83305380A EP83305380A EP0103487B1 EP 0103487 B1 EP0103487 B1 EP 0103487B1 EP 83305380 A EP83305380 A EP 83305380A EP 83305380 A EP83305380 A EP 83305380A EP 0103487 B1 EP0103487 B1 EP 0103487B1
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Prior art keywords
radical
polymer
aromatic
carbon atoms
article according
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EP83305380A
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English (en)
French (fr)
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EP0103487A2 (de
EP0103487A3 (en
Inventor
Stephen Leroy Tondre
Hans Edmund Lunk
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Raychem Corp
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Raychem Corp
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Priority to AT83305380T priority Critical patent/ATE21462T1/de
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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
    • 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

  • This invention relates to insulation for electrical articles.
  • electrical insulation must meet a variety of electrical and physical requirements under normal service conditions. In addition, for many purposes the insulation must meet test requirements which are intended to ensure that if the insulation is exposed to very high temperatures, e.g. in a fire, it will not evolve excessive amounts of toxic products or smoke. These requirements are particularly severe for electrical cable which is to be used in aircraft and similar equipment.
  • the term "cable” is used herein to include a single electrically insulated elongate conductor often referred to in the art as "wire"), an article comprising a plurality of separate elongate conductors each of which is separately insulated, and an article comprising a plurality of elongate conductors which are physically joined together but electrically insulated from each other by insulating material, e.g. ribbon cable.
  • Fluorocarbon polymers especially ethylene/tetrafluoroethylene (ETFE) copolymers such as Tefzel, are used extensively for electrical insulation, in particular for aircraft wire. Particularly when crosslinked, such polymers can exhibit an excellent combination of physical and electrical properties under normal service conditions.
  • EFE ethylene/tetrafluoroethylene
  • Tefzel ethylene/tetrafluoroethylene copolymers
  • U.S. Patents Nos. 3,580,829, 3,738,923, 3,763,222, 3,840,619, 3,894,118, 3,911,192, 3,947,525, 3,970,770, 3,985,716, 3,995,091, 4,031,167, 4,155,823, 4,121,001, and 4,176,027 Other polymers which have been used for electrical insulation include other olefin polymers (both homopolymers and copolymers) and various high-melting aromatic polymers.
  • Examples of the use of such polymers include the wire and cable described in EP-A-56510 in which an ethylene tetrafluoroethylene or a tetrafluoroethylene coated polyimide primary insulation is provided with a solution coated polyimide topcoat followed by a layer of polyvinylidine fluoride.
  • Another form of cable is described in US ⁇ A ⁇ 3,217,084, in which a tape of polyethylene terephthalate or polycarbonate is wrapped under tension around a solid polyethylene or polypropylene insulating layer.
  • the olefin polymer forming the inner layer preferably has a tensile (Young's) modulus of at least 138 MPa (20,000 p.s.i.) especially at least 207 MPa (30,000 p.s.i.) and particularly at least 276 MPa (40,000 p.s.i.) in order to minimize wrinkling of the outer layer when the article, e.g. in the form of a wire, is bent.
  • a tensile (Young's) modulus of at least 138 MPa (20,000 p.s.i.) especially at least 207 MPa (30,000 p.s.i.) and particularly at least 276 MPa (40,000 p.s.i.) in order to minimize wrinkling of the outer layer when the article, e.g. in the form of a wire, is bent.
  • the insulation of the article to the invention provides a valuable combination of physical and electrical properties.
  • the outer layer provides excellent resistance to physical abuse.
  • the inner layer is more flexible than the outer layer and thus provides insulation which is more flexible, for a particular dielectric strength, than insulation which is composed only of the aromatic polymer.
  • the aromatic polymers often have poor resistance to stress-cracking which can seriously reduce their dielectric strength, the olefin polymers do not suffer from this disadvantage, and the inner jacket will therefore provide continuous insulation even in environments which cause stress-cracking of the outer jacket.
  • olefin polymer as used herein is defined as being a polymer of one or more unsubstituted and/or substituted olefins. Where the polymer includes substituted olefins as monomers or comonomers they are preferably polar monomers and especially fluorine-containing monomers, e.g. tetrafluoroethylene, or a carboxylic ester, in particular an alkyl acrylate, e.g. methyl or ethyl acrylate, or a vinyl ester, e.g. vinyl acetate.
  • the olefin is preferably a fluorocarbon polymer as explained below.
  • the inner layer is composed of a cross-linked fluorocarbon layer.
  • the combination of an inner layer of a cross-linked fluorocarbon polymer and an outer layer of an aromatic polymer results in a completely unexpected reduction in the smoke evolved under standard test conditions.
  • electrical wire which, when tested for smoke evolution by ASTM E 662-79 (flaming mode) has a D m value of less than 50, preferably less than 35, where D m is the maximum specific optical density.
  • fluorocarbon polymer is used herein to denote a polymer or mixture of polymers which contains more than 10%, preferably more than 25%, by weight of fluorine.
  • the fluorocarbon polymer may be a single fluorine-containing polymer, a mixture of two or more fluorine-containing polymers, or a mixture of one or more fluorine-containing polymers with one or more polymers which do not contain fluorine.
  • the fluorocarbon polymer comprises at least 50%, particularly at least 75% especially at least 85%, by weight of one or more thermoplastic crystalline polymers each containing at least 25% by weight of fluorine, a single such crystalline polymer being preferred.
  • Such a fluorocarbon polymer may contain, for example, a fluorine-containing elastomer and/or a polyolefin, preferably a crystalline polyolefin, in addition to the crystalline fluorine-containing polymer or polymers.
  • the fluorine-containing polymers are generally homo- or copolymers of one or more fluorine-containing olefinically unsaturated monomers, or copolymers of one or more such monomers with one or more olefins.
  • the fluorocarbon polymer usually has a melting point of at least 150°C, and will often have a melting point of at least 250°C, e.g.
  • the melting point being defined for crystalline polymers as the temperature above which no crystallinity exists in the polymer (or when a mixture of crystalline polymers is used, in the major crystalline component in the mixture).
  • the polymeric composition, prior to cross-linking has a viscosity of less than 10 4 Pa.s (10 5 poise) at a temperature not more than 60°C above its melting point.
  • a preferred fluorocarbon polymer is a copolymer of ethylene and tetrafluoroethylene and optionally one or more other comonomers (known as ETFE polymers), especially a copolymer comprising 35 to 60 mole percent of ethylene, 35 to 60 mole percent of tetrafluoroethylene and up to 10 mole percent of one or more other comonomers.
  • ETFE polymers comonomers
  • polymers which can be used include copolymers of ethylene and chlorotrifluoroethylene; polyvinylidene fluoride; copolymers of vinylidene fluoride with one or both of hexafluoropropylene and tetrafluoroethylene, or with hexafluoroisobutylene; and copolymers of tetrafluoroethylene and hexafluoropropylene.
  • Either or both of the inner and outer insulating layers can optionally contain suitable additives such as pigments, antioxidants, thermal stabilisers, acid acceptors and processing aids.
  • Such polymers include polyketones, polyether ketones, polyether ether ketones and polyether sulfones, polyether ketone/sulfone copolymers and polyether imides. Blends of different polymers can be used.
  • Preferred aromatic polymers are crystalline polymers with a melting point of at least 250°C, particularly at least 300°C.
  • the polymer comprises, and preferably consists essentially of, units of the general formula the units being the same or different, wherein Ar represents a divalent aromatic radical and Q represents ⁇ 0 ⁇ , ⁇ S ⁇ , ⁇ S0 2 ⁇ , ⁇ CO ⁇ , -NH-CO or -COO-, or Ar represents a polyvalent radical and Q represents each bond of the Q radical preferably being bonded directly to an aromatic carbon atom.
  • the aromatic polymer is a crystalline polyarylene ether comprising recurring units of the formula where E is the residue of a dihydric phenol and E' is the residue of an aromatic compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, the E and E' radicals being linked to the -0- radicals through aromatic carbon atoms.
  • E is a radical of the formula wherein R is a divalent radical; x is 0 or 1; Y is a radical selected from halogen atoms, alkyl radicals containing 1 to 4 carbon atoms and alkoxy radicals containing 1 to 4 carbon atoms; yisO, 1,2,3 or 4; Y' is a radical selected from halogen atoms, alkyl radicals containing 1 to 4 carbon atoms and alkoxy radicals containing 1 to 4 carbon atoms; z is 0, 1, 2, 3 or 4, and E' is a radical of the formula wherein R' is a sulfone, carbonyl, vinyl, sulfoxide, azo, saturated fluorocarbon, organic phosphine oxide or ethylidene radical.
  • polysulfones are those in which y and z are 0, x is 1, R' is a sulfone radical and R is a radical of the formula wherein each of R" and R"' is independently selected from the group consisting of hydrogen; alkyl radicals containing 1 to 4 carbon atoms; halogen-substituted alkyl radical containing 1 to 4 carbon atoms; aryl, alkaryl and aralkyl radicals containing 6 to 10 carbon atoms; and halogen-substituted aryl, alkaryl and aralkyl radicals containing 6 to 10 carbon atoms.
  • the polymer is a polyether imide or polysulfone imide which comprises recurring units of the formula where Q is -0- or -S0 2 , Z is a trivalent aromatic radical, R is a divalent aromatic radical and R' is a divalent organic radical.
  • Preferred aromatic polymers consist essentially of repeating units having one of the following formulae wherein each of x, m and n is 0 or 1, with n being 0 when x is 1, p is an integer from 1 to 4, with m being 1 and x being 0 when p is greater than 1, e.g.,
  • the insulated articles of the present invention can be produced by conventional techniques; the inner layer usually contacts the conductor, and the inner and outer layers generally constitute the total insulation of the article; however, other insulating layers can be present.
  • the olefin polymer is preferably cross-linked by radiation, and cross-linking can be effected before or after the aromatic polymer (which is generally not cross-linked by radiation) is applied.
  • the inner layer will usually be of annular cross- section of thickness for example 76.2 to 381 micrometres (3 to 15 mils), preferably 101.6 to 177.8 micrometres (4 to 7 mils) and the outer insulating layer will be a melt extruded layer which surrounds and contacts the inner insulating layer and preferably has a wall thickness of from 101.6 to 177.8 micrometres.
  • the cable can comprise a plurality of conductors, each of which has an inner insulating layer around it, with the conductors being joined together and further insulated by the outer insulating layer.
  • the invention is illustrated by the following Examples, Examples 1, 2, 3 and 8 of which are comparative.
  • a 20 AWG stranded (19/32) conductor was extrusion-coated with an inner insulating layer having the composition and thickness shown in the Table. Except in Examples 1 and 2, the inner insulating layer was then extrusion-coated with an outer insulating layer having the composition and thickness shown in the Table.
  • the coated conductor was irradiated to a dosage of about 10 Megarads to cross-link the inner coating; in these Examples, the inner coating also contained, when it was irradiated, a suitable amount of a radiation cross-linking agent.
  • the outer coating was substantially unaffected by this irradiation.
  • the coated conductor was annealed at 180°C for 1 hour.
  • PEEK, Ultem and PES are substantially linear aromatic polymers.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Claims (10)

1. Ein isolierter elektrischer Gegenstand, umfassend
(a) einen Stromleiter;
(b) eine schmelzgeformte innere Isolierschicht, umfassend eine erste organische Polymerkomponente, die ein vernetztes Olefinpolymeres ist; und
(c) eine schmelzgeformte äussere Isolierschicht, die die innere Isolierschicht berührt und eine zweite organische Polymerkomponente umfasst, die ein im wesentlichen lineares aromatisches Polymeres von einer Glasübergangstemperatur von mindestens 100°C ist.
2. Ein Gegenstand nach Anspruch 1, in dem das Olefinypolymere mindestens 75 Gew.% eines thermoplastischen kristallinen Polymeren umfasst, mindestens 25 Gew.% Fluor enthaltend.
3. Ein Gegenstand nach Anspruch 1 oder 2, in dem das Olefinpolymere im wesentlichen aus einem Ethylen/Tetrafluorethylencopolymeren, einem Ethylen/Chlortrifluorethylencopolymeren oder einem Vinylidenfluoridpolymeren besteht.
4. Ein Gegenstand nach einem der Ansprüche 1 bis 3, in dem das aromatische Polymere eine Glasübergangstemperatur von mindestens 130°C hat und/oder ein kristallines Polymeres von einem Schmelzpunkt von mindestens 250°C ist.
5. Ein Gegenstand nach einem der Ansprüche 1 bis 4, in dem das aromatische Polymere Einheiten der allgemeinen Formel
Figure imgb0028
umfasst, wobei die Einheiten gleich oder unterschiedlich sind und Ar einen zweiwertigen aromatischen Rest und Q einen Rest der Formel
Figure imgb0029
oder Ar einen mehrwertigen aromatischen Rest und Q
Figure imgb0030
darstellt, wobei jede Bindung des Q-Restes vorzugsweise direkt an ein aromatisches Kohlenstoffatom gebunden ist.
6. Ein Gegenstand nach einem der Ansprüche 1 bis 5, in dem das aromatische Polymere ein kristalliner Polyarylenether ist, der wiederkehrende Einheiten der allgemeinen Formel
Figure imgb0031
umfasst, worin E der Rest eines zweiwertigen Phenols und E' der Rest einer aromatischen Verbindung mit einer elektronenabziehenden Gruppe in mindestens einer der Stellungen ortho und para zu den Valenzbindungen ist und die Reste E und E' an die -O-Reste durch aromatische Kohlenstoffatome gebunden sind.
7. Ein Gegenstand nach Anspruch 6, in dem E ein Rest der Formel
Figure imgb0032
ist, worin R einen zweiwertigen Rest, X 0 oder 1, Y ein Halogenatom, einen Alkylrest mit 1 bis 4 C-Atomen oder einen Alkoxyrest mit 1 bis 4 C-Atomen, y 0 oder eine ganze Zahl von 1 bis 4, Y' ein Halogenatom, einen Alkylrest mit 1 bis 4 C-Atomen oder einen Alkoxyrest mit 1 bis 4 C-Atomen und z 0 oder eine ganze Zahl von 1 bis 4 und E' einen Rest der Formel
Figure imgb0033
darstellt, worin R' ein Sulfon-, Carbonyl-, Vinyl-, Sulfoxid-, Azo-, gesättigter Fluorkohlenstoff-, organischer Phosphinoxid-oder Ethylidenrest ist.
8. Ein Gegenstand nach Anspruch 7, in dem y und z 0 sind, x 1 ist, R' ein Sulfonrest und R ein Rest der Formel
Figure imgb0034
ist, worin jedes von R" und RU' unabhängig ein Wasserstoffatom, ein Alkylrest mit 1 bis 4 C-Atomen, ein halogensubstituierter Alkylrest mit 1 bis 4 C-Atomen, ein Aryl-, Alkaryl- oder Aralkylrest mit 6 bis 10 C-Atomen oder ein halogensubstituierter Aryl-, Alkaryl- oder Aralkylrest mit 6 bis 10 C-Atomen sind.
9. Ein Gegenstand nach einem der Ansprüche 1 bis 4, in dem das aromatische Polymere im wesentlichen aus wiederkehrenden Einheiten der Formel besteht
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
worin jedes von x, m und n 0 bis 1 ist, wobei n 0 ist, wenn x 1 ist, und p eine ganze Zahl von 1 bis 4 ist, wobei m 1 und x 0 ist, wenn p grösser als 1 ist.
10. Ein Gegenstand nach einem der Ansprüche 1 bis 9 in Form eines elektrischen Drahtes oder Kabels, dessen innere Isolierschicht eine schmelzextrudierte Schicht ist, die den elektrischen Leiter umgibt und berührt und vorzugsweise eine Wandstärke von 101,5 bis 177,8 Mikrometer hat und dessen äussere Isolierschicht eine schmelzextrudierte Schicht ist, die die innere lsolierschicht umgibt und berührt und vorzugsweise eine Wandstärke von 101,6 bis 177,8 Mikrometer hat.
EP83305380A 1982-09-15 1983-09-14 Elektrische Isolierung Expired EP0103487B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83305380T ATE21462T1 (de) 1982-09-15 1983-09-14 Elektrische isolierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41835582A 1982-09-15 1982-09-15
US418355 1982-09-15

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EP0103487A2 EP0103487A2 (de) 1984-03-21
EP0103487A3 EP0103487A3 (en) 1984-08-01
EP0103487B1 true EP0103487B1 (de) 1986-08-13

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EP (1) EP0103487B1 (de)
JP (1) JPS5973807A (de)
AT (1) ATE21462T1 (de)
CA (1) CA1214528A (de)
DE (1) DE3365309D1 (de)
GB (1) GB2127210B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH664230A5 (de) * 1984-02-08 1988-02-15 Huber+Suhner Ag Isolierte, elektrische leitung.
GB8716307D0 (en) * 1987-07-10 1987-08-19 Raychem Ltd Electrical wire
GB8716305D0 (en) * 1987-07-10 1987-08-19 Raychem Ltd Electrical wire
DE3852977T2 (de) * 1987-07-29 1995-07-06 Sumitomo Electric Industries Formkörper auf Basis einer Harzzusammensetzung.
JP3073545B2 (ja) * 1990-05-23 2000-08-07 株式会社フジクラ 絶縁電線及びこれを使用したケーブル
JPH04108810U (ja) * 1991-03-07 1992-09-21 古河電気工業株式会社 絶縁電線
JP3233655B2 (ja) * 1991-05-24 2001-11-26 株式会社フジクラ 難燃性電気ケーブル
TW374181B (en) * 1996-08-22 1999-11-11 Furukawa Electric Co Ltd Multilayer insulated wire and transformer using the same
GB2329278B (en) * 1997-07-14 2002-01-16 Delta Crompton Cables Ltd Co-axial cables
JP5258022B2 (ja) * 2008-02-18 2013-08-07 古河マグネットワイヤ株式会社 コイル用絶縁電線

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294604A (en) * 1960-12-20 1966-12-27 Anaconda Wire & Cable Co Method of making electric cable having compressed insulation
US3217084A (en) * 1960-12-20 1965-11-09 Anaconda Wire & Cable Co Electric cable having compressed insulation
US4184001A (en) * 1978-04-19 1980-01-15 Haveg Industries, Inc. Multi layer insulation system for conductors comprising a fluorinated copolymer layer which is radiation cross-linked
EP0040034A1 (de) * 1980-05-08 1981-11-18 BICC Limited Isolierte Drähte und elektrische Kabel
JPS57130304A (en) * 1981-02-02 1982-08-12 Chiyanpurein Cable Corp Insulating system for wire or cable

Also Published As

Publication number Publication date
GB8324662D0 (en) 1983-10-19
JPH0517642B2 (de) 1993-03-09
DE3365309D1 (en) 1986-09-18
CA1214528A (en) 1986-11-25
GB2127210A (en) 1984-04-04
EP0103487A2 (de) 1984-03-21
GB2127210B (en) 1986-01-22
JPS5973807A (ja) 1984-04-26
EP0103487A3 (en) 1984-08-01
ATE21462T1 (de) 1986-08-15

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