Anti-tarnish treatment of metal foil

Information

  • Patent Grant
  • 5057193
  • Patent Number
    5,057,193
  • Date Filed
    Friday, December 22, 1989
    35 years ago
  • Date Issued
    Tuesday, October 15, 1991
    33 years ago
Abstract
A method of imparting tarnish and corrosion resistance to a copper or copper alloy foil in which the foil is first coated with a thin layer of zinc on at least one side. Thereafter, the foil is treated with an aqueous solution of chromic acid and sulfuric acid. The foil may then be rinsed in a dilute basic solution having a pH greater than 8 and then dried.
Description
Claims
  • 1. A process for imparting tarnish and oxidation resistance to copper and copper alloy foil material having one relatively roughened surface and one relatively smooth surface, said process comprising:
  • applying a coating of zinc on the smooth side of the foil material, and thereafter.
  • applying an aqueous sulfuric acid-chromic acid solution to said materials.
  • 2. The process of claim 1 wherein said solution has a concentration of chromic acid in the range of about 0.1 g/1 to about 1.0 g/1 and a concentration of sulfuric acid in the range of about 0.02 g/1 to about 20 g/1.
  • 3. The process of claim 2 wherein said concentration of said chromic acid is in the range of about 0.1 g/1 to about 0.3 g/1 and the concentration of said sulfuric acid is in the range of about 0.02 to about 0.7 g/1.
  • 4. The process of claim 1 further comprising rinsing said material after applying said solution.
  • 5. The process of claim 4 wherein said rinsing step comprises:
  • applying an aqueous rinse solution having a pH greater than about 8 to said material.
  • 6. The process of claim 5 further comprising:
  • drying said material after said rinsing step.
  • 7. The process of claim 5 wherein said rinsing solution contains at least 1 ppm of a material selected from the group consisting of the salts of alkali metals, the salts of alkaline earth metals, the hydroxides of the alkali metals, and the hydroxides of the alkaline earth metals.
  • 8. The process of claim 7 wherein said rinse solution contains at least 1 ppm of a material selected from the group consisting of calcium hydroxides, sodium hydroxide, potassium hydroxide and ammonium hydroxide.
  • 9. The process of claim 1 further comprising applying a coating of zinc on said roughened side of said material, said coating on said roughened side having a thickness greater than the coating on said relatively smooth side.
  • 10. The process according to claim 1 wherein said coating of zinc on said relatively smooth side is from about 0.001 to about 0.06 mg/cm.sup.2.
  • 11. The process of claim 10 wherein a coating of zinc is applied to said roughened side, said coating on said roughened side being between about 0.3 to about 3.0 g/m.sup.2.
  • 12. The process of claim 11 wherein said coating of zinc on said roughened side is between about 0.5 to about 2.0 g/m.sup.2.
Parent Case Info

This application is a continuation of application Ser. No. 07/333,210 filed Apr. 5, 1989, now abandoned. The present invention relates broadly to the treating of metal foil to form a tarnish and oxidation resistant film thereon. More specifically, the present invention relates to the treatment of copper and copper base alloy foil materials to prevent tarnishing. One of the problems which faces manufacturers of both electrolytic and wrought copper and copper alloy materials is the tarnishing of the materials during storage and shipment. This tarnishing generally results from the exposure of the copper to normal atmospheric conditions. This tarnishing is aesthetically unpleasant as well as a potential source of serious problems during the manufacture of many products such as printed circuits. For example, tarnishing of copper foil prior to its lamination to a dielectric substrate can affect both the bond strength between the foil and the substrate material and the etching characteristics of the resultant laminate. In the past, tarnish resistance has been imparted to copper and copper base alloy materials by immersion of the copper material in an electrolyte containing chromate ions U.S. Pat. No. 3,625,844 to McKean describes a method of antitarnishing copper foil involving the electrolytic treatment of copper foil in an aqueous electrolyte under critical conditions of hexavalent chromium ion concentration, cathode current density, and treatment time. U.S. Pat. No. 3,853,716 to Yates et al discusses the McKean process and points out that it is not a completely satisfactory antitarnishing technique because a build-up of copper and chromium cations in the electrolyte bath interfere with the effectiveness of the antitarnishing. Yates et al attempt to overcome this problem by rendering the copper material cathodic as it passes through an aqueous electrolyte containing hexavalent chromium ion-containing anions and being of sufficient alkalinity to cause precipitation of copper and chromium cations. U.S. Pat. Nos. 4,131,517 to Mitsuo et al and 4,387,006 to Kajiwara et al illustrate still other chromate containing treatments for suppressing time dependent changes in color tone during storage. Still other antitarnishing techniques are illustrated in U.K. published patent applications 2,030,176A and 2,073,779A. Solutions of phosphoric acid, chromic acid and/or their salts have also been applied to various materials in an attempt to impart tarnish and corrosion resistance to the material. U.S. Pat. Nos. 3,677,828, 3,716,427 and 3,764,400, all to Caule, illustrate the use of phosphoric acid solutions to improve the tarnish resistance of copper and copper base alloys. Caule also describes in his '400 patent the use of a basic rinse solution after application of his phosphoric acid treatment. Phosphoric and/or chromic acid solutions have also been applied to zinc, zinc-coated articles, and aluminum foil and articles U.S. Pat. Nos. 2,030,601 to McDonald, 2,412,543 to Tanner, 2,418,608 to Thompson et al, 2,647,865 to Freud and 4,432,846 to Honeycutt III illustrate some of the applications of phosphoric-chromic acid solutions. The treatment of copper or copper alloy foil for use in printed circuit applications creates a somewhat unique problem that limits the suitability of some antitarnishing treatments. In the manufacture of printed circuits, copper sheet or foil is bonded to a dielectric substrate. Prior to bonding, at least one surface of the copper foil is generally roughened or treated to improve the bond strength between the foil and the substrate. While there are a variety of techniques available to roughen or treat the foil surface, one of the most commonly used involves the formation of a plurality of copper or copper oxide modules or dendrites on the foil surface. U.S. Pat. Nos. 4,468,293 and 4,515,671 both to Polan et al illustrate one such dendritic or nodular roughening treatment. The primary deficiency of many antitarnishing treatments is the concentration of chromic and/or phosphoric acid and/or their salts in the antitarnishing solution. Where the antitarnishing solution contains relatively high concentrations of chromic and/or phosphoric acid and/or their salts, immersion of the treated copper foil in the solution may lead to dissolution of the nodules or dendritic particles which may result in relatively weak bond strength characteristics. Copper or copper alloy foil is used in many printed circuit board applications, particularly with fiberglass or epoxy substrates. Such foil may require an electrodeposited zinc or brass coating on at least one side of the foil, usually the roughened side of electrodeposited foil bearing the nodules or dendrites of the roughening treatment. The zinc or brass coating is needed in some instances to provide adequate bond strength with the substrate. After the zinc or brass coating, the foil may be further treated to impart tarnish resistance during storage and further processing by the circuit board laminators and manufacturers. One such tarnish resistant treatment is described in U.S. Pat. No. 4,647,315 to Parthasarathi and Polan, which tends to overcome the problems mentioned above. Briefly, the process disclosed in that patent comprises the immersion of the copper or copper alloy foil in a dilute aqueous solution of a mixture of chromic acid and phosphoric acid followed by a rinse in a dilute basic solution having a pH greater than about 8. It has been found that in using the process of the type described in U.S. Pat. No. 4,468,293 to provide a nodule or dendritic roughened surface followed by zinc coating on the roughened surface and immersion in a dilute chromate solution such as an aqueous solution of CrO.sub.3 or Na.sub.2 Cr.sub.2 O.sub.7 at room temperature, while the foil has a relatively good peel strength, the tarnish resistance imparted by such a process is not entirely satisfactory as it does not prevent oxidation in air at 175.degree. C. for 30 minutes. On the other hand, utilizing the antitarnish treatment of U.S. Pat. No. 4,647,315 on such foil by immersion in a chromic acid phosphoric acid solution followed by a Ca(OH).sub.2 rinse provides good tarnish resistance but results in relatively poor peel strength. In accordance with the present invention, a technique is provided which results in both superior tarnish resistance and high peel strength for copper and copper alloy foil. According to the process of the present invention, a thin zinc coating is applied on the smooth or non-treated side of the foil followed by immersion in a chromic acid/sulfuric acid bath followed by a rinse in a dilute basic solution. As a result of this treatment, a thin zinc coating, from about 0.06 to 0.003 mg/cm.sup.2 is provided on the smooth side. Accordingly, it is an object of the present invention to provide a novel treatment useful in providing tarnish resistance to copper and copper base alloy materials. It is a further object of the present invention to provide an antitarnish treatment for treating copper or copper alloy foil and rendering it more particularly suitable for use in printed circuit applications. These and other objects of the present invention will become more apparent from the following description and to the accompanying drawings in which:

US Referenced Citations (31)
Number Name Date Kind
RE30180 Wolski et al. Dec 1979
2030601 McDonald Feb 1936
2412543 Tanner Dec 1943
2413608 Thompson et al. Apr 1947
2647865 Freud Aug 1953
3220897 Conley et al. Nov 1965
3293109 Luce et al. Dec 1966
3322656 Dahringer et al. May 1967
3585010 Luce et al. Jun 1971
3625844 McKean Dec 1971
3677828 Caule Jul 1972
3699018 Carlson Oct 1972
3716427 Caule Feb 1973
3764400 Caule Oct 1973
3853716 Yates et al. Dec 1974
3857681 Yates et al. Dec 1974
3918926 Wolski et al. Nov 1975
4049481 Morisaki Sep 1977
4053370 Yamashita et al. Oct 1977
4131517 Mitsuo et al. Dec 1978
4387006 Kajiwara et al. Jun 1983
4432846 Honeycutt, III Feb 1984
4468293 Polan et al. Aug 1984
4515671 Polan et al. May 1985
4529486 Polan Jul 1985
4532014 Polan et al. Jul 1985
4549950 Polan et al. Oct 1985
4568431 Polan et al. Feb 1986
4647315 Parthasaranthi et al. Mar 1987
4652346 Polan Mar 1987
4789438 Polan Dec 1988
Foreign Referenced Citations (5)
Number Date Country
112145 Mar 1975 DEX
1211494 Nov 1970 GBX
1293801 Oct 1972 GBX
2030176A Apr 1980 GBX
2073779A Oct 1981 GBX
Non-Patent Literature Citations (1)
Entry
U.S. Patent Application Ser. No. 07/333,212, filed Apr. 5, 1989-Lin et al., for "Treatment of Metal Foil".
Continuations (1)
Number Date Country
Parent 333210 Apr 1989