Method for etching non-conductive substrate surfaces
View Patent ↗An etching composition for non-conductive substrates such as polyester, polyether, polyimide, polyurethane, epoxy resin, polysulfone, polyethersulfone, polyetherimide, and polyamide, comprising a halogenide and/or nitrate of a metal selected from the group consisting of Na, Mg, Al, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ca, Zn, and combinations thereof such as FeCl 3 , FeCl 2 , TiCl 3 , CaCl 2 , CuCl 2 , CrCl 3 , ZnCl 2 , MgCl 2 , MnCl 2 , and Cr(NO 3 ) 3 ; and a related method for etching.
1. A method for etching a non-conductive surface of a substrate, the method comprising:
contacting the non-conductive surface with an etching composition comprising a compound selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Fe, Cu, Ti, Cr, Zn, Mg, Mn, and combinations thereof, and a coordinative fluoride having the general formula M 1 (HF 2 ) wherein M 1 is a counter-cation having a single positive charge.
2. The method of claim 1 wherein the plastic surface is a polyamide surface or an ABS surface.
3. The method of claim 1 wherein said compound is selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Fe and Cu.
4. The method of claim 1 wherein said compound is a ferric chloride.
5. The method of claim 1 wherein said compound is present in a concentration between about 0.5 M and about 10 M.
6. The method of claim 1 wherein said compound is present in a concentration between about 2 M and about 4 M.
7. The method of claim 1 wherein the etching composition further comprises a wetting agent in a concentration between about 0.001 M and about 0.5 M.
8. The method of claim 1 wherein the substrate is a plastic selected from the group consisting of polyester, polyether, polyimide, polyurethane, epoxy resin, polysulfone, polyethersulfone, polyetherimide, and polyamide.
9. The method of claim 1 wherein the etching composition is alcohol-free.
10. The method of claim 1 wherein the etching composition further comprises an acid.
11. The method of claim 10 wherein the acid has a pK S value of less than or equal to about 5.0.
12. The method of claim 10 wherein the acid is present in a concentration between about 0.1 M and about 5 M.
13. The method of claim 10 wherein the acid is present in a concentration between about 0.5 M and about 3.0 M.
14. A method for the metallization of a plastic surface which is a polyamide surface or an ABS surface, the method comprising:
etching the surface by contacting the non-conductive surface with an etching composition comprising a compound selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Na, Mg, Al, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ca, Zn, and combinations thereof;
contacting the etched surface with an activator solution selected from the group consisting of precious metal colloid activator solutions and ionogenic precious metal activator solutions to yield an activated surface;
contacting the activated surface with an accelerator solution; and
metallizing the surface by autocatalytic metallization bath or direct electrolytic metallization to yield a metallized plastic surface.
15. The method of claim 14 wherein said compound is selected from the group consisting of FeCl 3 , FeCl 2 , TiCl 3 , CaCl 2 , CuCl 2 , CrCl 3 , ZnCl 2 , MgCl 2 , MnCl 2 , and Cr(NO 3 ) 3 .
16. The method of claim 14 wherein said compound is selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Fe, Cu, Ti, Cr, Zn, Mg, Mn, and combinations thereof.
17. The method of claim 14 wherein said compound is a ferric chloride.
18. The method of claim 14 wherein said compound is present in a concentration between about 0.5 M and about 10 M.
19. The method of claim 14 wherein the substrate is a plastic selected from the group consisting of polyester, polyether, polyimide, polyurethane, epoxy resin, polysulfone, polyethersulfone, polyetherimide, and polyamide.
20. The method of claim 14 wherein the etching composition further comprises a soluble fluoride in addition to said compound.
21. The method of claim 20 wherein the soluble fluoride is present in a concentration between about 0.15 M and about 3.6 M.
22. The method of claim 20 wherein the soluble fluoride is present in a concentration between about 0.3 M and about 1.8 M.
23. The method of claim 20 wherein the soluble fluoride is a coordination compound having the general formula M 1 (HF 2 ) wherein M 1 is a counter-cation having a single positive charge.
24. The method of claim 23 wherein M 1 is a NH 4 group.
25. A method for etching a non-conductive surface of a substrate, the method comprising:
contacting the non-conductive surface with an alcohol-free etching composition having a pH less than about 3 and comprising:
a compound selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Fe, Cu, Ti, Cr, Zn, Mg, Mn, and combinations thereof,
a coordinative fluoride having the general formula M 1 (HF 2 ) wherein M 1 is a counter-cation having a single positive charge,
a wetting agent, and
an acid.
26. The method of claim 25 wherein said compound is selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Fe and Cu.
27. The method of claim 25 wherein said compound is a ferric chloride.
28. The method of claim 25 wherein said compound is present in a concentration between about 0.5 M and about 10 M.
29. The method of claim 25 wherein said compound is present in a concentration between about 2 M and about 4 M.
30. The method of claim 25 wherein the coordinative fluoride is present in a concentration between about 0.15 M and about 3.6 M.
31. The method of claim 25 wherein the coordinative fluoride is present in a concentration between about 0.3 M and about 1.8 M.
32. The method of claim 25 wherein the acid has a pK S value of less than or equal to about 5.0, and a concentration between about 0.5 M and about 3.0 M.
33. The method of claim 25 wherein the substrate is a plastic selected from the group consisting of polyester, polyether, polyimide, polyurethane, epoxy resin, polysulfone, polyethersulfone, polyetherimide, and polyamide.
34. A method for etching a non-conductive surface of a substrate, the method comprising:
contacting the non-conductive surface with an alcohol-free etching composition having a pH less than about 3 and comprising:
a compound selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of FeCl 3 , FeCl 2 , TiCl 3 , CaCl 2 , CuCl 2 , CrCl 3 , ZnCl 2 , MgCl 2 , MnCl 2 , and Cr(NO 3 ) 3 ; and
a coordinative fluoride having the general formula M 1 (HF 2 ) wherein M 1 is a counter-cation having a single positive charge,
a wetting agent, and
an acid.
35. The method of claim 34 wherein said compound is selected from the group consisting of halogenides and nitrate salts of a metal selected from the group consisting of Fe and Cu.
36. The method of claim 34 wherein said compound is a ferric chloride.
37. The method of claim 34 wherein said compound is present in a concentration between about 0.5 M and about 10 M.
38. The method of claim 34 wherein said compound is present in a concentration between about 2 M and about 4 M.
39. The method of claim 34 wherein the coordinative fluoride is present in a concentration between about 0.15 M and about 3.6 M.
40. The method of claim 34 wherein the coordinative fluoride is present in a concentration between about 0.3 M and about 1.8 M.
41. The method of claim 34 wherein the acid has a pK S value of less than or equal to about 5.0, and a concentration between about 0.1 M and about 5 M.
42. The method of claim 34 wherein the substrate is a plastic selected from the group consisting of polyester, polyether, polyimide, polyurethane, epoxy resin, polysulfone, polyethersulfone, polyetherimide, and polyamide.