U.S. patent number 3,804,669 [Application Number 05/186,787] was granted by the patent office on 1974-04-16 for flame-resistant resistor coatings.
This patent grant is currently assigned to Corning Glass Works. Invention is credited to Lawrence G. Bockstie, Jr..
United States Patent |
3,804,669 |
Bockstie, Jr. |
April 16, 1974 |
FLAME-RESISTANT RESISTOR COATINGS
Abstract
Flame resistant polyimide resistory coatings containing
chlorinated polyphenyl and antimony trioxide.
Inventors: |
Bockstie, Jr.; Lawrence G.
(Bradford, PA) |
Assignee: |
Corning Glass Works (Corning,
NY)
|
Family
ID: |
26882411 |
Appl.
No.: |
05/186,787 |
Filed: |
October 5, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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652412 |
Jul 11, 1967 |
3655607 |
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Current U.S.
Class: |
428/432; 428/702;
428/473.5; 428/921 |
Current CPC
Class: |
C09D
179/08 (20130101); C09D 179/08 (20130101); C08L
2666/04 (20130101); Y10T 428/31721 (20150401); Y10S
428/921 (20130101) |
Current International
Class: |
C09D
179/00 (20060101); C09D 179/08 (20060101); B44d
001/34 (); B44d 001/42 () |
Field of
Search: |
;117/232,201,161P,137
;106/15FP ;260/28TF |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Esposito; M. F.
Attorney, Agent or Firm: Zebrowski; Walter S.
Parent Case Text
This is a division of application Ser. No. 652,412, filed July 11,
1967.
Claims
1. A coated electrical resistor comprising a resistance layer
coated with a stable, intumescent coating composition consisting
essentially of a polyimide resin containing from about 1 percent to
about 60 percent of a chlorinated polyphenyl and from about 1
percent to about 50 percent antimony trioxide, all percentages
being weight percentages of the amount of polyimide resin, which
coated electrical resistor upon electrical
2. The resistor of claim 1 wherein said coating composition
contains from about 2 percent to about 10 percent of a chlorinated
polyphenyl and from
3. The resistor of claim 1 wherein said polyimide resin is one
having the recurring unit: ##SPC4##
wherein R is a tetravelent radical containing at least one ring of
six carbon atoms, said ring characterized by benzenoid
unsaturation, the four carbonyl groups being attached directly to
separate carbon atoms in a ring and each pair of carbonyl groups
being attached to adjacent carbon atoms in a ring of the R radical;
and wherein R' is a divalent benzenoid radical containing at least
two rings of six carbon atoms, each ring characterized by benzenoid
unsaturation, and in which no more than one of the valence
4. The resistor of claim 1 wherein said chlorinated polyphenyl is
one
5. The resistor of claim 3 wherein said coating composition
contains 20 percent chlorinated polyphenyl containing from 18 to 66
percent chlorine
6. The resistor of claim 1 comprising a substrate having coated
thereon a
7. The resistor of claim 6 wherein said substrate is glass.
Description
BACKGROUND OF THE INVENTION
The present invention relates to coating compositions for
electrical resistors. More specifically, the present invention
relates to flame-resistant organic coatings adapted for the
protection of electrical film resistors against burning due to
severe overload (up to 100.times. rated power).
THE PRIOR ART
Recently, electrical film resistors have come into wide use.
Normally, these film resistors comprise a substrate such as glass,
coated with a thin film of resistor material such as tin oxide, for
example. Also, it is known in the art to overcoat these film
resistors with a protective layer. The prior art is faced with the
problem, however, that these protective coatings due to the heat
resulting from severe overloads on the film resistor, very often
burn. This burning of the resistor coating not only results in the
destruction of the resistor itself but, very often, results in
damage to adjacent elements in the system in which it is employed.
The consequent damage to electrical equipment and systems from this
burning of resistor coatings has led to an intensive search for a
flame-resistant coating, which will not burn due to the heat
arising from severe overloads on the resistor.
The film resistors containing the protective coatings of the prior
art suffer from the further disadvantage that upon severe overload
the protective coatings not only burn, but become electrically
conductive. This very often results in external arcing and a
failure of the resistor to open the circuit in which it is
contained. Accordingly, an intensive search has been conducted for
a film resistor protective coating which will not burn under severe
overload, and also cause the resistor to open the circuit in which
it is contained.
It has been proposed to add several conventional flame-retardants
to film resistor protective coatings. These efforts, however, have
consistently met with failure. One drawback common to most of the
conventional flame-retardant coatings is the fact that they become
electrically conductive when the resistor is severely overloaded.
This causes the resistor to burn, promotes severe external arcing
and does not permit the resistor to open the circuit in which it is
contained. Moreover, many of these conventional flame-retardant
coatings were ineffective to inhibit burning at the extremely high
temperatures (500.degree.-600.degree.C) attained in film resistors
under severe overload.
An object of the present invention is to provide a flame-resistant
organic coating composition suitable for the protection of film
resistors.
A further object of the present invention is to provide a
flame-resistant coating composition suitable for the protection of
film resistors which will not burn at the high temperature attained
in film resistors upon severe overload.
A further object of the present invention is to provide a
flame-resistant coating composition suitable for the protection of
film resistors which is resistant to burning and which at the same
time promotes the destruction of the resistor during severe
overload and thereby opens the circuit.
A further object of the present invention is to provide a
flame-resistant coating composition suitable for the protection of
film resistors which is a stable mixture, with long pot life and
which forms a homogeneous, uniform layer upon coating film
resistors.
A further object of the present invention is to provide a
flame-resistant coating composition suitable for the protection of
film resistors wherein the flame-resistant additive is compatible
with the protective coating material and does not alter the
chemical or dielectric properties thereof.
BRIEF SUMMARY OF THE INVENTION
The objects of the present invention are achieved by the provision
of a film resistor protective coating composition comprising a
polyimide resin containing from about 1 to 60 percent, preferably
from about 2 percent to about 10 percent of a chlorinated
polyphenyl and from about 1 percent to about 50 percent, preferably
from about 2 percent to about 10 percent of antimony trioxide.
It has recently been discovered that polyimide resins are highly
suitable as coating compositions for the protection of film
resistors due to their exceptional dielectric properties, their
hardness and solvent resistant. Unfortunately, these polyimide
resins are suspceptible to burning, at the high temperatures
attained in film resistors due to severe overloads much in the same
manner as described above. Applicant has found that the addition of
from about 1 percent to about 60 percent of chlorinated polyphenyl
and from about 1 to 50 percent of antimony trioxide to a polyimide
resin results in a coating composition having vastly improved
flame-resistant properties. Thus, the coating compositions of the
present invention are stable against burning, when resistors
containing these coatings are placed under severe overload.
Moreover, the coating compositions of the present invention possess
the additional property of being somewhat intumescent. This results
in the phenomenon that, frequently, upon the film resistor
attaining a high temperature due to severe overload, the coating of
the present invention will swell and form a protective cocoon. This
cocoon adds further to the protective qualities of the coating of
the present invention in that it confines the external arcing. No
other coating composition has been found which possesses this
intumescent property. It is noteworthy that the polyimide resin
coatings alone, i.e., without the addition of chlorinated
polyphenyl or antimony trioxide, do not possess intumescent
properties. Furthermore, the coating compositions are homogeneous
and have long pot lives, unlike the heretofore employed
flame-resistant coating compositions .
DETAILED DESCRIPTION OF THE INVENTION
The polyimide resins suitable as a base material for the coating
compositions of the present invention are described in U.S. Pat.
No. 3,179,634. Generally, these cured resins are characterized by a
recurring unit having the following structural formula:
##SPC1##
Wherein R is a tetravalent aromatic radical, preferably containing
at least one ring of six carbon atoms, said ring characterized by
benzenoid unsaturation, the four carbonyl groups being attached
directly to separate carbon atoms in a ring and each pair of
carbonyl groups being attached to adjacent carbon atoms in a ring
of the R radical; and wherein R' is a divalent benzenoid radical
containing at least two rings of six carbon atoms, each ring
characterized by benzenoid unsaturation, and in which no more than
one of the valence bonds is located on any one of said rings of
said R' radical.
The most preferred of the polyimides is duPonts' RK-692, which is a
polyimide according to the above structural formula wherein R is
##SPC2##
and wherein R' is ##SPC3##
Generally, these polyimides are prepared by reacting an appropriate
organic diamine with a suitable tetracarboxylic acid dianhydride.
This and other processes for the preparation of these polyimides
are more specifically described in U.S. Pat. No. 3,179,634.
Generally, polyimides wherein the degree of polymerization is
controlled such that the resin has an inherent viscosity from about
30 to about 90 poises when measured at 25.degree.C. are suitable as
base materials for the coating compositions of the present
invention.
As mentioned above, the desirable flame-resistant and intumescent
properties are imparted to the polyimide resin base material by
incorporating therein from about 1 percent to about 60 percent of a
chlorinated polyphenyl and from about 1 percent to about 50 percent
of antimony trioxide.
The chlorinated polyphenyls are well known in the art, it being
preferred that a chlorinated polyphenyl like Aroclor 5460, made by
Monsanto, or similar chlorinated polyphenyls having about the same
degree of polymerization and degree of chlorination be employed as
one of the flame-resistant additives of the present invention.
Suitable chlorinated polyphenyl resins are those sold under the
name Aroclor. These materials are prepared by the chlorination of
crude biphenyl and are resinous materials possessing high melting
points and containing from 18 to 66 percent chlorine. Useful
chlorinated polyphenyl resins include Aroclor 1260, Aroclor 1262,
Aroclor 1268, Aroclor 1270, Aroclor 4465, Aroclor 5442, Aroclor
2565, and Aroclor 5460, the most preferred being the latter, which
has a softening point of about 100.degree. - 105.degree.C.
The incorporation of chlorinated polyphenyl and antimony trioxide
into the polyimide base material may be effected by any of the well
known, conventional methods.
Film resistors are well known in the art and are generally
manufactured as follows. A suitable substrate, such as glass, after
being appropriately sensitized according to methods well known in
the art is heated to a high temperature and coated with a thin
spray of a solution of stannic chloride. Upon contact of the
stannic chloride solution with the hot glass surface, the stannic
chloride is pyrolized to tin oxide which deposits out as an
extremely thin uniform layer on said glass surface. This tin oxide
layer acts as the resistor material. It is to be understood,
however, that the coating compositions of the present invention are
applicable for the protection of any resistor regardless of its
method of preparation, composition, shape or structure.
The coating compositions according to the present invention may be
applied to the film resistor by any of the well known coating
methods. For example, the composition may be solvent sprayed onto
the film resistor, or the film resistors may be dip-coated by
immersion thereof in a suitable solution of the coating
composition. The coatings may also be applied by brush or roller
coating applications. It is to be further understood that the
invention is not limited to any particular method of applying the
novel coating compositions of the present invention and that any of
the conventional, well known coating methods may be employed to
effect the deposition of the flame-resistant coating composition on
the resistor.
Suitable solvents for use in conjunction with the coating
compositions of the present invention are any organic liquids
capable of dissolving the components of the composition and which
are chemically inert with respect thereto. Suitable solvents
include the liquid dialkylcarboxylamides such as
N,N-diethylacetamide and dimethyl sulfoxide, and
N-methyl-2-pyrrolidone.
It should also be understood that the coating compositions may be
modified with inert pigments, dyes, inorganic and organic fillers
as desired. For example, titanium dioxide, carbon, earth pigments
or mixtures thereof may be added to the compositions to provide
desired colors. Fillers such as asbestos, bentonites, silica, etc.
may also be incorporated.
The invention is more specifically explained by the following
illustrative examples which are not necessarily intended to be
limiting. In these examples, all parts and percentages are by
weight except as noted.
EXAMPLE I ______________________________________ Parts
______________________________________ Polyimide (DuPont RK-692)
100 Chlorinated Polyphenyl (Monsanto Arochlor 5460) 10 Antimony
Trioxide 5 ______________________________________
A dimethylformamide solution of the above composition was solvent
sprayed onto a conventional film resistor. The resistor was
subjected to a severe electrical overload resulting in a body
temperature of between 500.degree. and 600.degree.C. No burning,
smoking or flaming of the coating was detected. Moreover, the
coating intumesced to form a protective cocoon around the resistor
thereby confining arcing and causing the resistor to open.
The following examples illustrate other coating compositions which
were coated onto resistors as in Example I and operated similarly
to protect the resistor.
EXAMPLE II ______________________________________ Parts
______________________________________ Polyimide (DuPont RK-692)
100 Chlorinated Polyphenyl (Monsanto Aroclor 5460) 20 Antimony
Trioxide 10 ______________________________________
EXAMPLE III ______________________________________ Parts
______________________________________ Polyimide (DuPont RK-692)
100 Chlorinated Polyphenyl (Monsanto Aroclor 5460) 10 Antimony
Trioxide 10 ______________________________________
The invention herein disclosed may be variously modified and
embodied within the scope of the following claims.
* * * * *