US005630950A

United States Patent (19) 11 Patent Number: 5,630,950

Cangelosi 45 Date of Patent: May 20, 1997
54 COPPER BRIGHTENING PROCESS AND 4238,279 12/1980 Tsubai et al. .......................... 252/79.2
BATH 4,308,091 12/1981 Schmitt et al. ........................ 252/79.4
4,376,057 3/1983 Angelo et al. ......................... 252/79.4
75) Inventor: Anthony R. Cangelosi, Clinton 4,437,929 3/1984 Wong ............... ... 252/79.4
Township, Mich. 4,518.519 5/1985 Lott et al. ... ... 252/48
4,767,661 8/1988 Battey et al. . . 252/79.2
73) Assignee: Enthone-OMI, Inc., Warren, Mich. 4,859,281 8/1989 Goltz ...................................... 252/79.4
4,875,972 10/1989 Williams et al. ...................... 252/79.2
4,880,495 11/1989 Petraitis et al. ........................ 252A79.2
21 Appl. No.: 322,109 5,030,373 7/1991 Kimura et al. ......................... 252/79.2
22 Filed: Oct. 11, 1994 5,098,517 3/1992 Tytgat et al. ........................... 252/79.2
FOREIGN PATENT DOCUMENTS
Related U.S. Application Data 57-155379 9/1988 Japan.
63 Continuation-in-part of Ser. No. 89,856, Jul. 9, 1993, aban OTHER PUBLICATIONS
doned.
(51 int. Cl. ... C09K13/06 "GAF Polyvinylpyrrolidone Polymers" Brochure.
(52 U.S. Cl. ....................... 216/106; 21.6/105; 252/79.2: Primary Examiner-T. Tung
252/79.4 Attorney; Agent, or Firm-Harness, Dickey & Pierce, P.L.C.
58 Field of Search .................................... 216/105, 106; 57 ABSTRACT
252/792, 79.4
A process and aqueous bath for bright dipping of a copper
56 References Cited containing substrate. The bath includes: an acid, hydrogen
U.S. PATENT DOCUMENTS peroxide and a bath soluble, peroxide stable constituent
effective for creation and stabilization of a dissolution
3,773,577 11/1973 Shibasaki et al. ..................... 252/79.4 inhibiting film over the brightened substrate.
4,022,703 5/1977 Bakes et al. ...... ... 252/79.4
4,233,111 11/1980 Valayil et al. ........................ 252/79.4 31 Claims, 1 Drawing Sheet

6, OO

5. OO
4. OO

3.00
2. OO
1.00
OOO
f 2
Virne frn Min.
U.S. Patent May 20, 1997 5,630,950

6, OO

5. OO
4. OO

5. OO

2 OO

1.00
OOO
f 2 3. 4
fire frn Min.

El. 1-.
 5,630,950
1. 2
COPPER BRIGHTENING PROCESS AND DETALED DESCRIPTION OF THE
BATH PREFERRED EMBODEMENTS
RELATED APPLICATIONS Thus, in accordance with the present invention, there is
provided a bath for bright dipping of copper which provides
This is a continuation in part of U.S. Ser. No. 08/089,856 improved levelling and brightening of the substrate surface
Entitled Copper Brightening Process and Bath filed Jul. 9, in a controlled manner, such that less of the substrate is
1993, now abandoned. consumed. Baths in accordance with the present invention
include aqueous acid and peroxide brightening baths which
BACKGROUND OF THE INVENTION also include a peroxide stable constituent, preferably a
10
The present invention relates to an improved chemical polymer, in an amount effective for creation and stabiliza
polishing bath for metal brightening. More specifically, the tion of a dissolution inhibiting film over the brightened
present invention relates to an improved composition and substrate.
method for chemical polishing of copper and copper alloy Baths of the present invention, generally comprise from
substrates. 15 about 1 g/l to about 35 g/l acid which typically ranges from
Chemical polishing or brightening of copper alloy about 2 g/l to about 12 g/l, and preferably from about 4 g/1
substrates, electroplates and the like has been known in the to about 8 g/l of an acid. The acid utilized in the present
art for preparing surfaces for further plating thereover and/or invention is selected from commonly used acids such as
commercial grade polish. Typical bright dipping baths sulfuric acids, hydrochloric acid, nitric acid, phosphoric acid
include mixtures of one or more acids such as concentrated 20 and acetic acid which have been utilized in brightening baths
Sulfuric, phosphoric, nitric, hydrochloric, acetic and chromic in the past. Extremely corrosive acids such as hydrofluoric
acids. These baths, while having tendency to brighten the acid are not useful in the present invention, as they provide
copper, are hard to control and resultin unwanted etching of unacceptable rapid degradation of the substrate. A particu
the copper if not utilized under strict process parameters. larly preferred acid of the present invention is sulfuric acid
In recent years, the use of hydrogen peroxide as an 25 which is utilized in the above percentages inits concentrated
form. The use of hydrochloric and nitric acids, while
additive to acid brightening baths has greatly increased the effective, may be undesirable since these acids may be
stability and useability of these baths. However, hydrogen subject to liberation of chlorine gas or nitric oxide and
peroxide rapidly degrades in such acid solutions, and nitrogen dioxide gases.
typically, such solutions typically include additives such as The peroxide component of the present invention is
chelating agents and chromic acids which require special 30
generally utilized in quantities of from about 45 g/1 to about
costly treatment of disposal. While these brightening baths 230 g/l HO, typically from about 50 g/l to about 200 g/l,
provide superior brightening of copper substrates, they have and preferably from about 60 g/l to about 175 g/l. Preferably,
a disadvantage in that the drag-out of chromic acid into the the peroxide of the present invention is added to the solution
rinse bath is so great that at times parts will be etched in the in the form of hydrogen peroxide, however, other peroxide
rinse water. While other additives are known to provide 35
advantageous brightening at reduced chromium levels, there sources may be used, but typically are not used because they
still remains a need in the art for improvement through are costly.
removal of chromic acid content, while providing better bath A critical constituent of the bath in the present invention
stabilization, improved levelling and reduced etching of is the peroxide stable constituent which forms the dissolu
parts, such that only high quality brightening is achieved. tion inhibiting film.
Generally, the peroxide stable constituentis a bath soluble
SUMMARY OF THE INVENTION non-polymeric pyrrolidone, a polyvinyl alcohol, or a poly
In accordance with the present invention, there is pro mer of a pyrrollidone or mixtures thereof.
vided a process and aqueous bath for bright dipping of a In a first preferred embodiment bath soluble pyrrolidone
copper containing substrate. The bath of the present inven 45 is provided in the bath in effective quantities for the creation
tion includes effective amounts of an acid, hydrogen perox of a dissolution inhibiting film. Suitable pyrrolidones
ide and a bath soluble peroxide stable constituent effective include N-methyl pyrrolidone, Cyclohexyl pyrrollidone,
for creation and stabilization of a dissolution inhibiting film N-Hydroxy Ethyl-2-pyrrolidone. Additionally, it is known
over the brightened substrate. that N-methyl pyrrolidone will break down in the presence
The present invention provides superior leveling and
50 of peroxide and acid in the bath to N-methyl succinate and
maintain film forming properties. Thus, succinates are also
brightening. The film created on the substrate produces a useful in the baths of the present invention. By bath soluble
self-attenuating brightening process whereby less copper herein it is meant that at least a concentration of 0.5% by
metal is removed from the substrate. Additionally, the weight of the composition must be in solution to provide
present invention produces these superior levelling and 55 dissolution inhibiting qualities. Typically, baths of the
brightening of substrates without the use of chromic acids, present invention will contain from about 5 to about 25 g/1
chelating agents or the like which present costly and prob of these non-polymerized pyrrollidones. Preferred quantities
lematic disposal problems. are from about 10 to about 22 g/l of the pyrrolidones.
Additional benefits and advantages of the present inven Advantages of these non-polymeric pyrrollidone are that
tion will become apparent upon review of the description of they do not break down as easily as some of the polymeric
the preferred embodiments set forth below in view of the constituents (set forth below) in the peroxide containing
accompanying examples and the claims appended hereto. baths. These baths can also be operated at higher tempera
BRIEF DESCRIPTION OF THE DRAWING tures to provide faster polishing times which may be desire
able for commercial purposes. Additionally, the breakdown
FIG. 1 is a graph demonstrating the self attenuation of the 65 of peroxide is reduced by use of the non-polymeric pyrroli
metal dissolution reaction as the dissolution inhibiting film dones. Thus, less bath additions are required in commercial
forms. operation. However, the dissolution inhibiting film, while
 5,630,950
3 4
still commercially viable, is slightly less effective than that self-regulating whereby excess etching of the base metal
realized when using the polymer additive discussed below. from too long a dwell time, or the like, is substantially
In some cases while dissolution is inhibited the self attenu reduced, if not in fact avoided via the presentinvention. This
ation characteristics are reduced or eliminated. However, is a great advantage for applications wherein process perim
etching of the substrate is avoided because of the protection eters may not be closely watched or controlled. This allows
of the film. Thus, this requires more attention to the polish for the brightening of parts with reduced concern with
ing process in commercial applications. respect to over-etching of the parts.
A second preferred constituent is a polyvinyl polymer of In a preferred embodiment of the present invention, a
a pyrrolidone, alcohol or acrylate. Polymers suitable in the surfactant is included for imparting anti-foam properties to
present invention must be peroxide stable in that they do not 10 the bath. The surfactant is preferably a block copolymer of
break down in the presence of peroxide, and must be propylene oxide and ethylene oxide. Aparticularly preferred
effective for the creation of a dissolution inhibiting film over surfactant is a pluronic L-42 surfactant. Other anti-foam
the substrates as the substrate is brightened. Thus, by the agents could also be utilized, provided that they do not
term "peroxide stable” it is meant that the polymer will not interfere with the advantageous characteristics of the bath.
significantly degrade over the useful brightening period of 15 The surfactant may be provided in effective amounts of from
the bath. Additionally, the polymer to be utilized must be about 0.01 g/l to about 5 g/l. Other suitable surfactants for
bath soluble. Preferred polymers also act to increase the use in the non-polymeric pyrrolidone baths include non
viscosity of the solution. Polymers useful in the present ionic and anionic surfactants which do not readily break
invention generally have a molecular weight of from about down in the peroxide and acid baths of the present invention.
5,000 to about 2,000,000; with preferred molecular weights 20 Particularly suitable surfactants include Flourads(8) available
being in the range of about 10,000 to about 1,280,000. The from 3M, Minneapolis, Minn., and DOWFAX6) surfactants
preferred polymers for use in the presentinvention are added available from Dow Chemical, Midland, Mich.
to the bath in an aqueous viscous solution. These solutions The baths of the present invention may be used to brighten
typically are viscous and have K-value viscosities in the any type of copper or its alloys such as zinc, brass, bronze
range of from about 15 to about 120 which typically ranges 25 or other copper containing metals although best performance
from about 30 to about 60. A preferred polymerfor use in the is realized with 70/30 brass. Depending on the copper
present invention is pyrrolidone polymer having a K-value content of the metal to be brightened, the peroxide content
in the range of about 20 to about 40. In particular, it is should be varied. The peroxide should be generally utilized
preferred that a polyvinyl pyrrolidone (PVP) in an aqueous at higher levels as the copper level of the base substrate
solution having the above setforth viscosities and molecular 30 increases and may be used at lower levels to prevent
weights is utilized. PVP's are particularly suitable for use in de-zincification in alloys which include reduced quantities
the presentinvention since they are produced in the presence of copper. It should also be noted that the film formation of
of hydrogen peroxide. This makes them inherently stable in the present invention is slower as the copper content is
baths containing peroxides. Suitable PVP polymers are increased. Thus, it may be desirable to provide longer bath
available from GAF Chemicals Corporation of Wayne, N.J. 35 dwell times or higher bath temperatures when brightening of
Additionally, an ISP polymer ACP-1021 PVP K-30, which alloys contain high quantities of copper. Additionally, when
includes hydrogen peroxide complexed in its structure, operating at higher levels of acid content it is also necessary
could also be used in the presentinvention without deviating to include higher levels of film forming polymers and/or
from the scope of the invention. It is believed that other higher temperatures.
polymers such as polyvinyl alcohols (PVA) and acrylate Thus, in accordance with the process aspects of the
polymers, may also be useful in the present invention, present invention, a bath as formulated above, is provided
provided they operate in the bath as described above. A in a quantity suitable for bright dipping of the copper alloy
particular PVA which has been found useful is a Elvanol parts at hand. The copper containing substrate is then dipped
90-50 Polyvinyl alcohol which can be obtained from E.I. du in the bath for sufficient time to brighten the metal and form
Pont de Nemours and Company, Wilmington, Del. 19898. 45 a dissolution inhibiting film over the substrate. Thereafter, in
Polymer content in the baths of the present invention is order to further process the metal or uncover the brightened
generally from about 2 g/l to about 25 g/l. Typically, from bare metal surface, the film must be removed by immersion
about 5 g/l to about 20 g/l is utilized with preferred amounts in a weak acid solution of, for instance phosphoric acid, in
of from about 8 g/l to about 16 g/l. These quantities reflect quantities from about 1% to about 5% by weight, which
the amount of polymer alone in its solid form. However, the 50 preferably is from about 2% to about 4% by weight.
viscosity values set forth above are characteristic of poly Typically, brightening baths of the present invention are
mers in an aqueous solution which are typically the form in operated at about 85° F to about 130° F. Higher tempera
which the polymers are added to the bath. tures may be used with non-polymeric pyrrollidone. Pre
The films produced in accordance with the present inven ferred temperatures with the polyvinyl pyrrolidone are
tion are typically a reddish-brown color. Without wishing to 55 between 85 F. and 100°F. since the polymeric pyrrollidones
be bound by theory, it is believed that the pyrrolidone, PVP tend to rapidly break down at temperatures above 100°F.
or other polymers, form a loosely complexed or cross-linked Operation above about 110° F tends to de-stabilize the
coating on the surface which includes copper oxides or the hydrogen peroxide in the solution when using polymeric
like which have been removed from the surface, which pyrrollidones. However when using non-polymeric pyrroli
would account for the reddish-brown color of the film. As dones the hydrogen peroxide is more stable allowing baths
the oxides are removed from the surface during brightening, to be operated at higher temperatures. Operation below
it is believed that the polymer?oxide coating is formed, about 85° F may tend to slow down the brightening process,
which builds up on the surface. As the film builds up on the however, the bath would still provide effective brightening
Surface, the active brightening ingredients are unable to if the parts are given sufficient dwell time in the bath.
reach the surface, inhibiting further dissolution of the base 65 Typically, dwell times in the baths for brightening of copper
metal. This prevents undesirable etching of the base metal. ranges from about 1 to about 10 minutes, with preferred
Thus, the brightening process of the present invention is ranges being from about 2 to about 5 minutes. It has been
 5,630,950
5 6
found that a 25% improvement in levelling over a scratch and re-weighed. The average dissolution rate was 4.67
polished part has been realized from merely a 5 minute mg/min for the first 7 minutes. Over the next 7 minutes, the
exposure to the baths of the present invention. Additionally, dissolution rate was found to be 3.55 mg/min. Thus, the
baths of the present invention have a reduced BTU output dissolution rate was 24% slower in the last 7 minutes of
which allows for a higher loading factor in the baths. A exposure. Both the copper wire surfaces were bright and
standard operating bath of the present invention, having a reflective without any etching.
loading factor of 2.52 ft/gallon, was found to have a BTU EXAMPLE IV
output of <380 BTU/hour. Thus, baths of the present inven
tion are capable of improved loading without boil- over A 500 ml polishing bath was made as follows: 150 ml
problems. 10 (30% by volume) of hydrogen peroxide (35% by weight
In order to further illustrate the present invention, the HO); 4 grams of sulfuric acid (8 g/l); 7.92 grams (15.84
following specific examples are provided. It will be under g/l) of polyvinyl pyrrolidone with an average molecular
stood that the examples as hereinafter setforth, are provided weight of about 40,000 to 60,000; 0.126 g (0.25 g/l) of a
for illustrative purposes and are not intended to be limiting block copolymer of propylene oxide and ethylene oxide; the
to the scope of this invention, as herein disclosed and as set 15 remaining volume was made up with deionized water and
the bath was heated to 85 F.
forth in the subsequent claims. Brass buttons of 1%6" diameter with a /16"lip made of an
EXAMPLE I Olin H-260 brass alloy (70% copper and 30% zinc) having
an average weight of 0.6469 g were processed.
A500mlaqueous brightening bath was prepared using 30 20 The process included a mild alkaline precleaning and
g/l PVP (14 g/l solid PVP obtained from GAF Chemicals) rinse and a postrinse with 1% to about 4% phosphoric acid
liquid having a K-value of 60 obtained from GAF, 200 g/l to remove the metal oxide/polymer film, then a rinse, and
hydrogen peroxide (35% by weight) and 10 g/lreagent grade finally a forced air drying.
sulfuric acid. The bath temperature was maintained at room A 125 piece load was placed in a plastic screened basket
temperature. Clean brass plated parts were immersed in the 25 and immersed into the bath and was shaken and moved up
bath and slow mechanical agitation was utilized. The parts and down in the solution to help expose all the parts to the
developed a dissolution inhibiting, reddish-brown film after solution. After 5 minutes, the temperature rose from 93.3°F.
about 2 to about 3 minutes. Parts where thereafter rinsed in to 97° F. The beaker was open on the top and bottom, and
water and then dipped in a 2% to about 4% phosphoric acid the sides were insulated with 0.5 inches of styrofoam. The
solution to dissolve and remove the film. The process 30 total dissolution weight loss was 1.8693 grams. The average
resulted in a highly reflective light colored brass surface weightloss was 0.0145 g/piece. The consumption of sulfuric
which did not tarnish upon standing. acid was 3.576 grams, determined by titration. The pH
EXAMPLE II
changed from 2.18 to 3.0. The hydrogen peroxide loss was
1.58% from the original 30% by volume.
An aqueous brightening bath additive having a volume of 35 For the next load of 25 pieces, sulfuric acid was added to
100 gallons is prepared utilizing 413 pounds PVP (peregal a 7.54 g/l level. The temperature was from 90°F. to about
ST), 2.1 pounds pluronic L-42 surfactant, and the remainder 100°F. After 5 minutes, the total weight loss was 0.385
water. To a commercial sulfuric acid and peroxide bright grams, with an average loss of 0.0154 g/piece.
ening bath is added 5% by volume of the additive. The bath Sulfuric acid was added after each load to maintain about
is maintained at room temperature. Copper plated parts are 7 g/l to about 8 g/l concentration. About 350 pieces were
immersed in the solution. The solution is mechanically processed before the end of the day. There was a gradual
agitated and the parts are left in the bath for an extended increase in metal dissolution rate from 0.015 g/piece to
period of time. A dissolution inhibiting, reddish-brown film about 0.035 g/piece, as the hydrogen peroxide was con
is formed within about 3 to about 5 minutes. The completed sumed down to a 21.8% by volume level. The bath was
brightened parts are immersed in about a 2% to about 4% 45 allowed to cool and sit overnight. In the morning, the
phosphoric acid solution to remove the reddish-brown film peroxide content was 20.5% by volume.
and are found to have good levelling and superior bright The bath was worked in the same manner until 250 more
ening without excessive removal of metal. The example is pieces were processed. The 35% by weight hydrogen per
repeated using 10% by volume of the additive, with the same oxide was found to be 13.8% by volume. A higher dissolu
results. 50 tion rate of 0.056 g/piece was realized and was trouble
forming a stable oxide film. This resulted in some etching on
EXAMPLE I the lip of the buttons. This was especially true of the Olin
A 500 ml brightening bath was prepared consisting of J-230 brass alloy (85% copper and 15% zinc) which needed
82.772% by weight water; 1.144% by weight HSO; about 25% by volume hydrogen peroxide where the 70/30
55 brass required about 15% by volume to about 12% by
11.14% by weight hydrogen peroxide (100% H2O); 4.92% volume to operate without etching. To this same bath,
by weight polyvinyl pyrrolidone and 0.024% by weight of a hydrogen peroxide was added to boost the concentration to
block copolymer of propylene oxide and ethylene oxide. 25% by volume and 150 more pieces were processed
The bath was heated to 90°F. and a +586 mv potential without etching.
was measured with a platinum and silver/silver chloride This example demonstrates that a chemical polishing bath
ORP probe. can be made and operated well by controlling the sulfuric
Two 16 gage copper wires of equal weight (1.8243 grams) acid content and monitoring the temperature through a wide
and length (6.5") were immersed in the bright dip bath. Both range of hydrogen peroxide levels.
wires were exposed to the bath solution for the first 7 EXAMPLE V
minutes, at the same time, to eliminate variations which may 65
be due to the bath chemistry. The second wire was removed A bath was prepared using 6 g/l reagent grade sulfuric
after 14 minutes. The two wires were then de-Smutted, dried acid (30% by volume); a 35% by weight hydrogen peroxide
 5,630,950
7
solution; and 10% by volume of an additive which was -continued
prepared in accordance with Example I. Witvol of
The bath was heated and maintained at a temperature of Acid Added Time Exposed Total Wt. Loss mg/minlin’
from about 85° F to about 90°F. A 70% copper and 30%
zinc, twelve square inch surface area hull cell panel was 10 g/l 6 minutes 0.4001 grams 5.56
placed in the bath and the weight loss was noted as set forth 12 gll 5 minutes 0.3148 grams 5.24
in Table 1. 14 g/1 6 minutes 0.3465 grams 481*
17 g/l 5 minutes 0.3868 grams 6.44k+
TABLE 1. *5 ml of bath titrated to pH of 4 with 8.4 ml of 0.1N NaOH.
10 **The panel placed vertical in the beaker was etched%" up from the bottom
DISSOLUTION OF BRASS PANELFORHULL CELL of the panel.
75% of the panel had a polished finish.
Time Wit
Part Tested Min. Loss Wt/Min. WithMin/In MV The film formed more difficulty as the acid was increased.
12 in 70/30 brass 5990 59.90 4.99 580.2 15 The bath dissolved 3.68 g/l of brass. Out of the 17 g/l acid
T5.20 75.20 6.27 580 added only 12 g/l remained as free acid. The peroxide
1. 6100 61.00 5.08 580.2 dropped 7% from the original level, 112.7 g/l to 104 g/l.
2
3
60.70
88.60
30,35
29.53
2.53
2.46
580
580
Sitting for 13 hours the peroxide dropped only 2% (102 g/l).
4 112.60 28.15 2.35 580 The bath gassing was minimal compared to PVP with more
than twice the dissolved solids.
20

The results are set forth in the graph of FIG.1. As can be EXAMPLE VII
readily appreciated from the graph, the dissolution rate
slows down substantially after about 2 minutes into the A500 ml bath was prepared as set forth below in Table II.
process. This coincides with the formation of the film on the 25 TABLE I
hull cell surface.
Constituents Quantity
EXAMPLE VI
hydrogen peroxide (35%) 140 ml
Various aqueous brightening baths are prepared in 500ml polyvinyl alcohol 50 ml
quantities as follows: 30 water 310 ml
sulfuric acid (66° Be") 4g
1 g/l sulfuric acid; 45 g/l H.O.; 2 g/l. PVP ph 2.0
2 g/l sulfuric acid; 50 g/l H.O.; 5 g/l. PVP surface tension 51 dynesicm
4 g/l sulfuric acid; 60 g/L H.O.; 8 g/l PVP *Elvanol 70-30 (4% aqueous solution)
8 g/l sulfuric acid; 175 g/l H.O.; 16 g/l. PVP 35
12 g/l sulfuric acid; 200 g/l H.O.; 20 g/l PVP The bath was tested for dissolution inhibiting film using
35 g/l sulfuric acid; 230 g/l HO; 25 g/l. PVP a copper disc having a diameter 24" with a surface area of
These solutions are prepared with 0.1% by weight sur 14 square inches. The bath was raised to a temperature of
factant. The solutions are found useful to form brightened 105°F. The disc was immersed in the bath and weighed after
metals with dissolution inhibiting layers thereover. The 40 1 minute and then again after 2 minutes. The weight loss
example is repeated utilizing various viscosities of PVP after 1 minute was found to be 0.0304 g/min and weight loss
polymer solutions ranging from K-15 to K-120, and are after 2 minutes was found to be 0.0636 g/min. A dissolution
found to form dissolution inhibiting films. inhibiting, reddish brown film is formed within about 2 to
about 1 minute. The finished part has an improved reflective
EXAMPLE VII 45 surface.

A 500 ml bath was made by dissolving 2.5 grams of EXAMPLE X

Elvanol 71-30 (a polyvinyl alcohol made by DuPont) into
350 ml of hot water with 3 grams of sulfuric acid reagent A500 m/I polishing bath was prepared as set for in Table
grade. The bath was cooled to 100° F and then 161 grams 50 II:
of hydrogen peroxide (35% by weight) was added to the
bath. The PVA used was not completely dissolved, more TABLE II
soluble forms of PVA having more acetate groups hydro 35% hydrogen peroxide 140 m
lyzed would make a more viscous bath possible, which polyvinyl alcohol 50 ml
would be beneficial. A 12 in 70/30 Brass Panel was 55 water 310 ml
immersed into the bath for 5 minutes, and the weight loss sulfuric acid (66° Be") 5g
pH 2.103
was recorded. Thereafter, 1 gram of acid was added to the surface tension 67 dynesicm
bath and the same panel was immersed again. This pattern
was continued until etching occurred. The results are set *Elvanol 90-50 (5.4 g/l solution)
forth below.
The dissolution test was again done using a copper disc
24" in. in diameter having an area of 14 square inches. In
Acid Added Time Exposed Total Wt. Loss mg/minlin’ this test the weight loss permitted in the first minutes was
0.0616 g/min and after 2 minutes was 0.1738 g/min a
6 g/1 5 minutes 0.1354 grams 2.25 65 reddish brown dissolution inhibiting filmis noted after about
8 g/l. 5 minutes 0.2572 grams 4.29 % to 1 minute interval. The finished part provides an
improved reflective finish.
 5,630,950
9 10
EXAMPLE X While benzotriazol (a known copper tarnishinhibitor) had
A 500 ml polishing bath is prepared as set forth in Table no affect on the formation of the film other agents such as
IV: aminotriazol seem to inhibit film formation.
EXAMPLE X
TABLE IV A900 ml bath is prepared in a 1000 ml beaker using 30%
Constituents Quantity by volume 35% peroxide, 10 grams of cyclohexyl
pyrrollidone, 8.6 g. 66'Be Sulfuric acid and the remainder
hydrogen peroxide (35%) 140 m water. The bath was raised to a temperature of 120°F. A 6.5
polyvinyl alcohol 50 m
Water 310 ml 10 inch long 12 gauge copper wire is immersed in the solution
sulfuric acid (66° Be') 4g in a first test. In a second test a 9 square inch panel was
pH 2,023 immersed in the bath. A reddish-brown dissolution inhibit
surface tension 51 dynes/cm ing film was found to form after about 4 to 1 minute. The
*Elvanol 51-05 (4% solution) part was found to be polished with no etching after about 2
15 to 3 minutes.
A dissolution test was accomplished with a copper disc EXAMPLE XIV
24" in. in diameter having an area of 14 square inches. The A900 ml bathis prepared in a 1000 ml beaker using 30%
bath was raised to a temperature of 105°F. The weight loss by volume 35% peroxide, 10 grams of N-hydroxy ethyl 2
per minute after 1 minute is 0.0595 grams and after 2 pyrrolidone, 8.6 g 66°Be Sulfuric acid and the remainder
minutes is 0.0784 g/min. Areddish brown dissolution inhib 20
water. The bath was raised to a temperature of 120°F. A 6.5
iting film is noted after about 4 to 1 minute. The finished inch long 12 gauge copper wire is immersed in the solution
part has an improved reflective surface. in a first test. In a second test a 9 square inch panel was
EXAMPLE XI immersed in the bath. A reddish-brown dissolution inhibit
25 ing film was found to form after about 4 to 1 minute. The
A 500 ml polishing bath was prepared with the constitu part was found to be polished with no etching after about 2
ents as set forth in Table V. to 3 minutes.
It is to be understood that the above description and
TABLE V examples of the preferred embodiments are not to be lim
Constituents Quantity 30 iting to the present invention. The present invention can be
practiced otherwise than as specifically disclosed above, as
hydrogen peroxide 140 ml it will be readily appreciated by those skilled in the art. Thus,
N-methyl pyrrolidone 5.9 ml it is appreciated that the invention is susceptible to
water 310 ml
sulfuric acid (66° Be') 4g modification, variation and change without departing from
pH 2.06 35 the proper scope and fair meaning of the accompanying
surface tension 67 dynesicm claims.
What is claimed is:
A dissolution test was accomplished using a copper disc 1. An aqueous copper brightening bath comprising:
24" in. in diameter having an area of 14 square inches. The an acid and a peroxide In effective amounts in water to
bath was raised to a temperature of a 105° F when the provide brightening of a copper containing substrate;
and
copper was immersed therein. After 1 minute of immersion a bath soluble, peroxide stable constituent effective for
the weight loss was 0.0654 g/min. After 2 minutes at formation of a dissolution inhibiting film upon bright
temperature of the weight loss was 0.0772 g/min. A reddish ening of the substrate thereby providing for substan
brown dissolution inhibiting film is found to form after 45 tially self-attenuating of the dissolution of the substrate
about 72 to 1 minute. The copper disc had an improved after brightening of the substrate.
reflective surface.
2. The bath of claim.1 wherein said constituentis selected
EXAMPLE XII from the group consisting of a source of bath soluble
non-polymeric pyrrollidone, succinates, polymers of
A750ml polishing bath was prepared as setforthin Table 50 pyrrolidones, alcohols, and acrylates, and mixtures thereof.
VI: 3. The bath of claim 2 wherein the pyrrolidone polymer is
a polyvinyl pyrrolidone.
TABLE VI 4. The bath of claim3 wherein the polyvinyl pyrrolidone
Constituents Quantity has a molecular weight of from about 10,000 to about
55 1,280,000.
hydrogen peroxide (35%) 200 m 5. The bath of claim3 wherein the polyvinyl pyrrolidone
N-methyl pyrrolidone 3.75 ml has a K-value viscosity at 25° C. of from about K-15 to
benzotriazol 375g about K-90.
Water 545 ml
sulfuric acid (66° Be') 13 g 6. The bath of claim 2 wherein the alcohol polymer is
polyvinyl alcohol.
7. The bath of claim 1 wherein the bath soluble peroxide
A dissolution test was accomplished by using a 70-30 stable constituent is selected from the group consisting of
brass plate the dissolution rate was found to be 9.25 ml per N-methyl pyrrollidone, cyclohexyl pyrrolidone, N-hydroxy
in perminute. A reddish brown dissolution inhibiting film ethyl-2-pyrrolidone, N-methyl succinate and mixtures
was noted on the part after about 4 to 1 minute. The bath is 65 thereof.
tested and found to contain N-methyl succinate. The brass 8. The bath of claim 1 wherein said bath soluble peroxide
plate was highly polished upon completion of polishing. stable constituent is N-methyl pyrrollidone.
 5,630,950
11 12
9. A process for bright dipping of a copper containing 20. The aqueous brightening bath of claim 19 wherein
substrate comprising the steps of: said polyvinyl polymer is selected from the group consisting
a) providing an aqueous bath comprising from about 1 g/l. of polyvinyl pyrrollidone, polyvinyl alcohol and mixtures
to about 35 g/l of an acid, from about 45 g/l to about thereof.
230 g/l of a peroxide, and from about 2 g/l to about 25 21. The bath of claim 20 wherein the polymer is added to
g/l of a peroxide stable constituent effective for creation the bath by way of an aqueous solution of the polymer
and stabilization of a dissolution inhibiting film over a having a K-value viscosity at 25°C. of from about K-15 to
brightened substrate; and about K-90.
b) immersing a copper containing substrate into a bath for 10
22. The bath of claim 21 wherein the viscosity at 25°C.
a sufficient time to brighten the metal and form a of said polymer solution when added to the bath is from
dissolution inhibiting film over the substrate and pro about K-30 to about K-60.
viding for self-attenuation of the dissolution of the 23. The bath of claim 20 wherein said polyvinyl pyrroli
substrate after brightening of the substrate. done polymer and peroxide constituents may be provided in
10. The process of claim 9 wherein said constituent is 15 the form of a polyvinyl pyrrollidone complexed with a
selected from the group consisting of a source of a bath hydrogen peroxide.
soluble non-polymeric pyrrolidone, succinates, pyrrollidone 24. The bath of claim 19 wherein the polymer has a
polymers, alcohol polymers, acrylate polymers, and mix molecular weight of from about 10,000 to about 1,280,000.
tures thereof.
25. The bath of claim.19 wherein the acid is selected from
11. The process of claim 10 wherein said polymer is a the group consisting of sulfuric acid, hydrochloric acid,
polyvinyl pyrrolidone polymer. 20
12. The process of claim 11 wherein said polymer has a nitric acid, and phosphoric acid.
molecular weight of from about 10,000 to about 1,280,000. 26. An aqueous brightening bath for brightening of a
13. The process of claim 11 wherein said polymer has a copper containing substrate comprising from about 1 g/l to
K-value viscosity at 25° C. of from about K-15 to about about 35 g/l of an acid, from about 45 g/l to about 230 g/l
K-90. 25 hydrogen peroxide, at least 0.5% by weight of a non
14. The process of claim 10 wherein said polymer is a polymeric pyrrolidone or succinate effective for formation
polyvinyl alcohol. of a dissolution inhibiting film over the substrate during
15. The process of claim 9 wherein said acid is selected brightening thereof which acts to substantially self-attenuate
from the group consisting of sulfuric acid, hydrochloric acid, 30
the dissolution reaction after brightening of the copper
nitric acid, and phosphoric acid. containing substrate.
16. The process of claim 9 wherein said peroxide is 27. The aqueous brightening bath of claim 26 wherein the
provided in the form of hydrogen peroxide. source of non-polymeric pyrrollidone is selected from the
17. The process of claim 16 further comprising the step of group consisting of N-methyl pyrrollidone, cyclo-hexyl
dipping said brightened substrate into a bath of phosphoric 35
pyrrollidone, n-hydroxyethyl-2-pyrrollidone, N-methyl suc
acid for removal of said film. cinate and mixtures thereof.
18. The process of claim 17 wherein the concentration of 28. The aqueous brightening bath of claim 26 wherein the
phosphoric acid in said bath is from about 1% by weight to source of non-polymeric pyrrollidone is N-methyl pyrroli
about 4% by weight. done.
19. An aqueous brightening bath for brightening of a 29. The aqueous brightening bath of claim 26 wherein
copper containing substrate, comprising from about 1 g/l to said succinate is N-methyl succinate.
about 35 g/l of an acid; from about 45 g/l to about 230 g/l 30. The brightening bath of claim 26 wherein the non
hydrogen peroxide; and from about 2 g/l to about 25 g/l of polymeric pyrrollidone is from about 5 g/l to about 25 g/l.
a polyvinyl polymer effective for formation of a dissolution 31. The brightening bath of claim 26 wherein the non
inhibiting film over the substrate during brightening thereof 45
polymeric pyrrollidone is from about 10 g/l to about 22 g/l.
which acts to substantially self-attenuate the dissolution
reaction after brightening of the copper containing substrate. ck :: * : *k
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,630,950 Page 1 of 3
DATED May 20, 1997
INVENTOR(S) :
Anthony R. Cangelosi
it is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
corrected as shown below:

Column 1, Line 29, delete 2nd occurrence of "typically".

Column 2, Line 47, "Cyclo" should be -cyclo--.
Column 2, Line 48, "N-Hydroxy Ethyl-2-pyrrolidone" should be --N-
hydroxy ethyl-2-pyrrolidone--.
Column 2, Line 59, "pyrrolidone" should be -pyrrolidones--.
Column 3, Line 44, "Polyvinyl" should be -polyvinyl
Column 4, Line 36, "contain" should be --containing--.
Column 4, Line 41, "bath as" should be --bath, as--.
Column 4, Line 53, "pyrrolidone" should be -pyrrolidones--.
Column 5, Line 28, "where" should be -were--.
Column 6, Line 50, after "and" insert --there--.
Column 7, Line 55, "Brass Panel" should be --brass panel--.
Column 8, Line 13, "difficulty" should be -difficultly--.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,630,950 Page 2 of 3
DATED : May 20, 1997
INVENTOR(S) : Anthony R. Cangelosi
it is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
corrected as shown below:

Column 8, Line 32, "ph" should be --pH-.

Column 8, Line 49, "for" should be --forth-.
Column 8, Line 52, insert headings: --Constituents-- above first
Column,
and --Quantity-- above second Column.
Column 8, Line 62, delete "in.".
Column 8, Line 63, "minutes" should be -minute--.
Column 9, Line 17, delete "in.".
Column 9, Line 39, delete "in.".
Column 9, Line 40, delete "a". (second occurrence)
Column 9, Line 42-43, delete "at temperature of".
Column 9, Line 63, "plate" should be --plate;--.
 UNITED STATES PATENT ANDTRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 5,630,950 Page 3 of 3

NV
ions(S) : Anthony
May 20, 1997
R. Cangelosi
It is certified that error appears in the above-indentified patent and that said Letters Patent is hereby
Corrected as shown below:

Column 9, Line 65, "is" should be --was--.

Column 10, Line 39, Claim 1 "in" should be --in--

Signed and Sealed this

Tenth Day of March, 1998

(a teen BRUCE LEHMAN

Attesting Officer Commissioner of Parents and Tradenarks