U.S. patent number 3,880,685 [Application Number 04/874,100] was granted by the patent office on 1975-04-29 for process and apparatus for etching copper and copper alloys.
This patent grant is currently assigned to Hans Hoellmueller Maschinenbau. Invention is credited to Winfried Eggert, Alfred Rehm.
United States Patent |
3,880,685 |
Rehm , et al. |
April 29, 1975 |
Process and apparatus for etching copper and copper alloys
Abstract
Copper and copper alloys, in particular copper-coated laminates,
are etched by immersing them in or spraying them with a solution of
cupric chloride and regenerating the formed cuprous chloride during
continuing operation by adding hydrogen peroxide and hydrochloric
acid to the etching solution, the amount of the addition being
controlled by measurements of the redox potential by means of a
redox electrode and the control being adjusted to add predetermined
amounts of the said two additives whenever the copper-I-ion
concentration reaches a predetermined value, preferably 0.4 g/l so
as to maintain a constant etching speed. An apparatus for use in
this method comprises a tank for the etching solution, means for
applying the solution to the copper or copper alloy material, a
redox electrode immersed in the said tank, supply vessels for
holding the regenerating additives, a conduit between said supply
vessels and the tank, valve means for passing the regenerating
liquid from the supply vessels to the tank and control means for
operatively connecting the valve means to the redox electrode.
Inventors: |
Rehm; Alfred (Villingen,
Schwarzwald, DT), Eggert; Winfried (Oberstadion,
DT) |
Assignee: |
Hans Hoellmueller Maschinenbau
(Gueltstein, DT)
|
Family
ID: |
5712562 |
Appl.
No.: |
04/874,100 |
Filed: |
November 5, 1969 |
Foreign Application Priority Data
Current U.S.
Class: |
216/93; 134/902;
422/119; 216/106; 134/57R; 422/107 |
Current CPC
Class: |
C23F
1/08 (20130101); C23F 1/46 (20130101); Y10S
134/902 (20130101) |
Current International
Class: |
C23F
1/08 (20060101); C23F 1/46 (20060101); C23b
003/00 () |
Field of
Search: |
;324/29,30 ;23/23A,253A
;156/19,345 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Greer, "Measurement and Automatic Control of the Etching Strength
of Ferric Chloride," pub. in Plating, pp. 1095-1096, Oct.
1961..
|
Primary Examiner: Lesmes; George F.
Assistant Examiner: Roche; R. J.
Attorney, Agent or Firm: Striker; Michael S.
Claims
I claim:
1. A method for continuously etching copper conductive plates which
comprises contacting the copper conductive plate to be etched with
an etching solution of cupric chloride (copper (II) chloride) and
regenerating the etching solution containing cuprous chloride
(copper (I) chloride) formed in the etching by reaction between
said copper conductive plate and said etching solution by
introducing hydrogen peroxide and hydrochloric acid into said
etching solution, the amounts of hydrogen peroxide and hydrochloric
acid introduced being regulated by continuously measuring the redox
potential of said etching solution by means of a redox electrode
and automatically introducing said hydrogen peroxide and
hydrochloric acid whenever the cuprous ion (Cu(I) ) concentration
in said etching solution exceeds 4 g/l in an amount at least
sufficient to reduce said cuprous ion (Cu(I) ) concentration below
said value whereby the cuprous ion concentration is continuously
maintained below said value and a constant etching speed is
maintained.
2. Method according to claim 1 wherein hydrogen peroxide and
hydrochloric acid are automatically introduced into said etching
solution whenever the cuprous ion concentration exceeds 0.4
g/l.
3. Method according to claim 1 wherein hydrogen peroxide and
hydrochloric acid are automatically introduced into said etching
solution whenever the cuprous ion concentration exceeds 2 g/l.
4. Method according to claim 1 wherein said hydrogen peroxide and
hydrochloric acid are introduced in a molar ratio of 1:2 hydrogen
peroxide to hydrochloric acid.
Description
BACKGROUND OF THE INVENTION
The invention concerns a process for etching printed circuit boards
in immersion and spray apparatus.
A variety of methods exists for etching conductor plates, e.g.,
printed circuits. Known etching agents are aqueous solutions of
ferric chloride (FeCl.sub.3), ammonium persulphate (NH.sub.4).sub.2
S.sub.2 O.sub.8), sodium chlorate and hydrochloric acid
(NaCIO.sub.3 + HCl), sodium chlorite (NaClO.sub.2), hydrogen
peroxide and sulfuric acid (H.sub.2 O.sub.2 + H.sub.2 SO.sub.4),
and cupric chloride (CuCl.sub.2) with various regenerating agents
such as air and oxygen. Immersion or spray apparatus is used for
etching, the latter, in particular, in the form of a continuous
process operation particularly suitable for manufacture of
conductive sheets on a conveyor belt. An economical conveyor
belt-type manufacture is conditional on maximum and constant
throughput speed. In most etching processes so far known increasing
copper content in the etching agent and decreasing etching agent
power meant lengthened etching times. If, for example, the copper
content rises from 0 to 50 g Cu/liter the etching time in an
ammonium persulphate bath rises from 6 to 33 minutes and in a
hydrogen peroxide/sulfuric acid bath from 5 to 21.5 minutes (German
published application 1,253,008). In another process using hydrogen
peroxide and sulfuric acid plus a catalyst, etching times of 1.5
minutes initially and 3 minutes at approximately 35 g Cu/liter have
resulted. At higher copper contents the etching time is further
lengthened and becomes uneconomical. With iron chloride as etching
agent, initial etching time is about 1 minute, but even when ferric
chloride is used as the etching agent the initially high etching
rate goes steadily down with rising copper contents and, in spray
apparatus, etching times become uneconomical at copper contents of
about 50 g resulting in low throughput rates.
It has already been proposed to use copper-II-chloride as etching
agent and to regenerate the copper-I-chloride which reduces the
etching speed, by means of hydrogen peroxide and hydrochloric acid.
However, this type of process was not suited for industrial
production since, on the one hand, even small amounts of
copper-I-chloride substantially reduce the etching speed and, on
the other hand, the addition of hydrogen peroxide is a highly
critical matter since, if too much hydrogen peroxide is added,
oxygen forms and the etching agent is subject to gassing. This
again reduces the etching speed. Besides, the gassing etching agent
can no longer be pumped with adequate pressure because the liquid
pumps which are in particular used in connection with a spraying
operation are not suited for moving liquid-gas mixtures.
If, on the other hand, the addition of hydrogen peroxide is too
small, an adequate regeneration of the copper-I-chloride does not
take place and the residual copper-I-chloride thus again
contributes to a reduction of the etching operation speed.
It is accordingly an object of the present invention to avoid the
shortcomings described and to provide for an etching process and
etching apparatus which is useful for industrial production, and in
particular for the etching of conductive plates in a dipping or
spraying operation.
SUMMARY OF THE INVENTION
This object is met by a method of etching conductive plates of
which the surface is formed by copper or a copper alloy, the said
method comprising the steps of applying an etching solution of
copper-II-chloride to the plate by immersion or spraying and
regenerating the formed copper-I-chloride in the etching solution
by adding hydrogen peroxide and hydrochloric acid to the solution
during continuing operation, the amount of the addition being
controlled by a continuous measurement of the redox potential of
the etching solution by a redox electrode and the said control
being adjusted to add predetermined amounts of hydrogen peroxide
and hydrochloric acid whenever the copper-I-ion concentration
reaches a predetermined value, so as to maintain a constant etching
speed.
The invention also embraces an apparatus for carrying out the
method just defined, comprising a tank for holding the etching
solution, means for applying the solution to the copper or copper
alloy surface, a redox electrode immersed in said tank for
measuring the redox potential, at least one supply vessel for
holding a regenerating liquid, a conduit between said vessel and
said tank, valve means for opening and closing said conduit and
passing liquid from said supply vessel to said tank, and control
means for operatively connecting said valve means with said redox
electrode.
The novel features which are considered as characteristic for the
invention are set forth in particular in the appended claims. The
invention itself, however, both as to its construction and its
method of operation, together with additional objects and
advantages thereof, will be best understood from the following
description of specific embodiments when read in connection with
the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1a is a graph plotting the Cu.sup.+ ion concentration of the
etching solution against the redox potential identified as u;
FIG. 1b is a partial enlarged view of the encircled portion of FIG.
1a;
FIG. 1c is a graph plotting the etching velocity v against the
redox potential; and
FIG. 2 is a diagrammatic view of the apparatus of the
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process of the invention permits to shorten the mean etching
time obtainable with iron chloride by a substantial amount, that is
by about 40%. This is of course of great significance for the
economies of the operation.
While the initial etching speed of the process of the invention as
compared with the customary iron-III-chloride process is somewhat
smaller, this initial speed, by virtue of the process of the
invention, can be maintained rather constant during the entire
operation irrespective of the number of plates or sheets which pass
through the etching apparatus and irrespective of the amount of
copper subjected to etching.
In the apparatus of the invention, the dimensions of the conduits
passing the regenerating liquid or liquids from the supply vessel
or vessels to the tank holding the etching solution should be
dimensioned so as to comply with the optimum amount-ratio of the
regenerating chemicals.
It is preferred if the valves which control the addition of
regenerating liquids are arranged to be actuated in succession so
that a small excess of hydrochloric acid may thus be supplied. This
will then definitely avoid the decomposition of the hydrogen
peroxide into hydrogen and oxygen.
In general, when the etching is effected by using
copper-II-chloride, copper-I-chloride will be formed according to
the equation Cu + CuCl.sub.2 = 2 CuCl. A comparatively minute
amount of copper-I-chloride, such as 4 g Cu.sup.+/l in the etching
solution, which latter may for instance contain 120 g
Cu.sup.+.sup.+/l in the form of copper-II-chloride, will noticeably
slow down the etching speed as appears from the curve in FIG. 1c.
However, it is of interest that the absolute value of the copper
content does not have to be particularly constant in order to
obtain a high etching speed. Rather, it may vary between 80 g Cu/l
and 130 g Cu/l. It is rather important to maintain the
Cu-I-chloride amount which is being formed during the etching
operation at a low value, for instance below 2 g/l, and to
reoxidize it as fast as possible to copper-II-chloride.
The regeneration, from the purely stoichiometric standpoint, takes
place following the equation:
2 CuCl + H.sub.2 O.sub.2 + 2 HCL.fwdarw.2 CuCl.sub.2 + 2 H.sub.2
O
However, the actual mechanism of the reaction between these
components is far more complex than expressed by the equation and
does not require discussion here. As the stoichiometric equation
shows, it is necessary to add the regenerating chemicals H.sub.2
O.sub.2 and HCl in required ratio, that is, for 34 g of H.sub.2
O.sub.2,2 HCl, i.e. 2 .times. 36.5 g, must be added. For instance,
if a 35% concentration H.sub.2 O.sub.2 solution and a 37.5%
concentration hydrochloric acid are used, the chemicals must be
added at a ratio of 1:2, which can easily be done by means of the
proper dimensioning of the conduits from the supply vessels.
The above equation of the reaction occurring during the
regeneration also shows that hydrochloric acid is used up during
the regeneration, resulting in a change of the pH of the etching
solution. One might at first think that the pH could therefore be
controlled by a pH electrode which would adjust the amount of
addition of the regenerating agent. However, in practical
applications, it has been found that in this manner optimum etching
conditions cannot be obtained. If, on the other hand, the amount of
addition is controlled by a redox electrode, as proposed in the
present invention, the desired object can be accomplished with
great precision.
During the etching operation there are present in the solution
Cu.sup.+.sup.+ ions and Cu.sup.+ ions. The potential of the
electrode depends on the concentration ratio, or more properly on
the activity ratio, as indicated by the following formula ##EQU1##
wherein the symbols have the following meaning: E electromotoric
force (EME)
r gas constant
T absolute temperature
F Faraday-equivalent
The potential of the electrode will be positive when the
concentration of the higher oxidation stage rises and it will reach
the maximum value when the Cu.sup.+ ion concentration is zero. With
increasing Cu.INTEGRAL. ion content, the potential of the solution
changes. This change will be comparatively stronger in the area of
small Cu ion concentration (0 to 4 g/l) than with higher increases
in the Cu.sup.+ ion as is illustrated by the curves in FIG. 1a and
FIG. 1b.
FIG. 1a illustrates qualitatively the interrelation between the
etching velocity v and the redox potential u. The redox potential
u, as will be seen, at 530 mV which occurs at a Cu.sup.+ ion
concentration of less than 0.4 g/l (see FIG. 1b) will afford an
optimally high and almost constant etching speed. It is therefore
preferred to practice the invention by maintaining this limit value
during the regeneration of the etching agent.
This change of potential is made use of in the apparatus of the
invention for controlling the addition of the regeneration
chemicals. With reference to FIG. 2 it will be seen that the
apparatus 1 may for instance be used to process conductive plates 2
which consist of a copper-coated laminate. The conductive plates
are passed by means of a conveyor belt 3 under the spray nozzles
4.
In order to regenerate the etching solution, the hydrogen peroxide
and hydrochloric acid are fed from the supply vessels 8 and 9
through magnet valves 10 and 11 and are furthermore pumped by pumps
12 and 13 into the etching solution in tank 5. The magnet valves
10, 11 and the pumps 12, 13 are controlled by the potential as
determined through the redox electrode 14 and the control measuring
device 15.
The control device comprises, in a preferred form, an amplifier, a
measuring device and a recording device which, through
amplification, indicate or record the potential differences. The
measuring device is provided with two adjustable sensors which
cooperate with the hand of the measuring device. The sensors and
the hand of the measuring device are designed to generate a signal
whenever the hand in response to a change of potential in the
etching solution moves from the area of the higher potential with a
gradually increasing Cu.sup.+ ion concentration into the area of a
lower potential and in so moving passes the sensors and causes a
response thereby.
This response thus occurs at a definitely determined value and
causes the opening of the magnet valves 10 and 11 in succession,
and likewise causes actuation of the pumps 12 and 13 successively.
Thus, the regenerating liquids H.sub.2 O.sub.2 and HCl are fed from
the supply vessels 8 and 9 into the etching solution in tank 5.
The two sensors of the control device, in order to attain a
constant high etching speed, are adjusted to prevent exceeding a
potential difference of about 150 mV and thus to maintain the
Cu.sup.+ ion content below 2 g/l.
The two sensors are also spaced from each other so that the first
valve which adjusts the hydrochloric acid flow from the vessel 9
will open earlier than the second valve which controls the H.sub.2
O.sub.2 flow. Conversely, when the hand moves in the other
direction, the hydrochloric acid valve will be closed at a definite
time interval prior to the closing of the H.sub.2 O.sub.2 valve.
This type of adjustment will assure that there is always a small
HCl excess in the solution.
A particular advantage of the process of the invention is that the
regenerating liquids can be supplied during the etching operation
and that used-up etching solution can be withdrawn likewise during
the operation. Thus, an interruption of the process, which
heretofore has always been necessary, is avoided.
The spent etching solution also has a high re-use value since it
consists of a hydrochloric acid-containing Cu-II-chloride solution
without addition of other salts, and can therefore be used in the
manufacture of various kinds of copper compounds. The cumbersome
and expensive decontamination and neutralization of the drainage
water, which in conventional etching apparatus is always necessary,
is thus dispensed with.
EXAMPLE
This example illustrates a preferred method of practicing the
invention by means of the apparatus above described.
The material treated in this example were laminates with a facing
of pure copper. The solution in the tank at the commencement of the
operation comprised 100-130 g copper II-chloride per liter and a
10% concentration of hydrochloric acid. The solution was sprayed
onto the plates at a temperature of 40.degree.-50.degree.C which
developed during the reaction.
After 0.4 g/l Cu.sup.+ -ion-concentration corresponding to a redox
potential of 530mV was reached, the Redox-electrode by means of the
control device opened the valve of the supply vessel holding HCl
and at the same time actuated the pump to feed HCl into the main
tank. The delayed action valve and pump of the supply vessel
holding H.sub.2 O.sub.2 opened shortly thereafter.
An etching speed of 35.mu. copper was thus reached in about 75
seconds and kept practically constant.
* * * * *