Metal surface treatment composition
View Patent ↗A process is described for treating metal surfaces with roughening compositions that use poly(ethyleneamino propionitrile) polymer as an additive in the composition to improve adhesion of polymeric materials to the metal surfaces and to improve peel strength for thermal stability. The polymer of the invention may be added to compositions containing for example, cupric chloride and hydrochloric acid and is also usable in compositions containing an oxidizer/acid/azole mixture. Other additives, such as adiponitrile may also be beneficially added to compositions of the invention.
1. A method of increasing the adhesion of a polymeric material to a metal surface, the method comprising the steps of:
a) contacting the metal surface with a composition comprising:
i) an oxidizer comprising a source of cupric ions;
ii) at least one of an organic acid or an inorganic acid;
iii) a source of halide ions; and
iv) poly(ethyleneamino propionitrile) polymer; and
b) thereafter, bonding a polymeric material to the metal surface;
wherein said metal surface comprises copper.
2. The method according to claim 1 , wherein the source of cupric ions is selected from the group consisting of cupric chloride, cupric bromide, cupric hydroxide, cupric salts of organic acids and combinations of one or more of the foregoing.
3. The method according to claim 2 , wherein the source of cupric ions is cupric chloride.
4. The method according to claim 1 , wherein the source of halide ions is selected from the group consisting of hydrochloric acid, hydrobromic acid, sodium chloride, calcium chloride, potassium chloride, ammonium chloride, potassium bromide, copper chloride, zinc chloride, iron chloride, iron bromide, tin bromide, copper bromide, and combinations of one or more of the foregoing.
5. The method according to claim 4 , wherein the source of halide ions comprises hydrochloric acid.
6. The method according to claim 1 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.01 to 1.0 grams/liter.
7. The method according to claim 6 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.15 to about 0.70 g/l.
8. The method according to claim 1 , wherein the composition further comprises adiponitrile.
9. The method according to claim 8 , wherein the concentration of adiponitrile is between about 0.1 and 1.0 mill.
10. The method according to claim 1 , wherein the metal surface is contacted with the composition by immersion or by spraying.
11. A roughening composition for increasing the adhesion of a polymeric material to a metal surface, the composition comprising:
a) an oxidizer comprising a source of cupric ions;
b) at least one of an organic acid or an inorganic acid;
c) a source of halide ions; and
d) poly(ethyleneamino propionitrile) polymer;
wherein said metal surface comprises copper.
12. The roughening composition according to claim 11 , wherein the source of cupric ions is selected from the group consisting of cupric chloride, cupric bromide, cupric hydroxide, cupric salts of organic acids and combinations of one or more of the foregoing.
13. The roughening composition according to claim 12 , wherein the source of cupric ions is cupric chloride.
14. The roughening composition according to claim 11 , wherein the source of halide ions is selected from the group consisting of hydrochloric acid, hydrobromic acid, sodium chloride, calcium chloride, potassium chloride, ammonium chloride, potassium bromide, copper chloride, zinc chloride, iron chloride, iron bromide, tin bromide, copper bromide, and combinations of one or more of the foregoing.
15. The roughening composition according to claim 14 , wherein the source of halide ions comprises hydrochloric acid.
16. The roughening composition according to claim 11 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.01 to 1.0 grams/liter.
17. The roughening composition according to claim 16 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.15 to about 0.70 g/l.
18. The roughening composition according to claim 11 , wherein the composition further comprises adiponitrile.
19. The roughening composition according to claim 18 , wherein the concentration of adiponitrile is between about 0.1 and 1.0 ml/l.
20. A method of increasing the adhesion of a polymeric material to a metal surface, the method comprising the steps of:
a) contacting the metal surface with a composition comprising:
i) an oxidizer;
ii) at least one acid;
iii) a corrosion inhibitor;
iv) poly(ethyleneamino propionitrile) polymer;
v) optionally, a source of halide ions; and
b) thereafter, bonding a polymeric material to the metal surface;
wherein said metal surface comprises copper.
21. The method according to claim 20 , wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates.
22. The method according to claim 21 , wherein the oxidizer is hydrogen peroxide.
23. The method according to claim 20 , wherein the corrosion inhibitor is selected from the group consisting of triazoles, benzotriazoles, imidazoles, benzimidazoles, tetrazoles, and mixtures of one or more of the foregoing.
24. The method according to claim 20 , wherein the composition further comprises a source of adhesion enhancing ions, which ions are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, and mixtures of one or more of the foregoing.
25. The method according to claim 24 , wherein the source of adhesion enhancing ions comprise molybdate ions.
26. The method according to claim 20 , wherein the at least one acid is a mineral acid.
27. The method according to claim 20 , wherein the source of halide ions is selected from the group consisting of alkaline metal halide salts and oxohalide salts.
28. The method according to claim 20 , wherein the source of halide ions is a source of chloride ions.
29. The method according to claim 20 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.01 to 1.0 grams/liter.
30. The roughening composition according to claim 29 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.15 to about 0.70 g/l.
31. The method according to claim 20 , wherein the composition further comprises adiponitrile.
32. The method according to claim 31 , wherein the concentration of adiponitrile is between about 0.1 and 1.0 ml/l.
33. The method according to claim 20 , wherein the metal surface is contacted with the composition by immersion or by spraying.
34. The method according to claim 20 , wherein the polymeric material is a resist or a prepreg.
35. A roughening composition for increasing the adhesion of a polymeric material to a metal surface, the composition comprising:
a) an oxidizer;
b) at least one acid;
c) a corrosion inhibitor;
d) a polymer comprising a reaction product of polyethylenimine and acrylonitrile; and
e) optionally, a source of halide ions;
wherein said metal surface comprises copper.
36. The roughening composition according to claim 35 , wherein the oxidizer is selected from the group consisting of hydrogen peroxide and persulfates.
37. The roughening composition according to claim 36 , wherein the oxidizer is hydrogen peroxide.
38. The roughening composition according to claim 35 , wherein the corrosion inhibitor is selected from the group consisting of triazoles, benzotriazoles, imidazoles, benzimidazoles, tetrazoles, and mixtures of one or more of the foregoing.
39. The roughening composition according to claim 35 , wherein the composition further comprises a source of adhesion enhancing ions, which ions are selected from the group consisting of molybdates, tungstates, tantalates, niobates, vanadates, and mixtures of one or more of the foregoing.
40. The roughening composition according to claim 39 , wherein the source of adhesion enhancing ions comprise molybdate ions.
41. The roughening composition according to claim 35 , wherein the at least one acid is a mineral acid.
42. The roughening composition according to claim 35 , wherein the source of halide ions is selected from the group consisting of alkaline metal halide salts and oxohalide salts.
43. The roughening composition according to claim 35 , wherein the source of halide ions is a source of chloride ions.
44. The roughening composition according to claim 35 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.01 to 1.0 grams/liter.
45. The roughening composition according to claim 44 , wherein the concentration of the poly(ethyleneamino propionitrile) polymer in the composition ranges from about 0.15 to about 0.70 g/l.
46. The roughening composition according to claim 35 , wherein the composition further comprises adiponitrile.
47. The roughening composition according to claim 46 , wherein the concentration of adiponitrile is between about 0.1 and 1.0 mill.