U.S. patent number 3,743,584 [Application Number 05/149,335] was granted by the patent office on 1973-07-03 for acid bright copper plating bath.
This patent grant is currently assigned to Schering AG. Invention is credited to Wolfgang Clauss, Wolfgang Dahms, Hans-Gunther Todt.
United States Patent |
3,743,584 |
Todt , et al. |
July 3, 1973 |
ACID BRIGHT COPPER PLATING BATH
Abstract
Polymeric phenazonium compounds, their method of preparation and
their use in acid electrolytes for the deposition of bright,
leveling, copper coatings on surfaces.
Inventors: |
Todt; Hans-Gunther (Berlin,
DT), Clauss; Wolfgang (Berlin, DT), Dahms;
Wolfgang (Berlin, DT) |
Assignee: |
Schering AG (Berlin,
DT)
|
Family
ID: |
25759264 |
Appl.
No.: |
05/149,335 |
Filed: |
June 2, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Jun 6, 1970 [DT] |
|
|
P 20 28 803.3 |
|
Current U.S.
Class: |
205/298 |
Current CPC
Class: |
C07D
241/46 (20130101); C25D 3/38 (20130101); C08G
73/0694 (20130101) |
Current International
Class: |
C07D
241/00 (20060101); C07D 241/46 (20060101); C25D
3/38 (20060101); C08G 73/00 (20060101); C08G
73/06 (20060101); C23b 005/18 () |
Field of
Search: |
;204/52R,DIG.2 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Edmundson; F. C.
Claims
What we claim is:
1. In an acid electrolyte for the deposition of bright copper
coatings comprising (a) an oxygen containing high molecular weight
compound selected from the group consisting of polyvinyl alcohol,
carboxymethyl cellulose, polyethylene glycol, stearic acid
polyglycol ester, oleic acid polycol ester, and nonylphenol
polyglycol ester; (b) an organic thio compound selected from the
group consisting of sodium salt of N.sub.1 N-diethyl-dithiocarbamic
acid (sulfopropyl ester), sodium
mercaptobenzothiazol-5-propanesulfonate, sodium
3-mercapto-propane-1-sulfonate, bis-(3-sodium
sulfopropyl)-disulfide, disodium salt of thiophosphoric
acid-O-ethyl-bis-(sulfopropyl) ester, trisodium salt of
thiophosphoric acid-tri-(sulfopropyl) ester, and thioglycollic
acid; the improvement which comprises a compound of the formula:
##SPC4##
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, and R.sub.9 are individually selected from the
group consisting of hydrogen, lower alkyl, aryl, and substituted
aryl; R.sub.5 and R.sub.8 being additionally a monomeric or
polymeric phenazonium radical; A is an acid radical; and n is an
interger from 2 to 100.
2. An electrolyte as set forth in claim 1, characterized in that it
contains the identified compounds in quantities of 0.0005 to 0.1
g/liter, preferably 0.0005 to 0.03 g/liter.
3. An electrolyte according to claim 2, characterized in that it
additionally contains oxygen-containing, high-molecular compounds
and organic thio compounds with water-solubilizing groups.
4. Electrolyte according to claim 3, characterized in that it
contains the oxygen-containing, high-molecular compounds in
quantities of 0.01 to 20.0 g/liter, preferably 0.02 to 8.0 g/liter
and the organic thio compounds with water-solubilizIng groups in
quantities of 0.0005 to 0.2 g/liter, preferably 0.01 to 0.1
g/liter.
5. An electrolyte for the deposition of bright copper coatings
comprising at least one compound of the structure: ##SPC5##
wherein R.sub.1 through R.sub.9 are individually selected from the
group consisting of hydrogen, lower alkyl, aryl, and substituted
aryl, R.sub.5 and R.sub.8 being additionally a monomeric or
polymeric phenazonium radical; A is an acid radical; and n is an
integer from 2 to 100.
Description
The invention relates to new polymeric phenazonium compounds,
methods for their production, as well as their use in acid
electrolytes for the deposition of bright, leveling copper
coatings.
It has long been known that certain organic substances can be added
in small quantities to acid copper electrolytes, in particular to
the most widely used copper sulfate electrolytes, in order to
obtain bright copper coatings instead of a crystalline-dull
deposition. For this purpose there have become known, for example,
polyethylene glycol, thiourea and derivatives thereof,
thiohydantoin, thiocarbaminic acid ester and thiophosphoric acid
ester, which, however, no longer have any practical importance
since the quality of the copper coatings obtained with them does
not meet today's requirements. Thus the coatings are either too
brittle or they have too little luster or, within certain current
density ranges, they turn out with a relief type finish.
Also the addition of certain safranines, either alone according to
the proposal of German Pat. No. 947,656 or in mixture with thiourea
or the substitution products thereof according to German Pat. No.
1,004,880, leads to copper coatings with such unsatisfactory
properties.
Further there has been proposed the addition of
thiourea-formaldehyde condensates (German Pat. Nos. 1,152,863 and
1,165,962) and of certain compounds with C=S groups in the molecule
(German Pat. No. 1,218,247).
While one obtains bright copper deposits with these additions, they
do not always satisfy the increased requirements of the practice
either, since their leveling action is unsatisfactory.
There has been proposed moreover the addition of polyalkylenimines
in conjunction with organic thio compounds (German Pat. No.
1,246,374) and polyvinyl compounds in mixture with
oxygen-containing high-molecular compounds and organic
thio-compounds (German Pat. application No. 1,521,062). Such copper
electrolytes, however, do not permit the use of higher cathodic
current densities, and the deposited copper coatings can be
nickel-plated only after intermediate treatment.
It is the object of the present invention to avoid the
disadvantages of the known acid copper baths and moreover to
improve these baths so that they can be operated also at higher
current densities and in conjunction with other known brighteners
to permit the deposition of especially uniform copper deposits,
which can be nickel-plated without intermediate treatment.
This is solved according to the invention by an acid copper
electrolyte which is characterized by a content of at least one
compound of the general formula ##SPC1##
Wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, and R.sub.9 are identical or different and
represent hydrogen, a low alkyl or possibly substituted aryl, and
R.sub.5 and R.sub.8 represent moreover monomeric or polymeric
phenazonium radicals, A is an acid radical, and n an integer from 2
to 100, preferably from 4 to 20.
As lower alkyl radicals there may be named for example methyl and
ethyl propyl, etc.
An aryl radical may be, for example, phenyl, which may be
substituted by methyl, ethyl, methoxy or ethoxy, etc.
As acid radicals there enter into consideration, for example, those
of hydro-chloric acid (Cl.sup.-), sulfuric acid (HSO.sub.4 .sup.-),
nitric acid (NO.sub.3 .sup.-) and acetic acid (CH.sub.3 coo.sup.-),
etc.
The radicals R.sub.5 and R.sub.8 may signify moreover, for example
phenazonium radicals of the parent substance.
The quantities in which the identified compounds must be added to
the copper baths in order to obtain a clear improvement of the
copper deposition are surprisingly very small and amount to about
0.0005 to 0.1 g/liter, preferably 0.0005 to 0.03 g/liter.
Table I contains examples for substances according to the invention
and data on the preferred concentrations in the electrolyte.
The linkage points of the radicals are not fully clarified. The
linkage may take place, besides through the 3-position of the
phenazonium radical, also through the 5-and the 7-position.
##SPC2##
These substances can be prepared, for example, as follows:
2 moles of an amine sulfate, e.g.,
2-methyl-3-amino-6-dimethylamino-9-phenyl-phenazonium sulfate, are
suspended with 4.5 liter of 20 percent sulfuric acid and diazotized
within 3 hours at -5.degree. C with 650 ml nitrosylsulfuric acid
containing 2.2 moles of nitrous acid. The excess nitrous acid is
destroyed with amino-sulfonic acid and the reaction solution is
heated to 20.degree. C, nitrogen evolving vigorously. After the
nitrogen evolution has come to an end, one neutralizes with a base,
e.g., potash lye.
On standing, 800 g of a blue reaction product of substance No. 3
(Table I) crystallize out. After drying, and after proper dilution,
this product can be charged immediately into acid copper
electrolyte. The molecular weight is about 8,000.
In the following, the preparation of some other substances
according to the invention is described.
Preparation of substance No. 1
1 mole of
3-amino-5-methyl-6-dimethylamino-9-phenyl-phenazonium-hydrogen
sulfate is suspended in 2 liters of 25 percent sulfuric acid and
diazotized within 4 hours at -10.degree. C with 300 ml
nitrosylsulfuric acid containing 1.1 mole of nitrous acid. The
excess nitrous acid is destroyed with urea and the reaction
solution slowly heated to 30.degree. C, nitrogen evolving
vigorously. After the nitrogen evolution has come to an end, one
neutralizes with gaseous ammonia. On standing, 350 g of a polymeric
blue phenyl phenazonium salt crystallize out. After drying, this
polymeric dye, which has a mean molecular weight of about 5,000,
can be charged in proper dilution directly into acid copper
electrolyte.
Preparation of substance No. 2
1 mole of 2-methyl-3-amino-6-diethylamino-9-phenyl-phenazonium
chloride is suspended in 2 liters of 30% HCl and carefully
diazotized within 5 hours at 10.degree. C with 1.1 mole NaNo.sub.3
.sub.' dissolved in 250 ml of water. The excess nitrous acid is
destroyed with aminosulfonic acid and the reaction solution heated
to 20.degree. C, nitrogen evolving vigorously. After the nitrogen
evolution has come to an end, one neutralizes with potassium
hydroxide. After letting stand, 300 g of the blue polymeric dye
having a mean molecular weight of 4,000 can be suctioned off.
Preparation of substance No. 4
0.1 mole of 3-amino-6-dimethylemino-9-methyl-phenazonium acetate is
suspended in 250 ml of glacial acetic acid and carefully diazotized
at -5.degree. C with 0.12 mole of sodium nitrite, dissolved in 50
ml of water. The excess nitrous acid is destroyed with urea and the
reaction solution briefly heated to boiling. After concentrating to
100 ml and cooling, the precipitated polymeric dye of a mean
molecular weight of about 8,000 can be suctioned off. The yield is:
20g.
Preparation of substance No. 5
0.1 mole of
2-m35hyl-3-amino-6-phenylamino-9-phenyl-phenazonium-hydrogen
sulfate is suspended in 250 ml of 35 percent sulfuric acid and
diazotized at -20.degree. C with 30 ml of nitrosylsulfuric acid
containing 0.12 mole of nitrous acid. The excess nitrous acid is
destroyed with aminosulfonic acid and the reaction mixture slowly
heated to 50.degree. C. After the nitrogen evolution has come to an
end, one neutralizes with soda lye, and the polymeric dye
contaminated with some sodium sulfate and having a mean molecular
weight of about 300 is suctioned off. The yield is: 15g.
Preparation of substance No. 6
0.05 mole of 2-methyl-3-amino-6-dimethylamino-phenazonium hydrogen
sulfate is suspended in 50 ml of 40 percent sulfuric acid and
diazotized at -5.degree. C with 15 ml of nitrosylsulfuric acid
containing 0.06 mole of nitrous acid. The excess nitrous acid is
destroyed with aminosulfuric acid and the acid neutralized with
ammonia. After standing for a short time, a blue polymeric dye
having a mean molecular weight of about 10,000 can be suctioned
off. The yield is: 5g.
Preparation of substance No. 7
0.05 mole of 3-amino-6-methylamino-9-phenylphenazonium acetate is
suspended in 200 ml of glacial acetic acid and diazotized at
-10.degree. C with 0.06 mole of sodium nitrite, dissolved in little
water. After destruction of the excess nitrous acid with urea, the
reaction solution is heated to 40.degree. C, concentrated, and the
precipitated dye having a mean molecular weight of about 5,000 is
suctioned off. The yield is 8g.
Preparation of substance No. 8
0.05 mole of 2-phenyl-3-amino-6-3thylamino-9-phenyl-phenazonium
chloride is suspended in 400 ml of 30 percent hydrochloric acid and
diazotized within 1 hour with 0.06 mole of sodium nitrite,
dissolved in little water. After destruction of the excess nitrous
acid with aminosulfonic acid, the temperature is raised to
30.degree. C; after the nitrogen evolution has come to an end, the
product is extensively concentrated, and the precipitated dye
having a mean molecular weight of about 2,000 is suctioned off. The
yield is: 4g.
Preparation of Substance No. 9
0.05 mole of
1,2,5,8-6365amethyl-3-amino-6-diethylamino-9-phenyl-phenazonium
hydrogen sulfate is dissolved in 500 ml of 50 percent sulfuric acid
and diazotized at -10.degree. C with 15 ml of nitrosylsulfuric acid
containing 0.06 mole of nitrous acid. The excess nitrous acid is
destroyed with aminosulfonic acid, the diazonium salt is boiled
down, and the sulfuric acid neutralized with ammonia. The
precipitated dye having a mean molecular weight of about 2,000 is
suctioned off. The yield is: 10g.
Preparation of substance No. 10
0.05 mole of
2,7-dimethyl-3-amino-6-diethylamino-9-tolyl-phenazonium chloride is
suspended in 50 ml of 30 percent hydrochloric acid and carefully
diazotized at -5.degree. C with 0.06 mole of sodium nitrite,
dissolved in little water. The excess nitrous acid is destroyed
with aminosulfonic acid, the reaction solution heated to 80.degree.
C, extensively concentrated, and the precipitated dye having a mean
molecular weight of about 4,000 is suctioned off. The yield is:
8g.
Preparation of substance No. 11
0.05 mole of
2,8-diphenyl-3-amino-5-methyl-6-dimethylamino-9-phenyl-phenazonium
hydrogen sulfate is dissolved in 500 ml of 50 percent sulfuric acid
and diazotized at -10.degree. C with 15 ml nitrosylsulfuric acid
which contains 0.06 mole of nitrous acid, and then the excess
nitrous acid is destroyed with aminosulfonic acid. After the
diazonium compound has been boiled down, one neutralizes with
ammonia and the precipitated blue dye having a mean molecular
weight of about 1,500 is suctioned off. The yield is: 9g.
Preparation of substance No. 12
2 moles of 2,7-dimethyl-3,6-diamino-9-phenyl-phenazonium hydrogen
sulfate are suspended with 4.5 liter of 20 percent sulfuric acid
and diazotized within 5 hours at -10.degree. C with 650 ml of
nitrosylsulfuric acid which contains 2.2 moles of nitrous acid. The
excess nitrous acid is destroyed with aminosulfonic acid and the
reaction solution is heated to 25.degree. C, nitrogen evolving
vigorously. After the nitrogen evolution has come to an end, one
neutralizes with ammonia, and the polymeric red-brown dye
precipitated upon standing having a mean molecular weight of about
5,000 is suctioned off. The yield is: 750g of dye (contaminated
with ammonium sulfate).
The invention, therefore, further relates to a method for the
production of the compounds identified above.
As has been described, this method proceeds from compounds of the
general formula ##SPC3##
in which the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6, R.sub.7, R.sub.8, R.sub.9 signify hydrogen, a low alkyl or
possibly substituted aryl, and A is an acid radical, from which
then the desired reaction products are formed by diazotizing in
acid solution and subsequent boiling down of the resulting
diazonium salts.
Advantageously the diazotizing of the amino compounds is effected
in sulfuric acid, hydrochloric acid, or acetic acid solution. These
acids then form the above-mentioned acid radical A. As diazotizing
agents that are suitable are sodium nitrite or nitrosylsulfuric
acid, etc.
The so-called boiling down of the formed diazonium salts may take
place at temperatures of about 5.degree. to 100.degree. C,
preferably about 10.degree. to 25.degree. C.
The reaction products precipitate from the acid reaction solution
or can be precipitated therefrom by neutralization with bases,
e.g., ammonia, soda or potash lye. Isolation is then effected by
common methods.
As electrolyte for the deposition of copper coatings with addition
of the substances according to the invention, there is generally
used a sulfuric acid copper sulfate solution of the following
composition:
Copper sulfate CuSo.sub.4 .sup.. 5 H.sub.2 O -- 125-260 g/liter
Sulfuric acid H.sub.2 SO.sub.4 -- 20-85 g/liter
Instead of copper sulfate, at least in part, other copper salts may
be used. The sulfuric acid may be replaced partly or wholly by
fluoroboric acid, phosphoric acid and/or other suitable acids. The
electrolyte may be chloride-free, or this being usually
advantageous for improving the luster and the leveling, it may
contain chlorides, such as, alkali chlorides or hydrochloric acid,
in quantities of 0.001 to 0.2 g/liter.
If one or more of the substances of the invention are added to such
copper baths, the normally crystalline-dull precipitate turns out
bright in a wide current density range. Besides, the cathodic
current density may be increased by about 50 percent without the
formation of flaws, in particular budding, in the range of high
current densities. To attain a certain layer thickness, therefore,
the time of exposure may be reduced accordingly and in a unit of
given size more merchandise can be put through.
The substances according to the invention are also particularly
suited for depositing haze-free and high-brighteners coatings in
conjunction with other common luster-formers and/or wetting agents.
Electrolytes containing the substances of Table I show also
excellent ageing. Even after a current passage of 200-400 Ah/ltr
and more, the copper coatings turn out just as highly lustrous,
leveling and ductile as in a fresh batch of electrolyte. No harmful
decomposition products of these substances are formed that would
require purification, for example, with active carbon.
One obtains an especially clear and sudden improvement of the
luster and of the leveling effect by adding the substances
according to the invention to copper electrolytes which contain as
brighteners oxygen-containing, high-molecular compounds and organic
thio compounds, preferably comprising one or more
water-solubilizing groups.
The quantities of these compounds to be added to the copper
electrolyte are comprised approximately within the following
limits:
Oxygen containing high molecular compounds--0.01-20.0 g/liter
preferably--0.02-8.0 g/liter.
Organic thio compounds with water
solubilizing groups -- 0.0005-0.2 g/liter,
preferably--0.01-0.1 g/liter.
Table II below contains examples of oxygen-containing,
high-molecular compounds and their preferred concentrations.
TABLE II
No. Substance Preferred concentration g/liter 1 Polyvinyl alcohol
0.05-0.4 2 Carboxymethyl cellulose 0.05-0.1 3 Polyethylene glycol
0.1-5.0 4 Polypropylene glycol 0.05-1.0 5 Stearic acid polyglycol
ester 0.5-8.0 6 Oleic acid polyglycol ester 0.5-5.0 7 Stearyl
alcohol polyglycol ether 0.5-8.0 8 Nonylphenol-polyglycol ether
0.5-6.0
Table III below contains examples of organic thio compounds with
water-colubilizing groups and their preferred concentrations.
TABLE III
No. Substance Preferred concentration g/liter 1
N,N-diethyl-dithiocarbaminic acid-(sulfopropyl)-ester, sodium salt
0.01-0.1 2 Sodium mercaptobenzothiazol- S-propanesulfonate 0.02-0.1
3 Sodium 3-mercaptopropane-1 sulfonate 0.005-0.1 4 Bis-(3-sodium
sulfopropyl)- disulfide 0.005-0.2 5 Thiophosphoric acid-O-ethyl-
bis-(sulfopropyl(-ester, disodium salt 0.01-0.15 6 Thiophosphoric
acid-tris- (sulfopropyl)-ester, tri- sodium sulfonate 0.05-0.2 8
Thioglycolic acid 0.001-0.003
The addition of substances of Table I to copper electrolytes which
contain brighteners of Tables II and III thus brings about two
decisive technical advantages:
1. The applicable cathodic current density is increased up to 50
percent;
2. The leveling effect, i.e., the reduction of roughness of the
ground material, is increased (measured at a layer thickness of 24
microns) from 40-50 percent to about 70-80 percent.
The concentration ratios of the individual compounds in the copper
electrolyte may vary within wide limits. It has proved favorable to
have a weight ratio of the substances, listed by way of example in
Tables I, II and III, of about 1 : 10 : 2 to about 1 : 200 :
20.
The following examples will elucidate the use of the products
according to the invention:
EXAMPLE 1
In a copper bath of the composition
220 g/liter copper sulfate (CuSO.sub.4 .sup.. 5 H.sub.2 )
50 g/liter sulfuric acid, concentrated brass sheets or
pre-nickel-plated steel sheets are copper plated at an electrolyte
temperature of 20.degree. to 25.degree. C with cathode movement.
The deposits are crystalline-dull. When the current density exceeds
4 A/dm.sup.2, there occur at the corners of the cathode sheets
loosely adhering powdery copper depositions. If one now adds to the
electrolyte 0.06 g/liter of substance No. 1 (Table I), the current
density can be increased to 6 A/dm.sup.2 under the same operating
conditions without causing the flaws referred to above. Besides,
the deposit turns out bright.
EXAMPLE 2
To a copper bath of the composition
200 g/liter copper sulfate (CuSO.sub.4 .sup.. 5 H.sub.2 O)
60 g/liter sulfuric acid, concentrated
0.05 g/liter sodium chloride
there are added as brighteners
0.6 g/liter polypropylene glycol and
0.02 g/liter sodium 3-mercaptopropane-1 sulfonate.
Although at an electrolyte temperature of 20.degree. to 25.degree.
C one obtains with a current density of 6.0 A/dm.sup.2 and air
agitation bright and haze-free copper coatings, the leveling of
rugosities of the ground material at a layer thickness of 24
microns is only 45 percent. When adding to the bath 0.008 g/liter
of substance No. 3 (Table I), the leveling increases under the same
operating conditions to 76 percent, that is, it increases by 70
percent.
EXAMPLE 3
To the electrolyte according to Example 2 there are added
4.0 g/liter nonylphenol-polyglycol ether and
0.02 g/liter N,N-diethyl-dithiocarbaminic acid-(sulfopropyl)-ester,
sodium salt.
At an electrolyte temperature of 20.degree. to 25.degree. C, a
current density of 5.0 A/dm.sup.2 and movement of the cathode rod,
the leveling effect at a layer thickness of 24 microns copper is
about 50 percent. By adding 0.01 g/liter of substance No. 6 (Table
I), the leveling increases to 78 percent, the increase thus being
56 percent.
* * * * *