U.S. patent number 3,617,450 [Application Number 04/750,947] was granted by the patent office on 1971-11-02 for automatic stripping of electrodeposited starting sheets.
This patent grant is currently assigned to Mitsubishi Kinzoku Kogyo Kabushiki Kaisha. Invention is credited to Ryuzo Kawaguchi, Kizo Nara, Izumi Sukekawa.
United States Patent |
3,617,450 |
Kawaguchi , et al. |
November 2, 1971 |
AUTOMATIC STRIPPING OF ELECTRODEPOSITED STARTING SHEETS
Abstract
Starting sheets (copper sheets electrolytically deposited on
cathode base sheets) can be readily stripped from their base sheets
by pulling with suction disk when a layer of air is formed in the
interface between each starting sheet and its base sheet by a
simple physical process such as rolling or vibration applied to one
part of the sheet. Stripping is further facilitated and the
starting and base sheets are protected by the application on the
base sheets before electrolysis of at least one coating agent
containing an organic compound of an acid such as phosphoric acid,
xanthic acid, thiocarbonic acid, or thiocarbamic acid or an organic
ester such as organic phosphorous ester.
Inventors: |
Kawaguchi; Ryuzo (Akita-shi,
JA), Nara; Kizo (Osaka-shi, JA), Sukekawa;
Izumi (Musashino-shi, JA) |
Assignee: |
Mitsubishi Kinzoku Kogyo Kabushiki
Kaisha (Chiyoda-ku,Tokyo-to, JA)
|
Family
ID: |
25019809 |
Appl.
No.: |
04/750,947 |
Filed: |
August 7, 1968 |
Current U.S.
Class: |
205/76;
204/281 |
Current CPC
Class: |
C25C
7/08 (20130101) |
Current International
Class: |
C25C
7/08 (20060101); C25C 7/00 (20060101); C23b
007/02 (); B01k 001/00 () |
Field of
Search: |
;204/3,4,12,281,106 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Williams; Howard S.
Assistant Examiner: Tufariello; T.
Claims
We claim:
1. In the preparation of starting sheets for cathode base sheets by
electrolysis of metal, including the step of first coating the
surface of each cathode base sheet with a coating agent to prevent
strong bonding of a starting sheet to the surface thereof, then
carrying out electrolysis to deposit the starting sheet on the
surface of the cathode base sheet, subsequently forming a layer of
air by a physical process at one portion between the starting sheet
thus deposited and the cathode base sheet upon completion of the
electrolysis, and stripping the starting sheet from the cathode
base sheet by means of lower pressure or vacuum suction discs, an
improvement comprising
performing said coating step with said coating agent selected from
the group consisting of solutions and emulsions of organic
compounds of phosphoric acid and thiophosphoric acid, organic
phosphorus esters, organic thiophosphorus esters, compounds of
xanthic acid, organic compounds of thiacarbonic acid, compounds of
thiacarbonic acid, and thiazole compounds.
2. The method as claimed in claim 1 in which the layer of air is
formed by applying vibration to a part of the starting sheets.
3. The method as claimed in claim 1 in which the layer of air is
formed by applying percussion to a part of the starting sheets.
4. A method as claimed in claim 1 in which the coating agent is at
least one member selected from the group consisting of solutions
and emulsions of organic compounds representable by the general
formulas:
(RO).sub.n PO (OX).sub.3.sub.-n
where
R is a chain hydrocarbon radical,
X is a member selected from the group consisting of hydrogen,
sodium, potassium, and amino alcohol, and
n assumes the values of 1, 2, and 3; (RO).sub.n PO
(SX).sub.3.sub.-n
where
R is a chain or aromatic hydrocarbon radical,
X is a member selected from the group consisting of hydrogen,
sodium, potassium, and amino alcohol, and
n assumes the values of 1, 2, and 3;
where
R.sub.1 is a chain hydrocarbon radical and has eight or more carbon
atoms when R.sub.2 and R.sub.3 are hydrogen,
each of R.sub.2 and R.sub.3 is a member selected from the group
consisting of chain and ring hydrocarbon radicals, hydrogen,
sodium, potassium, amines, and
each of Z.sub.1, Z.sub.2, and Z.sub.3 is a member selected from the
group consisting of oxygen and sulfur; and
where
R is a hydrocarbon radical,
X is a nucleophilic reagent selected from the group consisting of
oxygen, sulfur, nitrogen, and imino group,
Y is a radical selected from the group consisting of sulfur,
nitrogen, and imino radicals, and
Z is a radical selected from the group consisting of hydrogen,
metal, and hydrocarbon radicals,
5. A method of preparing starting sheets for cathode base sheets by
electrolysis of metal, comprising the steps of first coating the
surface of each cathode base sheet with a coating agent to prevent
strong bonding of a starting sheet to the surface thereof, then
carrying out electrolysis to deposit the starting sheet on the
surface of the cathode base sheet, said coating agent being
selected from the group consisting of solutions and emulsions of
organic compounds of phosphoric acid and thiophosphoric acid,
organic phosphorus esters, organic thiophosphorus esters, compounds
of xanthic acid, organic compounds of thiocarbonic acid, compounds
of thiocarbonic acid, and thiazole compounds.
Description
BACKGROUND OF THE INVENTION
This invention relates generally to electrolytic processing of
copper and more particularly to a new method and apparatus for
automatic stripping of starting sheets in electrolytic refining and
winning of copper (hereinafter referred to as "copper
electrolysis").
Starting sheets for use in copper electrolysis are ordinarily
prepared by electrodeposition of copper on cathode base sheets of
smooth rolled copper sheets or stainless steel sheets. In the case
of rolled copper sheets, if their surfaces are clean, the
electrodeposited copper, i.e., the starting sheets, will adhere
intimately to their cathode base sheets and be bonded firmly
thereto and give rise to great difficulty in stripping of the
starting sheets. Accordingly, it has been the common practice to
apply onto the surfaces of the rolled copper sheets coating
materials such as oils, fats, asphalts, and soaps thereby to
prevent excessively strong adhesion. In the case of stainless steel
sheets, polishing has been resorted to in order to prevent such
bonding of the starting sheets.
Heretofore, starting sheets which have been electrodeposited on
cathode base sheets have been stripped by a manual procedure which
comprises inserting a knife-edged tool between each starting sheet
and its cathode base sheet and prying open a gap between the two
sheets thereby to separate them by manually applied force. In this
procedure, the resistance to stripping, i.e., the force necessary
for stripping the starting sheet from the cathode base sheet,
differs extremely depending on the nature of the coating material.
For example, when a mixture of 90 percent of a boiled oil and 10
percent of asphalt primer is applied, this stripping force is from
1.0 to 2.5 kg. per 25 mm. of width.
Such a manually stripping procedure depending on human power,
however, is accompanied by extreme danger and, moreover, by the
risk of damaging the surfaces of the cathode base sheets since a
knife-edged tool is used. Since starting sheets adhere strongly to
damaged surfaces of the cathode sheets, the subsequent stripping
operations after succeeding electrodepositions are more
difficult.
Furthermore, when starting sheets are stripped by hand, curvatures
and warping to a certain extent in the stripped starting sheets
cannot be avoided. According to our experience, it is not possible
to accomplish practical stripping by hand without inserting a
knife-edged tool between the starting sheet and the cathode base
sheet. On the other hand, however, a mechanical stripping procedure
is difficult because of the thinness of the starting sheets and is
accompanied by the risk of applying excessive force and thereby
damaging the cathode base sheets and other parts.
With the aim of overcoming these difficulties, we attempted to
accomplish mechanical stripping by attaching low-pressure or vacuum
suction cups of disks to starting sheets electrodeposited on
cathode base sheet and applying pulling force away from and
perpendicularly to each cathode base sheet. However, we found it
impossible to separate the starting sheets from their cathode base
sheets, irrespective of the size of the suction disks and the
magnitude of the pulling force.
The reason for this is that, since the bond between the cathode
base sheet and the starting sheet with a layer of a coating agent
for facilitating stripping interposed therebetween is due to
electrodeposition, no layer of air, whatsoever, exists in the
interface parts related to this bond, and a powerful adhesion due
to vacuum acts between the cathode base sheet and the starting
sheet to resist separation thereof.
Therefore, one solution to this problem is to cause an air layer to
be created between the cathode base sheet and each starting sheet
to eliminate the adhesion therebetween due to the absence of an air
layer.
Another expedient for facilitating stripping is to use a greatly
improved coating agent for stripping. Examples of coating agents
used or known heretofore are sodium sulfide, calcium sulfide,
mercurous chloride, silver nitrate, chain hydrocarbons such as fuel
oils, light oils, and paraffin, fatty acids, sodium soaps, boiled
oils, asphalts, and emulsions containing light oils.
These coating agents, however, have numerous disadvantages such as
short life, the tendency to produce copper powder on the cathode,
and the tendency to impair the properties of the electrolytic
copper sheets. While oily coating agents are particularly excellent
for facilitating the stripping action, they impair the
electrodeposition of the copper. While the use of water-soluble
coating agent results in good electrodeposition, the subsequent
stripping is caused to be somewhat difficult.
Accordingly, the ordinary practice when using new cathode base
sheets has been to use, first, an oily coating agent. For example,
a coating mixture of a boiled oil and asphalt primer (10 percent)
is initially applied, and then, from the succeeding operation, the
cathode base sheets are dipped in a 5-percent solution of a
water-soluble soap each time electrolytic copper sheets are
produced. Ordinarily, after from 7 to 10 cycles of use, copper
particles and other impurities are formed as electrolytic copper is
electrodeposited on the cathode base plates. Accordingly, an oily
coating agent as, for example, a light oil or a boiled oil, is
again applied for stripping.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method for
automatically stripping starting sheets from cathode base sheets in
a safe manner without damaging the sheets and thereby to decrease
the rate or rejection of defective starting sheets and increase
production efficiency and economy.
Another object of the invention is to provide a relatively simple
apparatus for thus automatically stripping starting sheets from
cathode base sheets.
Still another object of the invention is to provide effective
coating agents for application on the surfaces of cathode base
sheets to prevent strong bonding thereto of electrodeposited
starting sheets thereby to facilitate stripping.
A further object of the invention is to provide coating agents of
the above stated character which will not adversely affect the
state, properties, and uniformity of the copper starting sheets
electrolytically deposited on the cathode base sheets.
According to the present invention, briefly summarized, there is
provided a method, and apparatus for automatically stripping
starting sheets from cathode base sheets in the preparation of
starting sheets in copper electrolysis, the method being
characterized by the steps of creating an air layer in one part of
the adhering part of each starting sheet electrodeposited on a
corresponding cathode base sheet by a physical process such as
vibration, percussion, or rolling between rolls and thereafter
separating the two sheets by means of low-pressure or vacuum
suction disks.
According to the present invention there is further provided a
simple apparatus for carrying out the above described method in a
practical manner.
According to the present invention, in a further aspect thereof,
there is provided a group of new coating agents for application on
cathode base sheets before electrolysis which coating agents not
only reduce the resistance to stripping of the starting sheets but
also cause substantial improvement in the state, properties, and
uniformity of the electrodeposited copper.
The nature, principle, details, and utility of the invention will
be more clearly apparent from the following detailed description
with respect to preferred embodiments of the invention when read in
conjunction with the accompanying drawing, in which like parts are
designated by like reference numerals.
BRIEF DESCRIPTION OF THE DRAWING
In the drawing:
FIG. 1 is a side elevational view showing one example of a
stripping apparatus constituting an embodiment of the
invention;
FIG. 2 is an elevational view orthogonal to FIG. 1;
FIG. 3 is a fragmentary elevational view showing one example of a
rotating hammer device for creating an air layer between each
starting sheet and its cathode base sheet; and
FIGS. 4, 5, and 6 are, respectively, a fragmentary plan view, a
fragmentary elevational view, and an elevational view showing one
example of a roll device for imparting rolling action to starting
sheets and cathode base sheets thereby to create air layers
therebetween.
DETAILED DESCRIPTION
Referring first to FIGS. 1 and 2, the apparatus shown therein is
provided with a suitable horizontally moving conveyor 10
(fragmentarily shown in FIG. 1) supporting a number of cathode base
sheets 1 (only one sheet shown) suspended therefrom and moved
thereby at a constant speed in the arrow direction of FIG. 1. Each
cathode base sheet 1, which bears starting sheets 2, 2
electrodeposited on opposite sides thereof, is thus caused to pass
through or by an air layer creating device 3, which may be a
vibration percussion device or a rolling device, whereby air layers
are created between the cathode base sheet 1 and the starting
sheets 2, 2 at one part thereof.
The cathode base sheet 1 and starting sheets 2, 2 thus provided
with air layers thereafter move into position between opposed
groups of suction disks 4 supported on arms 5 on respective
transverse sides of the travel path of the sheets, the arms 5 being
pivotally supported on a carriage or bogie truck 7, which can
travel in the same direction as the sheets, and being in their
closed (inward) position at this time. With the arms 5 thus closed,
the suction disks 4 are then caused by a hydraulic (oil-pressure)
cylinder for suction attachment to move perpendicularly to the
electrodeposited surface and thereby be attached by suction to the
surfaces of the starting sheets 2,2.
At the same time, the speed of the truck 7 is synchronized with
that of the traveling cathode base sheet 1. Then, as the truck 7 is
thus moved, the arms 5 are caused to open transversely and
outwardly with a pivotal movement by a hydraulic (oil-pressure)
cylinder 8 and gears 9, and, since the cathode base sheet 1 is held
by guide rollers 10a and thereby prevented from moving
transversely, the starting sheets 2, 2 are stripped from the
cathode base sheet 1.
The starting sheets 2, 2 thus stripped and still held by suction by
the suction disks 4 are conveyed to suitable means (not shown) for
temporary storage, while the cathode base sheet 1 is conveyed at
constant speed by the conveyor 10. Each truck 7 is returned to its
original position upon completion of one stripping operation to
repeat the operation.
In accordance with the invention as mentioned briefly hereinbefore,
an air layer is created between each starting sheet 2 and its
cathode base sheet 1 by the application thereto of a physical
action such as vibration, percussion, or rolling action. Example of
devices 3 for applying such action are illustrated in FIGS. 3
through 6.
In one example of a device as shown in FIG. 3 vibratory percussion
is applied to the starting sheets and cathode base sheet by a
rotating hammer which comprises a shaft 11 rotated at high speed by
motive power means 3a and rings 12 having large inner diameters and
adapted to be forced outward by centrifugal force due to the
rotation of the shaft 11. By suitably positioning this rotating
hammer device with respect to the path of the cathode base sheet
and starting sheets, it is possible to create an air layer at one
part of the bond therebetween.
In one instance of actual practice, a rotating hammer device of the
above described organization was operated at a rotational speed of
162,000 r.p.m. to impart vibratory percussion to starting sheets
each measuring 680.times.760 mm. (approximately 3.0 kg./sheet) and
conveyed at a speed of 16 cm./sec. by a conveyor. As a result, it
was possible to carry out fully automatic stripping with a
stripping time of 15 seconds/sheet with maximum stripping force of
300 kg. at the upper part and 200 kg. at the lower part.
An example of a roll device suitable for creating air layers
between starting sheets and cathode base sheets according to the
invention is illustrated in FIGS. 4, 5, and 6. This device
comprises, essentially, a pair of opposed rolls 13, 13 rotatable
about vertical axes at a peripheral speed equal to the linear speed
of each cathode base sheet 1 and deposited starting sheet passed
therebetween and therepast, force applying means 14, 14 such as
hydraulic piston cylinder motors rotatably supporting respective
rolls 13, 13 and being operable to move the rolls toward and away
from the sheet 1 on respectively opposite sides thereof, and
driving means for rotating the rolls 13, 13.
The driving means comprises an electric motor 15, the output power
of which is transmitted through shafts and gears 16, 16 to the
rolls 13, 13.
Each of the rolls 13, 13 may be of a cylindrical shape with a
straight-line generatrix or with a generatrix of suitable
curvature. The roll surface may be knurled with a certain pattern
to prevent slipping, or it may be provided with gearlike teeth.
Furthermore, a plurality of rows of similar rolls may be used in
combination.
In operation the rolls 13, 13 press against and impart rolling
action simultaneously to the starting sheets and the cathode base
sheet, whereby metallographical strain is produced in these sheets
and gives rise to strain in the bond interface between the starting
sheets and the cathode base sheet. As a result, a layer of air
forms in the interface at one part of the sheets. This rolling
action is advantageous in that it does not generate excessive
noise, as in the case of vibratory and percussive action, and in
that the rolling force can be readily adjusted.
Thus, the present invention provides a method and apparatus whereby
air layers can be created between cathode base sheets and starting
sheets deposited thereon without stopping the moving sheets, and
the operation of stripping starting sheets in copper electrolysis,
which operation comprises attaching suction disks onto the starting
sheet surfaces by vacuum or low pressure, stripping, and moving and
conveying the cathode base sheets and starting sheets, can be made
fully continuous and automatic.
It is possible, of course, to carry out discontinuous or successive
but intermittent operation also in accordance with the invention.
Furthermore, the teachings of the invention can be applied also to
the stripping of other metals such as zinc and cadmium which are
also processed electrolytically by electrodeposition onto cathode
base sheets and stripping therefrom.
The present invention, in another aspect thereof, provides a new
group of coating agents for application on the surfaces of cathode
base sheets for the purpose of preventing excessively strong
bonding between the base sheets and starting sheets deposited
thereon. The nature and utility of these coating agents will be
apparent from the following detailed description beginning with
general considerations and concluding with specific examples of
embodiment of the invention.
We have found that organic compounds of phosphoric acid and of
thiophosphoric acid, organic phosphorous esters, organic
thiophosphorous esters, organic compounds of thiocarbonic acid,
compounds of thiocarbamic acid, and thiazole compounds having
properties as described hereinafter and used in accordance with the
invention as described hereinafter are highly suitable as coating
agents.
We have found that by applying one or more of these coating agents
on the surfaces of cathode base sheets, it is possible to prevent
strong bonding of electrolytic copper to the cathode base sheets
and thereby to reduce remarkably the rate of rejection of
electrolytic sheets due to defective stripping and the force
necessary for stripping.
The coating agents according to the invention have the following
characteristics and properties. ##SPC1## ##SPC2##
The above specified compounds are respectively applied on the
surfaces of cathode base sheets to produce electrolytic copper
sheets in the following manner.
A solution or emulsion of one or more coating agents selected from
organic phosphoric acid compounds and organic thiophosphoric acid
compounds, with or without one or more known coating agents, is
applied onto the cathode base sheets by brushing, swabbing,
dipping, spraying, or any other suitable method, and electrolytic
copper sheets are produced in an electrolyte of a sulfuric acid and
copper sulfate solution.
For the second application and applications thereafter, the above
described coating agent or a solution or emulsion of one or more
compounds selected from organic phosphoric acid or thiophosphoric
acid compounds is ordinarily applied by the above described
procedure each time. By this simple procedure, the electrolytic
copper sheets can be readily stripped from their cathode base
sheets over a long period of operation. We have found that a
concentration of the organic phosphoric acid or thiophosphoric acid
compounds of at least 0.2 percent is suitable.
When an organic phosphoric acid or thiophosphoric acid compound is
used as a coating agent, the resulting resistance to stripping
between the cathode base sheet and each electrolytic copper sheet
differs with the number of carbon atoms in the chain hydrocarbon
radical of the compound. In general, the resistance to stripping
decreases with increase in this number of carbon atoms. However, as
this number of carbon atoms increases, the compound becomes
oleophilic. Therefore, in contrast to a compound in which this
number of carbon atoms is small, and which can be used in the form
of an aqueous solution, a compound in which this number is large
must be dissolved in an organic solvent.
A coating agent in which n=2, R is an alkyl radical, X is ethanol
amine, and the number of carbon atoms is 10 or higher is soluble in
oils and, in general, is suitable for use as a coating agent for
new cathode base sheets. In contrast, such a coating agent in which
the above-mentioned number of carbon atoms is eight or less is
water soluble or water dispersible and, therefore, is generally
suitable as a coating agent for regular stripping, i.e., for the
second coating agent application and thereafter.
The aforementioned organic phosphorous ester or organic
thiophosphorous esters are ordinarily used in the form of solutions
of at least 0.2-percent concentration, being applied on cathode
base sheets either singly or as a mixture of two or more thereof.
Electrolytic copper sheets are then produced on the cathode sheets
in an electrolyte consisting of a sulfuric-acid and copper sulfate
solution. By merely applying this coating agent in this manner each
time on the cathode base sheets, electrolytic copper sheets can be
easily stripped from the cathode base sheets over a long period of
operation.
When one of the above-mentioned esters is used thus as a coating
agent, the resulting resistance to stripping, in general, decreases
with an increase in the number of carbon atoms in the hydrocarbons
of the radicals R.sub.1, R.sub.2, and R.sub.3, particularly the
chain hydrocarbons. As this number increases, however, the
solubility of the ester in organic solvents decreases. We have
found that, when R.sub.2 and R.sub.3 are not chain or aromatic
hydrocarbon radicals and the radical forming R.sub.1 does not
contain more than eight carbon atoms, stripping cannot be readily
accomplished when R.sub.2 and R.sub.3 are hydrogen unless there are
at least eight carbon atoms in the radical forming R.sub.1.
The aforementioned organic thiocarbonic acid compounds,
thiocarbamic acid compounds, and thiazole compounds produce equally
effective stripping results when applied either singly or as a
mixture of two or more thereof as a coating agent on cathode base
sheets. These coating agents are ordinarily used in concentrations
of at least 0.2 percent.
When one of these coating agents is used, the resulting resistance
to stripping between each cathode base sheet and electrolytic
copper sheet deposited thereon differs with the hydrocarbon radical
R. In general, with the same number of carbon atoms, a chain
hydrocarbon radical results in a lower resistance to stripping than
an aromatic hydrocarbon radical, the minimum resistance to
stripping resulting from the use of a coating agent with a straight
chain.
An important feature of the present invention is that, by producing
electrolytic copper sheets with the use of the above described
coating agents according to the invention, not only is the
stripping greatly facilitated, but the resulting electrodeposition
surface is extremely smooth and uniform, and the purity of the
product is comparable to that obtained by known methods wherein
boiled oil and asphalt primer (10 percent) or soap solutions are
used. The cell voltage of the electrolyte and current efficiency
also do not vary from those of conventional practice.
Furthermore, when a conventional coating agent is used, the
electrolytic copper sheets become firmly bonded to their cathode
base sheets unless the sheets are placed in the main electrolytic
cell, and electrolysis is started immediately after immersion of
the cathode base sheets into soap solution. However, when a coating
agent according to the present invention is used, stripping can be
easily carried out even when the starting sheets are dried, after
the coating is applied thereto, placed in the electrolytic cell,
and subjected to electrolysis.
As a result, the present invention affords improvement in the
electrolytic conditions relative to those of known practice. For
example, since the adhesivity of these coating agents of the
invention with respect to cathode base sheets is excellent, there
is almost no change in the resistance to stripping even when the
electrolyte temperature is raised. This is only one example of the
indirect advantages that are afforded. Furthermore, while
expedients such as covering the peripheral parts of cathode base
sheets with electrically insulative material and providing grooves
are resorted to in order to facilitate physically or
electrochemically the stripping of electrolytic copper sheets, the
present invention has further advantageous features such as the
remarkable reduction of damage to these parts.
In order to indicate still more fully the nature and utility of the
invention, the following specific examples of procedure
constituting preferred embodiments of the invention and comparisons
with conventional practice are set forth, it being understood that
these examples are presented as illustrative only, and that they
are not intended to limit the scope of the invention, which is
defined in the appended claims.
EXAMPLE 1
With an electrolyte composed of a solution of 42 grams/liter of
copper and 175 grams/liter of free sulfuric acid and under the
conditions of a temperature of 55.degree. C. and a cathode current
density of 207 A/dm.sup.2, values such as resistance to stripping
in the case of electrolysis for 24 hours with the use of rolled
copper sheets (measuring 40.times.80 mm.) for cathode base sheets
were measured for cases wherein coating agents of the invention
were used and compared with the results of cases wherein
conventional coating agents were used. The comparative results are
set forth in table 1.
The resistance of stripping (or bond strength between each starting
sheet and its cathode sheet) is represented in the unit of kg. per
40 mm. of width, by the force required to separate an electrolytic
copper sheet deposited on a 40.times.80 mm. cathode from one end of
a width of 40 mm. by means of vacuum suction disks (this definition
being applicable to all other examples set forth hereinafter).
##SPC3##
This example indicates the results in the case wherein new cathode
base sheets are used. While the coating agents of the organic
phosphoric or thiophosphoric series according to the invention do
not differ greatly from conventional coating agents on the point of
resistance to stripping, they are superior in interior appearance
and properties as well as uniformity of electrodeposition.
Furthermore, aqueous solutions of organic compounds of phosphoric
acid, in general, produce better properties of electrodeposition
than coating agents having oiliness.
EXAMPLE 2
Under the same electrolytic conditions as in example 1, values of
resistance to stripping (kg./40 mm. width) were measured over a
long period of operation. The results are indicated in table 2.
##SPC4##
The electrodeposition with the use of a mixture of boiled oil and
asphalt primer as the coating agent for the initial application was
slightly poor, but the use of coating agents of organic phosphoric
acid compounds resulted in good electrodeposition and also somewhat
low stripping resistance. As a regular coating agent, a
conventional soap produced a stripping resistance of more than 5
kg./40 mm. of width on the 11th stripping (after 11th day) and
thereafter, while coating agents of organic phosphoric acid
compounds produced stripping resistances of 1 kg./40 mm. of width
or less.
In the case of a soap used as a regular coating agent, the
stripping resistance increased in all instances at the seventh
application and thereafter. However, when the coating agent for a
new cathode base sheet was a thiophosphoric acid compound, its life
was relatively long. Furthermore, when the regular coating agent
was an organic phosphoric acid or thiophosphoric acid compound, a
substantially constant stripping resistance was produced over a
long period.
EXAMPLE 3
Under the same electrolytic conditions as those set forth in
example 1, the following emulsion was used as a coating agent
according to present invention. In 80 percent of fluid paraffin, 20
percent of dilauryl triethanolamine phosphate was thoroughly
dissolved, and an oil-in-water emulsion containing 10 percent of
the solution thus obtained was prepared and used as the coating
agent for the second application and subsequent applications by
dipping. The values of stripping resistance in this case over a
long period are shown in table 3. ##SPC5##
These results indicate that an emulsion is also effective as a
coating agent.
EXAMPLE 4
Under the same electrolytic conditions as in example 1, stripping
resistances were measured with respect to cathode base sheets of
stainless steel (each measuring 40.times.80 mm.). The stainless
steel was of Japanese Industrial Standards designation SUS 36
(containing max. 0.03 percent C, 12.00-16.00 percent Ni,
17.00-19.00 percent Cr, 1.20-2.75 percent Mo, and 1.00-2.50 Cu)
which was polished with No. 80 emery (sieve number according to
Japanese Industrial Standard K-6001, corresponding to sieve No.
80-85 of ASTM). The results are shown in table 4. ##SPC6##
These results indicate that similar effective results can be
attained also in the case wherein a stainless steel sheet is used
as a cathode base sheet and coated with an organic phosphoric acid
compound.
EXAMPLE 5
A copper electrolysis plant having two electrolytic cells was
operated in accordance with the new method of the invention and the
former conventional method each for 10 days with the use of
rolled-copper cathode base sheets for producing electrolytic copper
sheets measuring 680.times.760 mm. under the operational conditions
of Cu 40 to 44 g./liter, free sulfuric acid 170 to 180 g./liter,
and electrolyte temperature of from 51.degree. to 54.degree. C.
A mixture of a boiled oil and asphalt primer was used as a coating
agent for the first application of all new base sheets. From the
second application, a conventional aqueous soap solution was used
in the former method, and an aqueous solution (1.3 percent) of
dilauryltriethanolamine phosphate, which is an organic phosphoric
acid compound, was used in the new method, these coating agents
being applied by dipping the base sheets therein.
The comparative results of these two operations are shown in table
5. ##SPC7##
These results indicate that the use of coating agent containing an
organic phosphoric acid compound results in a stripping efficiency
which is approximately 5 percent higher and an electrolytic copper
sheet rejection rate which is approximately 0.8 percent lower than
corresponding values attainable through the use of a conventional
coating agent. Furthermore, since the quantity of organic
phosphoric acid compound adhering to the electrolytic copper sheets
is extremely minute, it has no effect whatsoever on the quality of
the product.
EXAMPLE 6
Under the same electrolytic conditions as those set out in example
1, stripping resistances and other conditions were measured with
respect to the coating agent and organic phosphorus ester after
application of the present invention. The following table 6, shows
a comparison between them. The value of the stripping resistance is
denoted in units of force (Kg./40 mm. width) required for stripping
the electrolytic copper starting sheet off the cathode base sheet
of 40.times.80 mm. by means of vacuum suction discs from the end of
the base sheet of 40 mm. width. ##SPC8##
This example indicates the effectiveness of the coating agents when
used on new cathode base sheets. Even when the alkyl radical in the
organic phosphorous ester is an octyl radical, a mere 1 percent of
the ester results in a stripping resistance which approximately the
same as that attainable with a conventional coating agent, and an
organic phosphorous ester having an alkyl radical with a larger
number of carbon atoms has an even higher performance, producing
excellent results in the state, properties, and uniformity of the
electrodeposition.
EXAMPLE 7
The same performance values as those of example 6 were determined
for coating agents containing organic thiophosphorous esters by
carrying out electrolysis under the same electrolytic conditions as
in example 1, whereupon the results shown in table 7 were obtained.
##SPC9##
As indicated in table 7, coating agents containing organic
thiophosphorous esters are superior in performance to conventional
coating agents on the points of stripping resistance and
electrodeposition state, properties, and uniformity.
EXAMPLE 8
Organic thiophosphorous esters as indicated in table 8 were tested,
and the resulting values of stripping resistance (kg./40 mm. width)
were measured over a long period under the same electrolytic
conditions as in example 1. The values of stripping thus measured
are shown in table 8. ##SPC10##
As indicated in table 8, coating agents containing organic
thiophosphorous esters are superior to the conventional mixture of
boiled oil and asphalt primer in stripping resistance also over a
long period of operation.
Example 9
The performance of coating agents containing compounds of xanthic
(xanthogenic) acid represented by the general formula
in which radical X represents an oxygen atom, and Y and Z represent
atoms of sulfur and potassium, respectively, were compared with
those of a conventional coating agent by carrying out electrolysis
under the same electrolytic conditions as in example 1 and with new
cathode base sheets, whereupon the results shown in table 9, were
obtained. ##SPC11##
It can be observed from table 9 that the stripping resistance
decreases somewhat as the alkyl radical R increases in size and
that the stripping resistance also decreases with increases in the
concentration of the xanthogenate solution.
EXAMPLE 10
The procedure of example 9 was carried out with coating agents
containing dixanthic acid compounds represented by the general
formula
in which radical X represents an oxygen atom, and Y and Z,
respectively, represent a sulfur atom and
under the same electrolytic conditions as in example 1 and with new
cathode base sheets, whereupon the results shown in table 10 were
obtained. ##SPC12##
These dixanthogenates are insoluble in water but are soluble in
organic solvents. As indicated in table 10, these dixanthogenates
are superior to a conventional coating agent of boiled oil and
asphalt primer, with respect to outer appearance properties and
uniformity of electrodeposition.
EXAMPLE 11
Coating agents consisting of aqueous solutions of dithiocarbamates
of the general formula
, where the radical X is a nitrogen atom, and Y and Z are
respective atoms of sulfur and sodium, were tested under the same
electrolytic conditions as in example 1 and with the use of new
cathode base sheets, whereupon the results shown in table 11 were
obtained. ##SPC13##
As indicated in table 11, these dithiocarbamates are superior to
conventional coating agents.
EXAMPLE 12
Coating agents containing a compound of thiazole of the general
formula
, in which the radical X represents a sulfur atom, and Y and Z
represent, respectively, atoms of sodium and hydrogen, were tested
on new cathode base sheets under the same electrolytic conditions
as in example 1, whereupon the results shown in table 12 were
obtained. ##SPC14##
EXAMPLE 13
The stripping resistances (kg./40 mm. width) of coating agents
containing a dixanthogenate and a dithiocarbamate were compared
with those of a conventional coating agent under the same
electrolytic conditions as in example 1 over a long period,
whereupon the results shown in table 13 were obtained.
##SPC15##
As indicated in table 13 these coating agents according to the
present invention are superior to the conventional mixture of
boiled oil and asphalt primer in stripping resistance over a long
period of operation.
It should be understood, of course that the foregoing disclosure
relates to only preferred embodiments of the invention and that it
is intended to cover all changes and modifications of the examples
of the invention herein chosen for the purposes of the disclosure,
which do not constitute departures from the spirit and scope of the
invention as set forth in the appended claims.
* * * * *