U.S. patent number 3,625,844 [Application Number 04/830,789] was granted by the patent office on 1971-12-07 for stainproofing process and products resulting therefrom.
This patent grant is currently assigned to Circuit Foil Corporation. Invention is credited to Walter A. McKean.
United States Patent |
3,625,844 |
McKean |
December 7, 1971 |
STAINPROOFING PROCESS AND PRODUCTS RESULTING THEREFROM
Abstract
An electrolytic process for imparting stain resistance to sheet
copper comprising rendering the copper sheet cathodic in an
electrolytic cell containing an aqueous electrolyte containing
about 0.4-0.8 grams/liter of hexavalent chromium ions and
subjecting said foil to a current density of about 2-4
amps/ft..sup.2 for about 6-8 seconds. Products resulting
therefrom.
Inventors: |
McKean; Walter A. (Colonia,
NJ) |
Assignee: |
Circuit Foil Corporation
(Bordentown, NJ)
|
Family
ID: |
25257695 |
Appl.
No.: |
04/830,789 |
Filed: |
June 5, 1969 |
Current U.S.
Class: |
205/704; 205/283;
205/142 |
Current CPC
Class: |
C25D
11/38 (20130101); H05K 3/282 (20130101) |
Current International
Class: |
C25D
11/38 (20060101); C25D 11/00 (20060101); H05K
3/28 (20060101); C23b 001/00 (); C23b 005/58 ();
C23b 009/00 () |
Field of
Search: |
;204/140,28,56 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Tufariello; T.
Claims
What is claimed is:
1. An electrolytic process of imparting stain resistance to sheet
copper comprising rendering said copper sheet cathodic in an
electrolytic cell containing an electrolyte comprised of an aqueous
solution containing about 0.4 to 0.6 grams/liter hexavalent
chromium ions (determined as CrO.sub.3) and subjecting said sheet
copper to a current density of about 2 to 4 amps/ft..sup.2 for
about 6 to 8 seconds.
2. A process as defined in claim 1 wherein said copper is copper
foil.
3. A process as defined in claim 1 wherein said electrolyte is
substantially free of impurities.
4. A process as defined in claim 1 wherein said electrolyte
contains dissolved chromium trioxide.
5. The product of the process of claim 2.
6. The product of the process of claim 1.
Description
BACKGROUND OF THE INVENTION
One of the problems with which manufacturers of copper foil (both
of the electrolytic and rolled variety) are faced is the staining
of the copper foil between the time of shipment and the time of use
by the ultimate purchaser. This staining results from the exposure
of the copper to normal atmospheric and other conditions and,
particularly for applications of the copper foil in critical areas
such as printed circuitry, is an extremely undesirable
characteristic.
In the past, various suggestions have been made for stainproofing
copper foil. While a number of the approaches used in the past have
served to stainproof such foil, one of the difficulties related to
the use of such techniques is that they have created one or more
collateral problems negatively affecting the desirability of the
treated copper for use in printed circuit applications and the
like. Such problems include:
a. a decrease in the bond strength of the stainproofed foil;
b. an increase in the etching resistance of the foil;
c. a decrease in the solvent resistance of the adhesive/treatment
interface; and/or
d. a decrease in the solderability of the shiny side of the
foil.
SUMMARY OF THE INVENTION
In accordance with the present invention, a novel stainproofing
technique is provided which provides to copper foil a finish having
superior tarnish and oxidation resistance but which does not
deleteriously affect such foil in any of the manners described
above. This technique involves the use of an aqueous electrolyte
under critical conditions of hexavalent chromium ion concentration,
cathode current density and treatment time.
OBJECTS OF THE INVENTION
It is accordingly an important object of the present invention to
provide a novel stainproofing technique useful in stainproofing
copper foil rendering such foil particularly adapted for use in
printed circuit applications.
It is a further important object of the present invention to
provide an improved electrolytic stainproofing technique for
stainproofing copper foil involving the use of a novel electrolyte
bath as well as products resulting therefrom.
These and other important objects and advantages of the present
invention will become more apparent as this description
proceeds.
DESCRIPTION OF THE DRAWINGS
The figure is a front elevation, partly in section, illustrating an
electrolytic tank for carrying out the process of the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
As previously noted, the material to be subject to the improved
stainproofing treatment of the present invention is sheet copper.
While electrodeposited copper foil is preferred (particularly for
printed circuit applications), other types of sheet copper (such as
rolled foil) may be used.
The preferred method for stainproofing such foil is to use an
elongated sheet of such foil and to pass such elongated sheet
through an appropriate electrolyte using an apparatus such as is
illustrated in the figure. The apparatus illustrated therein
comprises a tank 10 containing an electrolyte inlet 12 and
electrolyte outlet 14 by means of which electrolyte 16 respectively
enters and is withdrawn from tank 10. The positive bus bar 18 is
secured to one longitudinal top edge of tank 10 by means of
insulating strip 20. Supported on the bus bar 18 and insulating
strip 20 by means of copper bars 22 are a plurality of anodes 24.
These anodes 24 are shown in the form of thick, insoluble planar
lead plates (which may appropriately be also made of stainless
steel). A terminal lead 25, adapted to be connected to the positive
terminal of a power source (not shown), is connected to the bus bar
18. A support frame 26 is mounted on the tank 10.
In order to guide a sheet of copper 28 to be stainproofed, two
upper electrically connected idler rollers identified by the
numbers 30 and 32 are mounted on and are in electrical contact with
the support frame 26, and a polyvinyl chloride idler roll 34 is
rotatably mounted on a stainless steel bar 36 which, in turn, is
connected to the supporting frame 26 at its upper end. By virtue of
the electrical contact between rollers 30 and 32 and support frame
26, and by connecting the latter to the negative terminal of a
power source (not shown), copper sheet 28 may be rendered
cathodic.
The continuous sheet of copper 28 which is to be stain-proofed is
shown fed from a supply spool 38 mounted on the support frame 26,
over the first upper idler 32 and into the electrolytic bath 16.
The continuous sheet 28 is guided into and out of the electrolyte
16 in serpentine fashion by means of the idler roller 34 at the
bottom of the tank 10 and the upper idler roller 30. As the
stainproofed sheet 28 emerges from the electrolytic tank 10, it
passes by a pair of nozzle elements 40 and 42 which are connected
to a source of wash solution (not shown) to permit the sheet 28 to
be spray washed on both sides. The stainproofed sheet of copper is
then fed across idler roller 44, past a squeegee device 46 which
removes any excess material, past a pair of infrared lamps and an
idler roller 52, 48 and 50 to dry the stainproofed material and
finally to the take-up roll 54 which is provided with a suitable
drive mechanism (not shown) which provides the necessary force to
draw the sheet of copper 28 through the system.
By passing the copper foil through the system in the manner
indicated, the matte and shiny surfaces of the foil will receive an
electrochemical treatment and will have stain resistance imparted
thereto.
As will be apparent, electrolytic tank 10 can be enlarged and
additional anodes 24 added to increase the amount of exposure of
the moving sheet of foil to electrolytic treatment, though for the
purpose of the present invention, a 3-anode system is quite
adequate to expose the foil to the critical treatment time
mentioned below.
The electrolyte employed in the present invention is an aqueous
electrolyte containing hexavalent chromium ions which is preferably
substantially free of any impurities. Such an electrolyte may
conveniently be formed by dissolving chromium trioxide (CrO.sub.3)
in water to form chromic acid. This aqueous solution must contain
0.4-0.6 grams/liter of hexavalent chromium ions (determined as
CrO.sub.3). As the copper foil passes through the electrolyte, it
should be subjected to a cathode current density of about 2-4
amps/ft..sup.2 for about 6-8 seconds.
When foil is subject to conditioning as set forth above, the foil
has a remarkable degree of resistance to oxidation and tarnishing
as measured by several accelerated staining test procedures
(immersion in a sulfide test solution and a humidity exposure
test), while not suffering any of the disadvantages previously
noted as being associated with prior art techniques.
The particular hexavalent chromium ion concentration, cathode
current density and exposure time are critical in the carrying out
of the process of the present invention. More specifically, when
hexavalent chromium ion concentrations, cathode current densities
and exposure times below the aforementioned lower limits are used,
adequate stain protection is not provided to the copper foil;
similarly, the use of hexavalent chromium ion concentrations,
cathode current densities and exposure times above the
aforementioned upper limits hinders etching of the foil in printed
circuit applications.
In a specific example of the process of the present invention, one
ounce copper foil (which had been previously electrochemically
treated to improve bond strength) was passed in serpentine fashion
in the manner indicated above past insoluble lead anodes in an
aqueous chromic acid electrolyte containing 0.5 grams/liter of
hexavalent chromium ions (determined as CrO.sub.3). The electrolyte
was at a temperature of 25.degree. C., the cathode current density
was 3 amps/ft..sup.2 and the copper was immersed in the electrolyte
for 7 seconds. The resulting copper foil has excellent stain
resistance as measured by a standard sulfide stain resistance test
and passes a standard etchability test employed for printed circuit
applications.
The standard sulfide stain resistance test involves the immersion
of the foil in a filtered solution of 5 grams/liter of Zonax
Oxidizing Salt (a proprietary material produced by W. Canning Co.
in Birmingham, England which is likely an ammonium polysulfide
compound) in distilled water. The solution is maintained at room
temperature without agitation.
Stain resistance is proportional to the time after immersion that
an overall black film is produced on the shiny surface of the foil.
Untreated foil will stain in less than 5 seconds, ordinary prior
art stainproofed foil in 15 to 30 seconds, while foil stainproofed
in accordance with the process of the present invention may last
over 5 minutes without staining.
The standard etching test described above is as follows:
A. solutions
l. Etch solution (5 percent ferric chloride in water) a standard
42.degree. B. ferric chloride etch solution such as Hunt's RCE in
the ratio of one part concentrate plus 7 parts water.
2. Post-etch cleaning solution 10 percent by volume of concentrated
hydrochloric acid in water.
B. procedure
Immerse the sample to be tested in the 5 percent etch solution at
room temperature and without agitation for 60 seconds. Remove from
the etch and place in the 10% hydrochloric acid solution for 60
seconds. Remove and wash in running water. Dry and examine.
A properly etched specimen will exhibit a uniform matte surface of
a reddish pink color. Non-etchability shows shiny streaks or areas
in the immersed portion. Extreme cases of etch resistance appear
indistinguishable from the unetched areas.
This test applies only to the shiny surface of electrodeposited
foil.
The invention may be embodied in other specific forms without
departing from the spirit or essential characteristics thereof. The
present embodiment is therefore to be considered in all respects as
illustrative and not restrictive, the scope of the invention being
indicated by the appended claims rather than by the foregoing
description, and all changes which come within the meaning and
range of equivalency of the claims are therefore intended to be
embraced therein.
* * * * *