US 4,234,628 AGrant
Two-Step Preplate System for Polymeric Surfaces
Issue Date:1980-11-18
•8 Claims
Abstract
Non-metallic surfaces are prepared to receive an electroless metal deposit of copper, gold or nickel using a two-step adsorption procedure to sensitize the surface. The surface is first immersed in a bath containing copper in solution or suspension to adsorb the copper on the surface, followed by contact with a nickel or cobalt bath at a pH above 4 to encourage adsorption of the second metal. The adsorbed metals are then reduced with a borohydride reducing agent, with the nickel or cobalt serving to catalyze the reduction of the copper. The surface can be rinsed between the two adsorption steps without decreasing the effectiveness of the treatment.
Metadata
Assignee
- The Harshaw Chemical Company
Inventor
- Arthur H. DuRose
Application Information
Application Number:US 9643060
Filing Date:1978-11-28
Priority Date:1976-05-14
Art Unit:162
Classifications
IPC:
B05D 304C23C 302
Field of Search:
427304-306;430 A;404;419 R;343
Patent Drawings
This patent does not have any drawings.
Description
The following examples are presented to further illustrate the teachings of the present invention.
Example 1
A 1% CuCl.sub.2.2H.sub.2 O solution was prepared at an initial pH of 4.2. NaOH (1.9 N) is added with agitation at room temperature to form an insoluble hydrous copper compound. The addition was continued until a colloidal sol was formed at a pH of 5.3-5.5. The sol was milky blue-green in appearance.
A 3".times.4" panel of ABS (acrylonitrile butadiene styrene) was etched in CrO.sub.3 /H.sub.2 SO.sub.4 and was immersed in the copper sol for a period of three minutes at 60.degree. C. at a pH of 4.5. The panel was rinsed in water at a pH of between 7 and 7.7 and was then immersed in a 4% NiCl.sub.2 solution at a pH of 7.3 for a period of 2 minutes. At this pH, the nickel solution is close to turbidity. The panel was rinsed and then immersed in NaBH.sub.4 reducing solution for ten minutes. The panel was then compared with other ABS panels treated identically but without immersion in the nickel chloride solution.
The panels were then placed in an electroless copper bath and the time required to fully cover the panels was measured with the following results:
Example 2-7
In these examples, the following conditions and cycles were used:
(a) ABS panels 3".times.1/2" were etched for 5 minutes at 140.degree. C. in an etch solution of CrO.sub.3 /H.sub.2 SO.sub.4 after which they were rinsed.
(b) The panels were immersed for a period of 4 minutes in a copper bath followed by a water rinse.
(c) The panels were immersed for 2 minutes in a bath containing nickel or cobalt, again followed by a rinse.
(d) The panels were immersed for 5 minutes in a 1 g/l NaBH.sub.4 solution at room temperature followed by a rinse.
(e) The panel was then immersed with slow agitation into an electroless copper bath maintained at a pH of between 12 and 12.5.
The panels were graded according to the rate of visible coverage of the panels in the electroless copper bath, as follows: very good (VG)--coverage in less than 30 seconds; good (G)--coverage in 30-60 seconds; fair (F)--coverage in 1-2 minutes; poor (P)--at least 50% coverage in 2 minutes and complete coverage in 4 minutes; very poor (VP)--between 5 and 50% coverage in 2 minutes and no good (NG)--less than 5% coverage in 2 minutes.
Example 2
Ten panels were immersed in a copper hydrate sol prepared according to the teachings of Example 1 followed by immersion in four different nickel baths as follows:
2a--Nickel-Sorbitol (0.1 M NiSO.sub.4, 60 g/l sorbitol, pH 7.2)
2b--Ni-EN (0.1 M NiSO.sub.4, 0.3 M EN, pH 10.1)
2c--Ni-Gluconate (0.1 M NiSO.sub.4, 0.15 M gluconate)
2d--Ni-EDTA (0.1 M NiSO.sub.4, 0.1 M EDTA, pH 7.9)
Two panels were immersed in each nickel bath followed by reduction in the standard sodium borohydride solution at a pH of 10.4 or 11.7. In addition, another panel was immersed in bath 2a and in bath 2d, followed by reduction in 0.2 g/l sodium borohydride at a pH of 10.4. The results are as follows:
Example 3
Five panels were immersed in a copper complex bath composed of 0.1 m/l of copper sulfate and 0.2 m/l of ethylene diamine at a pH of 12.5. Each of the panels were then immersed in a nickel or cobalt complex followed by reduction and electroless plating. Panels 3a and 3b were immersed in the nickel-ethylene diamine bath of Example 2b followed by reduction of each at a different pH. Panel 3c was immersed in a nickel-ethylene diamine bath composed of 0.1 molar nickel sulfate and 0.3 molar ethylene diamine, at a pH of 10.1. Panel 3d was immersed in a nickel glycolate bath prepared from nickel nitrate (0.1 mol) and glycolic acid (0.2 moles) at a pH of 7.5. Panel 3e was immersed in a cobalt-sorbitol complex (0.1 mol CoSO.sub.4, 75 g/l of sorbitol and a pH of 7.5). The plating results are tabulated below:
Example 4
Several different copper immersion baths were prepared as follows:
Copper Tartrate (0.1 M CuSO.sub.4, 1.0 M rochelle salts, pH 6.1)
Cuprous Chloride-Calcium Chloride (5 g/l CuCl, 150 g/l CaCl.sub.2, 5 g/l resorcinol, pH 2.0)
Copper Acetate (0.1 M, pH 5.4)
Copper Acetate--dilute (0.0005 M, pH 6.75)
Copper Citrate #1 (0.1 M CuSO.sub.4, 0.1 M sodium citrate, pH 4.6)
Copper Citrate #2 (0.1 M CuSO.sub.4, 0.4 M sodium citrate, pH 6.5)
Copper-EDTA #1 (0.1 M CuSO.sub.4, 0.1 M EDTA, pH 6.5)
Copper-EDTA #2 (0.1 M CuSO.sub.4, 0.1 M EDTA, pH 10.85)
Cuprate (0.025 M CuCl.sub.2, 14 M NaOH)
Copper Acetate-Sorbitol (0.1 M Cu Acetate, 75 g/l sorbitol, pH 5.7)
The panels were immersed in these copper baths for four minutes followed by a two minute immersion in a nickel-sorbitol or nickel-ethylene diamine bath described in Examples 2 or 3 or in one of the following baths:
Nickel Acetate #1 (0.1 M, pH 7.1)
Nickel Acetate #2 (0.0005 M, pH 8.6)
Nickel Propionate (0.1 M NiSO.sub.4, 0.4 M propionic acid, pH 7.4) or
Nickel Acetate-Sorbitol (0.1 M Ni Acetate, 75 g/l sorbitol, pH 7.6)
The panels were then immersed for five minutes in sodium borohydride at the pH indicated in Table 4 followed by electroless copper deposition with the following results:
Example 5
Adhesion tests were carried out on four ABS panels, 3".times.4", that were initially immersed in copper and nickel baths and were reduced in sodium borohydride according to the treatment specified for panels 2b (copper hydrate/nickel-EN), 3e (copper-EN/Co sorbitol), 4c (copper acetate/nickel acetate) and 4k (copper acetate sorbitol/nickel acetate sorbitol). These panels were electroless copper plated for five to ten minutes and were then plated with 50 millimicrons of bright acid copper. The copper on each panel was then cut to form a 1" wide strip. A tab of this strip was clamped into a spring scale tensimeter, and the maximum force required to pull the strip is recorded on the scale as follows:
Panel 2b 6.5 pound per inch
Panel 3e 14 pounds per inch
Panel 4c 11 pounds per inch
Panel 4k 12.5 pounds per inch
In addition, an unetched ABS panel was alkaline cleaned and after rinsing was immersed in the baths used for panel 4c. Similarly, a panel was treated in the same baths used on panel 4k. Electroless coverage was obtained in less than 1 minute on panels reduced with borohydride at pH of 10 but not at pH of 12.
Example 6
The copper acetate-sorbitol/nickel acetate-sorbitol system of Example 4k was used as a pre-treatment on several other plastics including silica filled polypropylene, polyphenylene oxide and polyaryl ether. All three of the plastics were etched in CrO.sub.3 /H.sub.2 SO.sub.4 and the polypropylene was followed with an acid fluoride etch. In all instances, the rate of electroless copper coverage was comparable to that obtained on ABS plastic.
Example 7
Although sodium borohydride is the preferred reducing agent, hydrazine hydrate and dimethylamine borane can also be used under certain circumstances. A small ABS panel was immersed in the copper hydrate bath of Example 2 followed by immersion in the nickel-sorbitol bath of Example 2a. The panel was then reduced in a 10% solution of hydrazine hydrate at a pH of 13.5 and at a temperature of 70.degree. F. after which the panel was completely covered by electroless copper in 40 seconds. Generally, the hydrazine hydrate is useful only when copper hydrate is used as the first bath. The concentration of the hydrazine hydrate should be between 2 and 40%, and the pH should be above 12 (as measured at room temperature). Reduction should be carried out at a temperature above 40.degree. C., preferably between 65.degree. C. and 70.degree. C.
Two grams per liter of dimethylamine borane at a pH of 9.4 was used as a reducer on three panels immersed in the following baths: copper acetate-sorbitol followed by nickel acetate-sorbitol with very good results; copper tartrate followed by cobalt-sorbitol with no coverage and copper-EN followed by cobalt-sorbitol with good results. In general, the dimethylamine borane is not as effective as the sodium borohydride.
Example 8
A small etched ABS panel was immersed in a copper solution containing 12.5 grams of cuprous chloride, 28.4 grams of stannous chloride, 75 cc of HCl and 50 cc of water. After 4 minutes the panel was removed from the solution, was rinsed and was immersed in a sodium borohydride solution for 5 minutes. It was again rinsed and was then immersed in electroless copper solution. Complete coverage of electroless copper was obtained within 3 minutes.
Another ABS panel was treated in the same manner, but in addition was immersed in a nickel-sorbitol bath before reduction. A resultant copper coating in the electroless bath was formed much more quickly with complete coverage being obtained within 1-2 minutes.
Example 9
To determine the effect of various solvents on electroless plating, ABS panels were immersed in various copper solutions for 4 minutes and after rinsing was immersed in a 0.1 M nickel acetate solution for 2 minutes followed by reduction in borohydride for 5 minutes. The baths and time required to obtain complete coverage with electroless copper are as follows:
Although the rate of coverage of all of the panels was very good, slightly faster coverage was obtained with the solvents.
Example 10
ABS panels were immersed in 2.5 g of copper acetate in 100 cc of Cellusolve for 4 minutes and after rinsing were immersed for 2 minutes in either nickel acetate or nickel chloride solution prepared by adding 2.5 g of the respective salt to 100 cc of Cellusolve. After borohydride reduction for 5 minutes, coverage of electroless copper was obtained in 30 seconds or less. No coverage was obtained when the copper solution or the nickel solution was used by itself.
Example 11
Etched ABS panels pretreated according to Example 2b using copper hydrate followed by nickel-ethylenediamine and 4k using copper acetate-sorbitol followed by nickel acetate-sorbitol were plated in the electroless gold plating bath previously described at a temperature of 65.degree. C. The first panel (2b) was covered with gold in 20 seconds and the second panel (4k) was covered in 60 seconds.
Example 12
Etched ABS panels prepared according to Example 11 were treated in an electroless nickel bath using a hypophosphite reducing agent without success. However, using the electroless nickel bath described in Plating 54, 385 (1967), at a room temperature pH of 12, and an operating temperature below 50.degree. C. coverage was obtained in 25 seconds on the panel pretreated in copper hydrate and nickel sorbitol. Approximately 45 seconds was required to obtain coverage on the panel pretreated with copper acetate-sorbitol followed by nickel acetate-sorbitol.
Additional etched ABS panels were treated in copper hydrate followed by ethylenediamine and in copper acetate-sorbitol followed by nickel sorbitol and were then immersed in the nickel chloride electroless bath previously described using sodium borohydride as a reducer. Although no nickel deposition occurred at room temperature, the panels were coated with electroless nickel in 45-60 seconds at 60.degree.-63.degree. C.
The process of the present invention can be carefully controlled to allow the plating of etched non-metallic objects using racks or containers coated with plastisol without depositing copper on the plastisol. Baths that have been found to be effective for this purpose are cuprous chloride-calcium chloride followed by nickel chloride or by nickel sorbitol; copper chloride followed by nickel chloride, copper gluconate followed by nickel sorbitol; copper tartrate followed by nickel sorbitol; copper acetate-ammonium acetate followed by nickel sorbitol and copper acetate followed by nickel acetate.
Although it is possible to reverse the immersion process utilizing the nickel or cobalt bath followed by the copper bath, the results generally are not as favorable as those obtained by using copper immersion followed by nickel or cobalt immersion. If the nickel bath is used first, the conditions of the copper bath must be such that the nickel is not dissolved. For example, if a panel is immersed for 4 minutes in a nickel-sorbitol bath followed by immersion in a complexed copper bath using TEA, gluconate or tartrate as a complexer, the panels can be subsequently covered in 1-2 minutes with a layer of electroless copper.
In addition to the aforementioned advantages, the present process permits more uniform reduction than known prior art processes because the present invention does not depend upon drying of the copper and the nickel salts on the surface of the plastic prior to reduction. Stated differently, the ability to rinse the plastic substrate after the two immersion steps and before reduction helps to insure a uniform adsorption of the activator precursor on the surface prior to reduction.
The foregoing description and examples have been presented to clearly show the utility and applicability of the present invention in the preparation of non-metallic, polymeric surfaces to allow them to be plated with an electroless layer of copper, tin or gold. It is to be understood, however, that the present invention is not to be limited in scope of the specific parameters embodied in the examples.
Claims
Instead, the invention is to be measured in terms of the claims in which I claim:
1. A process of preparing a non-metallic surface for the electroless deposition of a metallic layer of copper, nickel or gold comprising the steps of (a) contacting the surface with a copper compound available from a bath selected from the group consisting of (1) a solution of a simple cupric compound; (2) a basic cupric hydrate suspension or colloid prepared by adding an alkali to the solution of (1); (3) a clear cuprate solution; and (4) a complex solution of copper containing a suitable complexing agent; (b) thereafter contacting the surface with an accelerator selected from the group consisting of (1) a nickel salt; and (2) a cobalt salt available as a simple solution, suspension or a complex solution; (c) rinsing the surface; and (d) contacting the surface with a reducing agent selected from the group consisting of a borohydride, hydrazine and a borane.
2. The process of claim 1 wherein the contact time with the copper compound is between 15 seconds and 10 minutes.
3. The process of claim 2 wherein the surface is rinsed following contact with the copper compound.
4. The process of claim 1 wherein a borohydride is used as the reducing agent in a concentration of less than 2 g/l.
5. The process of claim 2 wherein the copper is present as a copper hydrate colloid prepared by reacting in solution a copper salt selected from the group consisting of copper chloride, copper acetate and copper propionate with a base selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide and sodium carbonate in a pH range and temperature range at which coagulation does not occur.
6. A process according to claim 2 wherein the surface is contacted with a copper solution containing a simple cupric compound selected from the group consisting of copper sulfate, copper chloride, copper acetate, copper propionate, copper formate and copper nitrate.
7. The process according to claim 2 wherein a complex copper solution is prepared by adding a complexing agent to a soluble cupric compound at a pH above 4.
8. A preplating process for preparation of a polymeric article including the sequential steps of (a) immersing the article in a copper bath for a time interval ranging from 15 seconds to 10 minutes, said copper bath selected from the group consisting of (1) a clear aqueous solution containing a cupric compound wherein the copper is present in a concentration range of 0.0005 m/l to saturation; (2) a basic hydrate sol or suspension formed by adding an alkali to the clear solution of (1) until the final pH is between about 3.9 and about 10 wherein the concentration range of the copper in the sol is 0.0005 L to 0.6 m/l; (3) a clear cuprate solution formed by adding a high concentration of an alkali to the solution of (1); (4) a complex solution of copper formed by the addition of a complexing agent to the clear solution of (1) wherein the concentration range of the copper is 0.0005 to 2 m/l; (5) a momovalent complex of a copper halide or of a copper cyanide containing no excess cyanide; and (6) a clear or complexed cupric solution containing an organic solvent; (b) immersing the article in a nickel or cobalt bath maintained at a pH of 4 or above for a period of time between 15 seconds and 10 minutes, said bath selected from the group consisting of (1) a simple solution in which the concentration of the nickel or cobalt is between 0.0005 m/l and saturation; (2) a suspension formed by adding an alkali to the solution of (b) (1) in which the nickel or cobalt concentration is 0.0005 to 0.6 m/l; (3) a stable suspension formed by the addition of 1-100 g/l of a polyhydric alcohol to the suspension of (b) (2); and (4) a complex solution formed by the addition of a complexing agent to the simple solution of (b) (1) at an effective pH above 6.0; (c) rinsing the article with water to remove excess bath material; and (d) immersing the article in a bath containing a reducing agent selected from the group consisting of a borohydride, hydrazine and a borane.