Electrical insulation

Description

[0001] This invention relates to insulation for electrical articles.

[0002] 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.

[0003] 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. In this connection, reference may be made to 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.

[0004] 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.

[0005] We have discovered that insulation which has improved properties and which can be efficiently manufactured comprises an inner layer of a cross-linked melt-extruded olefin polymer covered by a layer of a melt extruded aromatic polymer having a glass transition temperature of at least 100°C. Accordingly, the present invention provides an insulated electrical article, especially an insulated electrical wire or cable comprising:

(a) a conductor;

(b) a melt-shaped, preferably melt-extruded, inner insulating layer which preferably contacts the conductor and comprises a first organic polymer component which is a cross-linked olefin polymer, particularly an ETFE copolymer, and

(c) a melt-shaped, preferably melt-extruded, outer insulating layer which contacts the inner insulating layer and which comprises a second organic polymer component which is a substantially linear aromatic polymer having a glass transition temperature of at least 100°C, preferably at least 130°C.

[0006] 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.

[0007] 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. Furthermore, 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.

[0008] The term "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.

[0009] Particularly useful properties are obtained when the inner layer is composed of a cross-linked fluorocarbon layer. We have discovered that 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. Thus it is possible, through use of the present invention, to manufacture 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.

[0010] The term "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. Thus 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. In one preferred class, 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. up to 350°C, 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). Preferably the polymeric composition, prior to cross-linking, has a viscosity of less than 10⁴ Pa.s (10⁵ 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. Other specific 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.

[0011] 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.

[0012] The aromatic polymers which are used in this invention are well known to those skilled in the art, and reference may be made for example to U.S. Patents Nos. 3,025,605, 3,354,129, 3,441,538, 3,442,538, 3,446,654, 3,658,938, 3,838,097, 3,847,867, 3,953,400, 3,956,240, 4,107,147, 4,108,837, 4,111,908, 4,175,175, 4,293,670, 4,320,224, and 3,446,654 and British Patents Nos. 971,227, 1,369,210 and 1,599,106. 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. In one class of such polymers 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―, ―S0₂―, ―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.

[0013] In another class of aromatic polymers 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. In one preferred sub-class, 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. In this class preferred 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.

[0014] In another class of aromatic polymers, the polymer is a polyether imide or polysulfone imide which comprises recurring units of the formula

where Q is -0- or -S0₂, Z is a trivalent aromatic radical, R is a divalent aromatic radical and R' is a divalent organic radical.

[0015] 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.,

[0016] 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. For electrical cable, 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. Alternatively, 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.

[0017] The invention is illustrated by the following Examples, Examples 1, 2, 3 and 8 of which are comparative.

Examples

[0018] In each of the Examples, 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. In some of the Examples, as designated 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. Samples of the resulting cable were tested in accordance with the procedure of ASTM E662-79 (flaming mode), and the Table shows the values obtained for the minimum transmittance, the transmittance after 10 minutes, the time taken to reach the point of minimum transmittance, and the maximum optical density (D_m).

[0019] The various polymers used in the Examples are further identified below

Tefze/280 is a copolymer of ethylene and tetrafluoroethylene available from du Pont.

Halar 300 is a copolymer of ethylene and chlorotrifluoroethylene avaiable from Allied Chemical.

Kynar 450 is polyvinylidene fluoride available from Pennwalt.

PEEK is a polyether ether ketone available from ICI.

U/tem is a polyetherimide available from General Electric.

Victrex 200P is polyethersulphone available from ICI.

[0020] "Tefzel", "Halar", "Kynar", "Ultem" and "Victrex" are Registered Trade Marks.

[0021] PEEK, Ultem and PES are substantially linear aromatic polymers.

Claims

1. An insulated electrical article, comprising

(a) a conductor;

(b) a melt-shaped inner insulating layer comprising a first organic polymer component which is a cross- linked olefin polymer, and

(c) a melt-shaped outer insulating layer which contacts the inner insulating layer and which comprises a second organic polymer component which is a substantially linear aromatic polymer having a glass transition temperature of at least 100°C.

2. An article according to claim 1, wherein the olefin polymer comprises at least 75% by weight of a thermoplastic crystalline polymer containing at least 25% by weight of fluorine.

3. An article according to claim 1 or claim 2, wherein the olefin polymer consists essentially of an ethylene/tetrafluoroethylene copolymer, an ethylene/chlorotrifluoroethylene copolymer or a vinylidene fluoride polymer.

4. An article according to any one of claims 1 to 3, wherein the aromatic polymer has a glass transition temperature of at least 130°C and/or is a crystalline polymer having a melting point of at least 250°C.

5. An article according to any one of claims 1 to 4, wherein the aromatic polymer comprises units of the general formula

the units being the same or different, wherein Ar represents a divalent aromatic radical and Q represents a radical of the formula

or Ar represents a polyvalent aromatic radical and Q represents

each bond of the Q radical preferably being bonded directly to an aromatic carbon atom.

6. An article according to any one of claims 1 to 5, wherein the aromatic polymer is a crystalline polyarylene ether comprising recurring units of the general formula

wherein 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.

7. An article according to claim 6, wherein E is a radical of the formula

wherein R represents a divalent radical; x is 0 or 1; Y is a halogen atom, an alkyl radical containing 1 to 4 carbon atoms or an alkoxy radical containing 1 to 4 carbon atoms; y is 0 or an integer from 1 to 4; Y' is a halogen atom, an alkyl radical containing 1 to 4 carbon atoms or an alkoxy radical containing 1 to 4 carbon atoms; and z is 0 or an integer from 1 to 4, and E' is a radical of the formula

wherein R' is a sulfone, carbonyl, vinyl, sulphoxide, azo, saturated fluorocarbon, organic phosphine oxide of ethylidene radical.

8. An article according to claim 7, wherein y and z are 0, x is 1, R' is a sulphone radical and R is a radical of the formula

wherein each of R" and R'" is independently a hydrogen atom; an alkyl radical containing 1 to 4 carbon atoms; a halogen-substituted alkyl radical containing 1 to 4 carbon atoms; an aryl, alkaryl or aralkyl radicals containing 6 to 10 carbon atoms; or a halogen-substituted aryl, alkaryl or aralkyl radicals containing 6 to 10 carbon atoms.

9. An article according to any one of claims 1 to 4, wherein the aromatic polymer consists essentially of repeating units of the formula







wherein each of x, m and n is 0 to 1, with n being 0 when x is 1, is an integer from 1 to 4, with m being 1 and x being 0 when p is greater than 1.

10. An article according to any one of claims 1 to 9 which is in the form of an electrical wire or cable, the inner insulating layer being a melt extruded layer which surrounds and contacts the conductor and preferably has a wall thickness of from 101.5 to 177.8 micrometres and the outer insulating layer being 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.

Ansprüche

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

umfasst, wobei die Einheiten gleich oder unterschiedlich sind und Ar einen zweiwertigen aromatischen Rest und Q einen Rest der Formel

oder Ar einen mehrwertigen aromatischen Rest und Q

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

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

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

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

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







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.

Revendications

1. Un article électrique isolé comprenant

(a) un conducteur;

(b) une couche isolante interne formée par façonnage de matière fondue, comprenant un premier composant polymère organique qui est un polymère d'oléfine réticulé et

(c) une couche isolante externe formée par façonnage de matière fondue qui est en contact avec la couche isolante interne et qui comprend un second composant polymère organique qui est un polymère aromatique essentiellement linéaire ayant une température de transition vitreuse d'au moins 100°C.

2. Un article selon la revendication 1, dans lequel le polymère d'oléfine comprend au moins 75% en poids d'un polymère cristallin thermoplastique contenant au moins 25% en poids de fluor.

3. Un article selon la revendication 1 ou la revendication 2, dans lequel le polymère d'oléfine est constitué essentiellement d'un copolymère d'éthylène/tétrafluoroéthylène, d'un copolymère d'éthylène/ chlorotrifluoroéthylène ou d'un polymère de fluorure de vinylidène.

4. Un article selon l'une quelconque des revendications 1 à 3, dans lequel le polymère aromatique a une température de transition vitreuse d'au moins 130°C et/ou est un polymère cristallin ayant un point de fusion d'au moins 250°C.

5. Un article selon l'une quelconque des revendiccations 1 à 4 dans lequel le polymère aromatique comprend des motifs de formule générale

les motifs étant semblables ou différents, dans laquelle Ar représente un radical aromatique divalent et Q représente un radical de formule

ou Ar représente un radical aromatique polyvalent et Q représente

chaque liaison du radical Q étant de préférence liée directement à un atome de carbone aromatique.

6. Un article selon l'une quelconque des revendications 1 à 5 dans lequel le polymère aromatique est un polyarylène-éther cristallin comprenant des motifs répétés de formule générale

dans laquelle E est le reste d'un phénol dihydroxylé et É est le reste d'un composé aromatique ayant un groupe attracteur d'électrons dans au moins une des positions ortho et para par rapport aux liaisons de valence; les radicaux E et E' étant liés aux radicaux -0- par des atomes de carbone aromatiques.

7. Un article selon la revendication 6 dans lequel E est un radical de formule

dans laquelle R représente un radical divalent; x est 0 ou 1; Y est un atome d'halogène, un radical alkyle contenant 1 à 4 atomes de carbone ou un radical alcoxy contenant 1 à 4 atomes de carbone; y est 0 ou un entier de 1 à 4; Y' est un atome d'halogène, un radical alkyle contenanat 1 à 4 atomes de carbone ou un radical alcoxy contenant 1 à 4 atomes de carbone; et z est 0 ou un entier de 1 à 4, et E' est un radical de formule

dans laquelle R' est un radical sulfone, carbonyle, vinyle, sulfoxyde, azo, fluorocarbure saturé, oxyde de phosphine organique ou éthylidène.

8. Un article selon la revendication 7 dans lequel y et z sont 0, x est 1, R' est un radical sulfone et R est un radical de formule

dans laquelle chacun de R" et R"' est indépendamment un atome d'hydrogène; un radical alkyle contenant 1 à 4 atomes de carbone; un radical halogénoalkyle contenant 1 à 4 atomes de carbone; un radical aryle, alkaryle ou aralkyle contenant 6 à 10 atomes de carbone; ou un radical halogéno-aryle, -alkaryle ou -aralkyle contenant 6 à 10 atomes de carbone.

9. Un article selon l'une quelconque des revendications 1 à 4 dans lequel le polymère aromatique est constitué essentiellement de motifs répétés de formule.







dans lesquelles chaque x, m et n est 0 à 1, n étant 0 lorsque x est 1, p est un entier de 1 à 4, m étant 1 et x étant 0 lorsque p est supérieur à 1.

10. Un article selon l'une quelconque des revendications 1 à 9 qui est sous forme d'un fil ou câble électrique, la couche isolante interne étant une couche formée par extrusion de matière fondue qui entoure le conducteur et est à son contact et a de préférence une épaisseur de la paroi de 101,5 à 177,8 micromètres - et la couche isolante externe étant une couche formée par extrusion de matière fondue qui entoure la couche isolante intérieure et est à son contact et a de préférence une épaisseur de la paroi de 101,6 à 177,8 micromètres.