[0001] This invention relates to an insulation system for wire and cable employing tinned,
silver or nickel coated electrical conductors having properties suitable for use in
aircraft applications.
[0002] More particularly, this invention relates to an electrical conductor insulated with
(A) a film selected from ethylene tetrafluoroethylene copolymer film and fluorinated
ethylene-propylene (FEP) copolymer coated polyimide film and (B) a topcoat insulation
system comprising (a) a first layer consisting essentially of modified polyimide,
(b) a second layer consisting essentially of polyvinylidene fluoride, and (c) a third
layer consisting essentially of cross-linked acrylic polymer.
[0003] U.S. patent 3,168,417, R. E. Smith and John M. Gardner, inventors, describes an improved
insulation system for electrical conductors in which the electrical conductors are
coated with a fluorocarbon polymer which in turn is insulated with a polyimide containing
the imide linkage as part of a 5-or 6-membered heterocyclic ring.
[0004] U.S. patent 3,408,453, Charles F. Shelton, Jr., inventor, describes an insulated
conductor suitable for use at high temperatures without breakdown. The electrical
conductor of U.S. patent 3,408,453 has a metallic conductor covered by a layer of
polytetrafluoroethylene film. One surface of this film is covered with a heat-sealable
fluorinated resin layer which does not contact the conductor. The heat-sealable layer
is sealed to a heat and oxidation resistant preshrunk polyimide film coated on both
sides by a first layer cf polytetrafluoroethylene and a second layer of heat-sealable
fluorinated resin.
[0005] U.S. patent 3,422,215, Karl R. Humes, inventor, describes an electrical cable having
fused insulation applied to wire. The insulation system comprises a first layer of
polytetrafluoroethylene or trifluoromonochloroethylene resin on the wire, which resin
is readily strippable from the wire, a second layer of a polyimide or polyamideimide
resin on the first layer, the second layer having at least one surface covered with
a layer of fluorinated ethylene polymer, a third layer of material similar to the
first layer and at least one of the first and third layers being bonded to the second
layer by a fluorinated ethylene polymer resins layer.
[0006] U.S. patent 3,504,103, Paul L. Anderson et al, inventors, describes an improved multilayer
electrical conductor assembly. The invention consists in providing an insulation system
comprising a plurality of thin plastic insulating sheets, at least one of the sheets
having a high dielectric constant and at least another of the sheets being characterized
by good mechanical strength and resistance to penetration and also by high dielectric
strength. Plastic films of polyvinyl fluoride are adhesively bonded to both sides
of a film of polyethylene terephthalate to form an insulation laminate, the polyethylene
terephthalate forming an interliner. The laminate is then adhesively secured between
conductors.
[0007] U.S. patent 3,616,177, Carl Gumerman, inventor, describes a laminar structure of
polyimides and a wire insulated therewith. The laminar structure described comprises
at least three layers, including a base layer of a polyimide, a layer of a fluoroethylene
propylene (FEP) copolymer and a layer of polytetrafluoroethylene (PTFE) polymeric
material.
[0008] U.S. patent 3,676,566, Richard T. McBride, inventor, describes a multilayer composite
useful as a shield for electrical conductors. The composite structure has adjacent
polyimide/perfluorocarbon/metal layers.
[0009] The insulated electrical conductor of this invention is fully described in the specification
and drawings which follow. In the drawings, FIGS. 1 and 2 are side views illustrating
two embodiments of the insulated electrical conductor of this invention.
[0010] In FIG. 1 an electrical conductor 10 has an ethylene tetrafluoroethylene copolymer
film 12 sealed about the exterior surface of conductor 10. The first layer 14 of the
topcoat insulation system is polyimide coating which adheres to the surface of film
12. The second layer 16 of the topcoat insulation system is polyvinylidene fluoride
which adheres to the first layer of insulation 14. The third layer-18 of the topcoat
insulation system is thermosetting acrylic polymer which coats the second layer of
insulation 16.
[0011] In FIG. 2 an electrical conductor 20 is wrapped with tetrafluoroethylene coated polyimide
film 22 and heat sealed about the exterior surface of conductor 20. The first layer
24 of the topcoat insulation system is polyimide coating which adheres to the surface
of film 22. The second layer 26 of the topcoat insulation system is polyvinylidene
fluoride which adheres to the first layer of insulation 24. The third layer 28 of
the topcoat insulation system is thermosetting acrylic polymer which adheres to the
second layer of insulation 26.
[0012] The electrical conductors which can be employed include any of the well known metallic
conductors used in wire and cable applications, stranded or unstranded. The metallic
conductors are preferably tinned or silver or nickel coated conductors.
[0013] The film which can be employed to initially cover the metallic conductors is selected
from polytetrafluoroethylene coated polyimide film and ethylene tetrafluoroethylene
copolymer film.
[0014] The fluorinated ethylene-propylene (FEP) copolymer coated polyimide film which can
be employed is available commercially from E. I. du Pont de Nemours and Company (Inc.),
Wilmington, Delaware 19898, and is sold under the trade name Kapton polyimide film
- type F. This film is heat sealed about the exterior surface of the conductor by
heating the conductor after it has been wrapped with said film. Information concerning
heat sealing of Kapton polyimide film - Type F is disclosed in DuPont Technical Information
Bulletin H-110-63. Information on properties of Kapton polyimide film - Type F is
contained in DuPont Bulletin F-66-lA, General Specification.
[0015] The ethylene tetrafluoroethylene copolymer film which can be employed to initially
cover the electrical conductor is available commercially from E. I. du pont de Nemours
and Company (Inc.), Wilmington, Delaware 19898, and is sold under the trade name Tefzel
ETFE fluoropolymer. This fluoropolymer is applied to the surface of electrical conductors
by melt extrusion techniques. The Tefzel ETFE fluoropolymer coated conductor is radiation
cured by exposure to 5-10 megarads of electron beam radiation. A particularly suitable
Tefzel ETFE fluoropolymer for use in coating the electrical conductor is Tefzel 280.
Information for melt extrusion of Tefzel ETFE fluoropolymers suitable for coating
electrical conductors in preparation of the insulated conductors of this invention
is disclosed in a publication by DuPont entitled "Tefzel", PIB 12 and dated February
1, 1970. The thickness of the film cover- : ings employed to cover the metallic conductor
will vary depending upon the application for which the wire is being insulated.'
[0016] The film covered conductors which can be employed with the topcoat insulation system
of this invention are initially surface etched prior to application of the first layer
of the topcoat insulation. Surface etching is accomplished by treating the surface
of the film coated conductor with an etching agent such as lithium sodium or a solution
of an alkali metal such as sodium or potassium metal in liquid ammonia, e.g., 1% of
sodium or 10% sodium in liquid ammonia, or a solution, e.g., a 5% solution of sodium
metal in molten naphthalene, sodium-naphthalene dissolved in tetrahydrofuran. Other
etching agents that can be employed include alkaline earth metals, e.g., calcium,
or magnesium or zinc, as shown in U.S. patent 2,789,065. Other materials capable of
etching the film surface of the conductor can be employed. Etching is accomplished
by passing the film covered wire through an etching bath for from a fraction of a
second to several seconds.
[0017] After application of the etching agent the etching agent remaining on the surface
of the film should be neutralized. Neutralization can be accomplished by passing the
etched film covered conductor through a solution of acetic acid or other mild acids,
preferably admixed with carbon tetrachloride.
[0018] Alternatively, the etched film covered conductor can be thoroughly washed with water
to remove the etching agent.
[0019] The polyimides which form the first layer of the topcoat insulation system of this
invention have (1) an aromatic ring, e.g., a benzene or a naphthalene ring system,
and (2) the heterocyclic linkage comprising a five- or six-membered ring containing
one or more nitrogen atoms and double-bonded carbon-to-carbon and/or carbon to nitrogen,
and/or carbonyl groups. Preferably, there are essentially no aromatic carbon atoms
with hydrogen atoms attached thereto. The linkage systems in the polyimides are, in
general, capable of assuming resonant double bond configurations. These resins are,
in general, linear polymers, but are extremely high melting by virtue of their high
molecular weight and strong intermolecular attraction. Suitable polymeric imides which
can be employed in the topcoat insulation system of this invention are disclosed in
U.S. patent 3,168,417, said disclosure being incorporated herein by reference. Preferred
polyimides which can be employed in the topcoat insulation system of this invention
are polybenzimide made by condensing equal molar amounts of an aromatic hydrocarbon
diamine with pyromellitic dianhydride and polybenzimidazoles. The first layer of insulation
can vary in thickness depending upon use but for many aircraft applications the first
layer of insulation is generally from about .07 mm to about .13 mm in thickness.
[0020] The polyimide is applied to the etched film coated electrical conductor as a solution
in any convenient solvent such as formic acid, dimethyl sulfoxide, N-methylpyrrolidone,
N-methyl caprolactam, dimethyl formamide, pyridine, p-cresol, m-p-cresol and the like.
The film coated wire is passed through a die dip coat bath and then through a series
of ovens to dry the film. The ovens are arranged in a vertical relationship to permit
the wire to pass through while maintained in a vertical configuration to promote even
application of the polyimide to the surface of the film coated conductor.
[0021] The polyvinylidene fluoride which comprises the second layer of the topcoat insulation
system of this invention is a crystalline, high molecular weight thermoplastic polymer
containing about 95% by weight fluorine. A preferred polyvinylidene fluoride polymer
is sold by Pennwalt Corporation, Philadelphia, Pa. under the tradename KYNAR. The
polyvinylidene fluoride polymer is applied to the polyimide coated conductor by a
dip-coating technique. In this process the polyimide coated wire is passed through
a conventional wet flow coating device commonly employed in the-wire industry. The
polyvinylidene fluoride coated wire then passes through drying and curing ovens. In
a typical procedure the wire is passed through several ovens operated at about 250°F.,
350°F. and 400°F. respectively. The wire passes through these heating zones while
being maintained in a vertical plane. The linear speed of the polyvinylidene fluroide
coated wire passing through the ovens is adjusted to insure complete drying of the
polyvinylidene fluoride prior to its exiting from the last oven.
[0022] The polyvinylidene fluoride is employed as a dispersion in a diluent. Diluents for
polyvinylidene fluoride which are compatible with the polyimide comprising the first
layer of the topcoat insulation can be employed. Suitable diluents include ketones
such as acetone, methylethyl ketone, isobutyl ketone, and aromatic solvents such as
toluol and naphtha. A preferred diluent is a mixture comprising 95% by-weight cellosolve
acetate and 5% isophorone. The polyvinylidene dispersion preferably contains from
about 15% to about 20% by weight of solids. The polyvinylidene solids can be pigmented
with suitable inorganic pigments such as titanium dioxide, chrome yellow, cadmium
red, cobalt green and violet, cerulean blue and the like. The polyvinylidene fluoride
is applied to form a continuous layer of insulation which may vary in thickness but
for many aircraft applications this layer is from about .07 mm to about 0.13 mm in
thickness.
[0023] The third or exterior layer of the topcoat insulation system of this invention is
a chemically crosslinked thermosetting acrylic polymer. The acrylic polymer is applied
to the conductor having a first layer of polyimide and a second layer of polyvinylidene
fluoride as defined above by passing the conductor having two layers of insulation,
as heretofore described, through an aqueous acrylic emulsion in a bath, said emulsion
comprising 10 to 12% by weight of acrylic solids. Suitable acrylic polymers which
are thermosetting and can be prepared as aqueous emulsions are polymethyl methacrylate
and copolymers prepared from methyl methacrylate and acrylic and methacrylic ester
monomers or vinyl monomers such as alphamethylstyrene and vinyl chloride. An acrylic
polymer which is preferable for use as the third layer of the topcoat insulation system
of this invention is available commercially under the tradename Rhoplex AC-172 from
the Rohm and Haas Company, Philadelphia, Pa. 19105. A crosslinking agent for the acrylic
polymer such as a methylated melamine is admixed with the emulsion. Any crosslinking
agent for acrylic polymer can be employed. A particularly suitable crosslinking agent
for acrylic emulsion is Cymel 385 available commercially from American Cyanamid Co.,
Resins Dept., Wayne, New Jersey. Cymel 385 is a methylated melamine.
[0024] The acrylic polymer is applied to the wire or cable having the first and second layers
of insulation to a desired thickness depending on the application for the wire and
is cured. For many aircraft applications the acrylic polymer insulation is from about
0.7 mm to about 0.13 mm in thickness.
[0025] The following examples illustrate this invention. In the examples and throughout
this specification, percentages are by . weight unless specified otherwise.
Examples 1-3
[0026] A fluorinated ethylene-propylene (FEP) copolymer coated polyimide film type-F is
wrapped about the exterior of conductor wires having AWG sizes as specified in Table
I. The polyimide film employed is Kapton polyimide film. The film is heat cured at
about 585°F. for about 10 seconds.
[0027] The first layer of the topcoat insulation system is applied as follows. An aromatic
polyimide which is a polybenzimide made by condensing equal molar amounts of an aromatic
hydrocarbon diamine with pyromellitic dianhydride and sold by Du Pont under the trade
name Pyre-ML is admixed in a normal methylpyrrolidone solvent. The solution contains
12-14% by weight of the aromatic polyimide. The solution of aromatic polyimide is
charged to a die dipcoat applicator. Wire is passed through dies in the die dipcoat
applicator a number of times as specified in Table 1. The polyimide coated wire is
cured by passing the wire through a series of drying ovens which are each five feet
long and which are arranged adjacent to each other in a vertical configuration. Each
oven is operated at the temperature specified in Table I.
[0028] The wire containing the first layer of topcoat insulation is then passed into a polyvinylidene
fluoride dispersion in a dipcoat bath. The polyvinylidene fluoride is dispersed in
a diluent comprising a mixture of cellosolve acetate (95% by weight) and isophorone
(5% by weight). The dispersion comprises 15-20% by weight of polyvinylidene fluoride.
After each pass through the dipcoat bath (wet passes) the wire is passed through a
series of adjacent, vertical drying ovens. After the last pass is complete through
the dipcoat bath and ovens, the wire is passed through the oven only to complete drying
(dry passes). The number of passes and drying conditions are as specified in Table
I.
[0029] The wire with the first and second layers of insulation is then passed to a third
dipcoat bath containing emulsion of acrylic polymer in water. The emulsion contains
a methylated melamine crosslinking agent dissolved therein. The wire is passed through
the acrylic emulsion bath under conditions as specified in Table 1. After each pass
through the bath the wire is dried by passing through a series of adjacent vertical
drying ovens. The wire emerging from the third dipcoat bath after drying is the insulated
electrical conductor of this invention.

[0030] The insulated electrical conductors of this invention can be used satisfactorily
in applications in which the wire will be exposed to temperature extremes of from
-65°C. to 150°C. The insulation has good chemical, abrasion and high temperature resistance.
The second layer of the insulation system renders the insulation system capable of
being pigmented for color coding purposes. The exterior surface of the insulation
system provides anti-blocking resistance, abrasion and chemical alkali resistance
and is capable of ink-jet printability. The insulated electrical conductor provides
a unique combination of physical, electrical and chemical protection particularly
desirable for use in aircraft applications.
1. An insulated electrical conductor comprising a metallic conductor insulated with
(A) a film selected from. ethylene tetrafluoroethylene copolymer and tetrafluoroethylene
coated polyimide, and (B) a topcoat insulation system comprising a first layer of
insulation consisting essentially of a modified polyimide coating adhering to said
film, a second layer of insulation consisting essentially of polyvinylidene fluoride
coating adhering to the surface of the polyimide coating and a third layer of insulation
consisting essentially of a crosslinked acrylic polymer coating adhering to the surface
of the polyvinylidene fluoride.
2. The insulated electrical conductor of claim 1 in which the film insulating the
metallic conductor .is ethylene tetrafluoroethylene copolymer film.
3. The insulated electrical conductor of claim 1 in which the film insulating the
metallic conductor is tetrafluoroethylene coated polyimide film.
4. The insulated electrical conductor of claims 1, 2 or 3 in which the polyimide coating
is prepared from a polybenzimide made by condensing equal molar amounts of an aromatic
hydrocarbon diamine with pyromellitic dianhydride.
5. The insulated electrical conductor of claims 1, 2 or 3 in which the polyimide is
polybenzimidazole. '