U.S. patent number 3,684,821 [Application Number 05/129,558] was granted by the patent office on 1972-08-15 for high voltage insulated electric cable having outer semiconductive layer.
This patent grant is currently assigned to Sumitomo Electric Industries, Ltd.. Invention is credited to Hironaga Matsubara, Hirokazu Miyauchi.
United States Patent |
3,684,821 |
Miyauchi , et al. |
August 15, 1972 |
HIGH VOLTAGE INSULATED ELECTRIC CABLE HAVING OUTER SEMICONDUCTIVE
LAYER
Abstract
This invention relates to an insulated cable having an outer
semiconductive layer, and more particularly relates to the
structure of an insulated cable chiefly consisting of a crosslinked
polyethylene or a crosslinked polyethylene copolymer, having an
outer semiconductive layer. The composition is a mixture of 10 - 90
percent by weight of ethylene-vinyl acetate copolymer having 15 -
55 percent by weight of vinyl acetate content with 90 - 10 percent
by weight of ethylene-vinyl acetate-vinyl chloride terpolymer, said
mixture being used as a base, said base being mixed with a
cross-linking agent and a conductivity imparting agent such as
carbon black.
Inventors: |
Miyauchi; Hirokazu (Osaka,
JA), Matsubara; Hironaga (Osaka, JA) |
Assignee: |
Sumitomo Electric Industries,
Ltd. (Osaka, JA)
|
Family
ID: |
22440575 |
Appl.
No.: |
05/129,558 |
Filed: |
March 30, 1971 |
Current U.S.
Class: |
174/102SC;
174/110PM; 427/118; 174/106SC; 174/120SC; 174/DIG.27 |
Current CPC
Class: |
H01B
3/004 (20130101); H01B 3/441 (20130101); H01B
9/027 (20130101); Y10S 174/27 (20130101) |
Current International
Class: |
H01B
3/44 (20060101); H01B 9/02 (20060101); H01B
3/00 (20060101); H01B 9/00 (20060101); H01b
007/00 () |
Field of
Search: |
;174/12A,12SC,12R,12SC,16SC,11PM ;117/216,232 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Goldberg; E. A.
Claims
What we claim:
1. An insulated electric cable having an easily strippable outer
semiconductive layer comprising an electric conductor having an
insulation layer thereon consisting of crosslinked polyethylene or
a crosslinked polyethylene copolymer as a chief constituent, and
characterized by an outer semiconductive layer extruded over said
insulation layer and composed of a mixture of 90 - 10 percent by
weight of an ethylene-vinyl acetate-vinyl chloride terpolymer with
10 - 90 percent by weight of ethylene-vinyl acetate copolymer
having 15-55 percent by weight of vinyl acetate content, a
cross-linking agent and a conductivity imparting agent.
2. An insulated cable as claimed in claim 1 characterized by the
use of Di-.alpha.-cumyl peroxide as a cross-linking agent of the
semiconductive layer.
3. An insulated cable as claimed in claim 1 characterized by the
use of 2.5-dimethyl-2'.5'-di-(tertiary butyl peroxy)-hexine-3 as a
cross-linking agent of the semiconductive layer.
4. An insulated cable as claimed in claim 1 wherein the insulation
layer is made of crosslinked polyethylene.
5. An insulated cable as claimed in claim 1 wherein the insulation
layer is made of crosslinked polyolefine consisting of
ethylene-vinyl acetate copolymer.
6. An insulated cable as claimed in claim 1 wherein an inorganic
filler is added to the composition of said insulation layer.
7. The insulated electric cable of claim 1 wherein antioxidant and
processing aids are included in the composition of said outer
semiconductive layer as required.
Description
In the conventional art, when covering the insulating layer of a
crosslinked polyethylene insulated cable with an extruded
semiconductive layer, wherein low density polyethylene, an
ethylene-vinyl acetate copolymer or a polymer mainly consisting of
these substances is used as the base thereof, to which are further
added talcum, clay, calcium-carbonate or the like inorganic
fillers, and also various antioxidants, processing aids and the
like as required, it is a usual practice to use a composition such
as a mixture of a ethylene-vinyl acetate copolymer,
di-.alpha.-cumyl peroxide or like crosslinking agents and
electric-conductive carbon black, or a mixture of a ethlene-ethyl
acrylate copolymer, di-.alpha. cumyl peroxide or the like
crosslinking agents, and electric-conductive carbon black. When
splicing and treating the end of a cross-linked polyethylene
insulated cable having an outer semi-conductive layer, it is
necessary to strip the semiconductive layer in the range from the
end of the cable to a certain length thereof, and in this case the
semiconductive layer must be completely removed, and when it is
removed, caution must be exercised not to impair the insulator.
Moreover, in recent years an art of splicing and terminating the
cable by the use of premolded accessories has been developed in
making connections and end disposition with the cross-linked
polyethylene insulated cable having an outer semiconductive layer.
The advantage of the art in that it makes it possible to provide a
product more uniform in quality and to deal or labor with the cable
in shorter time than a conventional process in which tape winding
and heat molding are carried out, has brought about a trend toward
generalizing such a process. In this case, as it is necessary that
the premolded accessories and cable must be assembled without
allowing any electrical faults, there is an increasing demand that
the semiconductive layer must be stripped in a shorter period of
time and in a more simple manner so as not to impair the
insulator.
When the described compositions in conventional use are extruded
over the insulator to cover the same therewith, it is not only very
difficult and takes much time but also tends to impair the
insulator to strip the covered compositions from the cable.
Therefore, such compositions cannot meet the requirements described
above. In contrast thereto, the inventors previously made an
application Ser. No. 77,918 filed Oct. 5, 1970, for a U.S. Pat. for
an invention that provided a crosslinked polyethylene insulated
cable having a semiconductive layer capable of being stripped
simply and positively without leaving a part of the semiconductive
layer over the insulator and without impairing the insulator.
The previous invention related to a cross-linked polyethylene
insulated cable having a semiconductive layer by extrusion-covering
the insulator, and provides the cable which has the property of
making itself very easy to strip the semiconductive layer from the
cable, and is characterized in that the semiconductive layer is
extrusion-covered with a composition of a mixture of
2.5-dimethyl-2'.5'-di(tertiary-butyl peroxy)-3 with ethylene-vinyl
acetate copolymer having 25-55 percent by weight of vinyl acetate
content preferably in a ratio of 0.3-5.0 parts by weight of the
former to 100 parts by weight of the latter copolymer. But in that
invention there was the limitation that the strippable strength
could not be reduced beyond a certain degree.
An object of the present invention is to obtain an excellent
insulated cable, and more particularly, to obtain an insulated
cable having an easily strippable semiconductive layer, consisting
of cross-linked polyethylene or cross-linked polyethylene copolymer
as a main constituent.
A detailed explanation will now be made of this invention in
conjunction with the accompanying single leaf of drawing showing an
embodiment of the invention.
The inventors have made researches into the strippable strength in
order to eliminate the disadvantages of the kind described, with
the result that they have succeeded in obtaining a cross-linked
polyethylene cable having an improved type semiconductive layer
capable of being easily stripped. Namely, this invention is
characterized in that a conductive layer having a composition of a
mixture of 90 - 10 percent by weight of ethylene-vinyl acetate
copolymer having 15 - 55 percent by weight of vinyl acetate content
and 10 - 90 percent by weight of ethylene-vinyl acetate-vinyl
chloride terpolymer with an ordinary cross-linking agent such as
dicumyl peroxide or 2.5-dimethyl-2'.5'-di(tertiary-butyl
peroxy)-hexine-3, preferably in a ratio of 0.3 - 50 parts by weight
of the latter to 100 parts by weight of the former copolymer, and
terplymer.
Of course, since the composition is to be made into a
semiconductive layer, all that is necessary is to mix a suitable
amount of carbon black for imparting conductivity to the
composition, and if necessary, other agents such as antioxidant,
processing aids, etc. in accordance with conditions of use.
The results of experiments obtained by the inventors have
demonstrated that the amount of carbon black (25 - 70 parts by
weight as against 100 parts by weight of polymer) and amine-based,
or phenol-based antioxidant and processing aids such as zinc
stearate have nothing to do with a tendency of the composition
toward easy stripping.
An embodiment of the invention in an insulated cable having an
outer semiconductive layer will now be described in the drawing in
which the numeral 1 designates a conductor; 2 an inner
semiconductive layer; 3 an insulated layer; and 4 designates an
outer semi-conductive layer. Examples and references are shown
below. The material and method of experiment used in the examples
are as follows: An ordinary inner semiconductive layer was extruded
over a stranded cable conductor of 100 mm.sup.2 in cross-section to
cover the conductor therewith, and the cable conductor thus covered
was then further covered by extrusion with the insulated layer and
semiconductive layer shown in Table 1. and the layer was subjected
to a cross-linking reaction in saturated steam of 15 atm. An
adhesion test was conducted by making a cut 10 mm wide and running
in the axial direction in the thus obtained semiconductive layer
covering the surface of the conductor. The results obtained are
shown in Table 1.
In the semiconductive layer in the table 50 parts by weight of
acetylene carbon black, 1 part by weight of antioxidant, and 1 part
by weight of zinc stearate were mixed with 100 parts by weight of
base polymer (of course, including mixtures of various polymers)
and the cross-linking agent was varied in type and amount, and the
semiconductive layer was varied in thickness.
TABLE 1
No. Insulated Semiconductive layer Peeling layer (over insulator)
strength Base cross- Thick- polymer linking ness (kg/10 mm) agent
(mm)
__________________________________________________________________________
Ref. More 1 Polyethylene E.VA*--1 X * -- 2 0.5 than 5 Specific
Vinyl gravity=0.92g/cc acetate 1% Slightly * -- 3 =15% left on M I
= 2 M I = 6 insulator * - 4 DCP=2.5% Antioxdant = 0.3% Ref. 2 Same
as E.VA Ref. 1 X*--2 0.5 Vinyl acetate = 3.9 25% 1% M I =6 Ref. 3
Same as E, VA X*-2 Ref. 1 Vinyl 0.5 3.5 acetate = 35% 1% M I = 6
Ref. 4 Same as E.VA X*-2 Ref. 1 Vinyl acetate = 0.5 2 50% 1% M I =
6 Ex. More 1 Same as E.VA X*-2 than 5 Ref. 1 Vinyl acetate = 0.5
10% 1% M I = 6 *--5 +SUMI- GRAFT 10% Ex. 2 Same as Ref. 1 X*--2
Ref. 1 +SUMI- 1% 0.5 3.0 GRAFT 10% Ex. 3 Same as Ref. 2 X*-2 Ref. 1
+SUMI 1% 0.5 2.8 GRAFT 10% Ex. 4 Same as Ref. 3 X*-2 Ref. 1 +SUMI-
1% 0.5 1.3 GRAFT 10% Ex. 5 Same as Ref. 2 X 0.5 2.0 Ref. 1 +SUMI-
1% GRAFT 10% Ex. 6 Same as Ref. 2 X Ref. 1 +SUMI- 1% 0.5 0.5 GRAFT
90% Ref. 5 Same as SUMI- X REF. 1 GRAFT 1% 0.5 0 100% Ref. 6 Same
as Same as None 0.5 Semiconduc- Ref. 1 Ref. 3 tive layer is cut and
not stripped Ref. 7 Same as Same as X 0.5 " Ref. 1 Ref. 3 0.2% Ref.
8 Same as Same as X 0.5 3.5 Ref. 1 Ref. 3 0.3% Ref. 9 Same as Same
as X 0.5 3.5 Ref. 1 Ref. 3 0.5% Ref. 10 Same as Same as X 0.5 3.5
Ref. 1 Ref. 3 1.0% Ref. 11 Same as Same as X 0.5 3.0 Ref. 1 Ref. 3
5.0% Ref. 12 Same as Same as X 0.5 0.3 Ref. 1 Ref. 3 6.0% Ex. 7
Same as Same as X 0.5 2.7 Ref. 1 Ex. 3 0.3% Ex. 8 Same as Same as X
0.5 2.0 Ref. 1 Ex. 3 5.0% Ref. 13 Same as Same as X 0.5 0 Ref. 1
Ex. 3 6.0% Ref. 14 Same as Same as X 0.1 Semiconduc- Ref. 1 Ref. 3
1.5% tive layer is cut and not stripped Ref. 15 Same as Same as X
0.2 3.3 Ref. 1 Ref. 3 1.5% Ref. 16 Same as Same as X 0.5 3.4 Ref. 1
Ref. 3 1.5% Ref. 17 Same as Same as X 1.0 3.3 Ref. 1 Ref.3 1.5%
Ref. 18 Same as Same as X 0.1 Semiconduc- Ref. 1 Ex.3 1.5% tive
layer cut and not stripped Ex. 9 Same as Same as X 0.2 2.7 Ref. 1
Ex.3 1.5% Ex. 10 Same as Same as X 0.5 2.6 Ref. 1 Ex.3 1.5% Ex. 11
Same as Same as X 1.0 2.7 Ref. 1 Ex.3 1.5% Ref. 19 Polyethylene
Same as X 0.7 3.5 Specific Ref. 3 2.0% gravity = 0.92g/cc MI = 4
DCP = 2.5% Antioxidant = 0.5% Ref. 20 30 parts by Same as X 0.7 3.0
weight of talc Ref.3 2.0% is added to 100 parts by weight of
composition of Ref. 19. Ref. 21 30 parts by Same as X 0.7 3.1
weight of clay Ref. 3 2.0% is added to 100 parts by weight of
composition of Ref. 19. Ref. 22 E.VA Vinyl acetate = Same as X 1.0
4.3 15% 1.5% MI = 3 Ref. 3 DCP = 2% Age-resistor = 0.5% Ref. 23 30
parts by Same as X weight of talc Ref. 3 1.5% 1.0 3.9 is added to
100 parts by weight of composition of Ref. 22. Ex. 12 Same as Same
as X Ref. 19 Ex.3 2.0% 0.7 2.7 Ex. 13 Same as Same as X Ref. 20 Ex.
3 2.0% 0.7 2.3 Ex. 14 Same as Same as X Ref. 21 Ex. 3 2.0% 0.7 2.4
Ex. 15 Same as Same as X Ref. 22 Ex. 3 1.5% 1.0 3.6 Ex. 16 Same as
Same as X Ref. 23 Ex. 3 1.5% 1.0 3.2 Ref. 24 Same as Same as DCP
More than 5 Ref. 1 Ref. 3 1.0% 0.5 Slightly left on insulator Ref.
25 Same as Same as DCP More than 5 Ref. 1 Ref. 3 5.0% 0.5 Slightly
left on insulator Ref. 26 Same as E.VA in Ref.3 Ref. 1 was changed
X into * --6 1.0% 0.5 " DPD--6169 Ex. 17 Same as Same as DCP Ref. 1
Ex. 3 1.0% 0.5 2.8 Ex. 18 Same as Same as DCP Ref. 1 Ex. 3 5.0% 0.5
2.0 Ref. 27 Same as E.VA in Ref. 1 ex. 3 was X More than 5 changed
1.0% 0.5 into DPD --6169
__________________________________________________________________________
In the previous application, it was possible to obtain an intended
easily and completely strippable semiconductive layer only when
2.5-dimethyl-2'.5'-di-(tertiary butyl peroxy)-hexine-3 was mixed
with an ethylene-vinyl acetate copolymer having 25 - 55 percent by
weight of vinyl acetate content, but as is apparent from the
examples shown, it is possible to obtain an intended easily and
completely strippable semiconductive layer and also to reduce the
strippable strength in a substantial degree even by the use of not
only 2.5-dimethyl-2'.5'-di-(tertiary butyl peroxy)-hexine 3, but
also an ordinary cross-linking agent such as di-.alpha.-cumyl
peroxide only when an ethylene-vinyl acetate-vinyl chloride
tertiary copolymer is mixed with an ethylene-vinyl acetate
copolymer having 15 - 55 percent by weight of vinyl acetate
content.
Namely, when an ethylene-vinyl acetate copolymer is less than 15
percent in its vinyl acetate content, ethylene-vinyl acetate-vinyl
chloride ternary copolymer is deprived of its effect and the layer
made thereof becomes difficult to strip, and when the copolymer
exceeds 55 percent, its adhesion to the insulator is reduced too
much to be suited for use in a cable.
Accordingly, when the vinyl acetate content is 15 - 55 percent,
SUMIGRAFT proves effective and shows its readily improved
strippability. Now, when the content of
2.5-dimethyl-2'.5'-di-(tertiary butyl peroxy)-hexine-3 is less than
0.3 part by weight on 100 parts y weight of said copolymer and
terpolymer mixture, the semiconductive layer is relatively small in
strength, and when the content exceeds 5 parts by weight, it
becomes too poor in adhesion with respect to the insulator to be
suitable enough for use in the cable.
When it is within the range of 0.3 - 5 parts by weight, it shows an
especially good result. As for the thickness of the layer, it
should be preferably more than 0.2 mm, because a layer of a
thickness of less than 0.2 mm tends to be cut off in stripping.
As described above, only when ethylene-vinyl acetate copolymer is
15 - 55 percent in vinyl acetate content and ethylene-vinyl
acetate-vinyl chloride terpolymer is added to said copolymer and
2.5-dimethyl-2'.5'-di-(tertiary butyl peroxy)-hexine-3 or DCP is
preferably in a ratio of 0.3 - 5.0 parts by weight to 100 parts by
weight of said copolymer and terpolymer mixture, it is possible to
obtain a readily and completely strippable semiconductive layer. It
has been demonstrated by experiments that the use of other types of
cross-linking agents has produced no such semiconductive layer of
desirable quality.
When ethylene-vinyl acetate-vinyl chloride terpolymer is less than
10 percent by weight in quantity in copolymer and terpolymer
mixture, it has no effect and when it is more than 90 percent by
weight, it cannot provide the required peeling strength. On the
other hand, even when ethylene-vinyl acetate-vinyl chloride
terpolymer is added to a high molecular (wight polymer or)
copolymer other than an ethylene-vinyl acetate copolymer, and even
when 2.5-dimethyl-2'.5'-di-(tertiary butyl peroxy)-hexine-3 or DCP
is used as a cross-linking agent, it has become apparent that no
good result can be obtained. Only the use of the formula provided
by the invention can produce a semiconductive layer excellent in
strippability.
Also, it should be understood that, irrespective of the size of the
cable and the purpose for which the cable is used, the invention
can be used in the cable, the insulated layer of which consists of
cross-linked polyethylene or a cross-linked polyethylene copolymer
as a chief constituent.
* * * * *