Selective catalytic activation of polymeric films

• US 4,910,072 A
• Filed: 03/07/1989
• Issued: 03/20/1990
• Est. Priority Date: 11/07/1986
• Status: Expired due to Term

• Current Assignee: Laird Technologies Incorporated (DuPont de Nemours, Inc.)
• Original Assignee: Monsanto Company (Bayer AG)
• Inventors: Morgan, Albert W., Brozek, James P., O'Connor, Michael T. Jr., Capistran, James D.
• Primary Examiner(s): Dees, Jose G.
• Assistant Examiner(s): RYAN, PATRICK J
• Application Number:
  US07/320,914
• Time in Patent Office: 378 Days
• Field of Search: 428/195, 428/209, 428/212, 428/409, 428/522, 428/901, 430/311, 430/319, 106/1.05, 106/1.11, 106/1.13, 106/1.15, 427/53.1, 427/96, 525/370
• US Class Current: 428/212
• CPC Class Codes: C23C 18/1612 through irradiation means
• CPC Class Codes: C23C 18/1641 Organic substrates, e.g. resin, plastic
• CPC Class Codes: C23C 18/1879 Use of metal, e.g. activation, sensitisation with noble metals
• CPC Class Codes: C23C 18/1882 Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
• CPC Class Codes: C23C 18/2033 Heat
• CPC Class Codes: C23C 18/204 Radiation, e.g. UV, laser
• CPC Class Codes: C23C 18/405 Formaldehyde
• CPC Class Codes: H05K 3/185 by making a catalytic pattern by photo-imaging
• CPC Class Codes: Y10S 428/901 Printed circuit
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/24851 Intermediate layer is discontinuous or differential
• CPC Class Codes: Y10T 428/24868 Translucent outer layer
• CPC Class Codes: Y10T 428/24917 including metal layer
• CPC Class Codes: Y10T 428/24942 including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/31 Surface property or characteristic of web, sheet or block
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

Catalytically inert films comprising complexes of polymer with a compound of a Group 1B or Group 8 metal at unusually low proportions of metal can be selectively activated, e.g. to provide a catalytic surface. Such films can be advantageously activatable to electroless deposition, e.g. of oxidation resistant layers of copper.

Claims

1. A film having a catalytically inert surface wherein at least one portion of a surface of said film comprises a polymeric phase consisting essentially of polyvinyl chloride complexed with at least one compound of a Group 1B or Group 8 metal in a molar ratio of vinyl chloride units to atoms of said metal of at least about 20 to 1, wherein said portion can be activated to electroless deposition by exposure to radiant energy or light.

2. A film according to claim 1 wherein said metal comprises palladium, platinum, iridium, rhodium, osmium, ruthenium, gold or silver.

3. An activatable film comprising a complex of at least one polymer with at least one compound of a Group 1B or Group 8 metal, wherein said film is catalytically inert and the concentration of metal is less than 0.1 atom percent of said metal at the film surface and higher in the interior of said film and said film is activatable to electroless deposition by exposure for up to 24 hours to UV radiation at about 7.5 milliwatts/square centimeter from a 254 nanometer wavelength mercury arc lamp at about 25 millimeters from said film surface or by exposure to heat in a 180°

C. oven for up to 5 minutes.

4. A film according to claim 3 wherein said polymer is unsaturated.

5. A film according to claim 4 wherein said polymer is polybutadiene or polychloroprene.

6. A film according to claim 5 wherein said polymer consists essentially of polychloroprene, said metal consists essentially of palladium and said polymer and metal are present in a molar ratio of chloroprene monomer units to atoms of said metal of at least about 28 to 1.

7. A film according to claim 5 wherein said polymer consists essentially of polybutadiene, said metal consists essentially of palladium and said polymer and metal are present in a molar ratio of butadiene monomer units to atoms of said metal of at least about 35 to 1.

8. A film according to claim 3 wherein said polymer is saturated and halogenated.

9. A film according to claim 8 wherein said polymer is a polyvinyl halide and said metal is palladium, platinum, iridium, ruthenium, rhodium, osmium, gold or silver and said polymer and metal are present in a molar ratio of vinyl halide monomer units to atoms of said metal of greater than about 15 to 1.

11. A film according to claim 3 wherein said metal is palladium, platinium, iridium, rhodium, osmium or ruthenium.

12. A film according to claim 11 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

13. A film according to claim 12 wherein said exposure will catalyze the electroless deposition of oxidation resistant copper from an agitated electroless deposition solution which comprises about 3 grams/liter formalin, about 2.5 grams/liter copper, and about 22 grams/liter ethylenediaminetetraacetic acid and which is maintained at pH 11.5-12.5 and 38°

C.

14. A film according to claim 13 wherein said metal is palladium.

15. A film according to claim 14 wherein said polymer is a vinyl polymer.

16. A film according to claim 15 wherein said polymer and metal are preset in a molar ratio of monomer units of said polymer to atoms of said metal of greater than about 15 to 1.

17. A film according to claim 3 wherein said metal is gold or silver.

18. A film according to claim 17 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

19. A film according to claim 18 wherein said exposure will catalyze the electroless deposition of oxidation resistant copper from an agitated electroless deposition solution with comprises about 3 grams/liter formalin, about 2.5 grams/liter copper, and about 22 grams/liter ethylenediaminetetraacetic acid and which is maintained at pH 11.5-12.5 and 38°

C.

20. A film according to claim 3 wherein said exposure will catalyze the electroless deposition of oxidation resistant copper from an agitated electroless deposition solution with comprises about 3 grams/liter formalin, about 2.5 grams/liter copper, and about 22 grams/liter ethylenediaminetetraacetic acid and which is maintained at pH 11.5-12.5 and 38°

C.

21. A film according to claim 20 wherein said exposure will catalyze said electroless deposition when said film is immersed for up to 5 minutes in said solution.

22. A film according to claim 21 wherein said metal is palladium, platinum, iridium, rhodium, osmium or ruthenium.

23. A film according to claim 22 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

24. A film according to claim 23 wherein said metal comprises palladium.

25. A film according to claim 21 wherein said metal is gold or silver.

26. A film according to claim 25 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

27. A film according to claim 3 wherein said polymer is a vinyl polymer.

28. A film according to claim 27 wherein said metal is palladium, platinum, iridium, rhdium, osmium or ruthenium.

29. A film according to claim 27 wherein said metal is gold or silver.

30. A film according to claim 4 wherein said metal is palladium platinum, iridium, rhodium, osmium or ruthenium.

31. A film according to claim 4 wherein said metal is gold or silver.

32. A film according to claim 8 wherein said metal is palladium, platinum, iridium, rhodium, osmium or ruthenium.

33. A film according to claim 8 wherein said metal is gold or silver.

41. An article consisting of a film according to claim 3 supported on a substrate.

42. A article according to claim 41 wherein said metal is palladium, platinium, iridium, rhodium, osmium or ruthenium.

43. An article according to claim 42 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

44. An article according to claim 43 wherein said exposure will catalyze the electroless deposition of oxidation resistant copper from an agitated electroless deposition solution which comprises about 3 grams/liter formalin, about 2.5 grams/liter copper, and about 22 grams/liter ethylenediaminetetraacetic acid and which is maintained at pH 11.5-12.5 and 38°

C.

45. An article according to claim 41 wherein said metal is gold or silver.

46. An article according to claim 45 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

47. An article according to claim 46 wherein said exposure will catalyze the electroless deposition of oxidation resistant copper from an agitated electroless deposition solution which comprises about 3 grams/liter formalin, about 2.5 grams/liter copper, and about 22 grams/liter ethylenediaminetetraacetic acid and which is maintained at pH 11.5-12.5 and 38°

C.

10. A film having at least one portion of its surface selectively activated to electroless deposition wherein said surface comprises a polymeric phase consisting essentially of a polymer complexed with at least one compound of a Group 1B or Group 8 metal wherein the molar ratio of the number of monomer units of said polymer to the number of atoms of said metal is at least b 15:

1.

34. A film according to claim 10 wherein said polymeric phase is activated to electroless deposition by exposure for up to 24 hours to UV radiation at about 7.5 milliwatts/square centimeter from a 254 nanometer wavelength mercury arc lamp at about 25 millimeters from said film surface or by exposure to heat in a 180°

C. oven for up to 5 minutes.

35. A film according to claim 34 having at least one other portion of its surface catalytically inert and activatable to electroless deposition by exposure to radiant energy or heat.

36. A film according to claim 10 wherein said metal is palladium, iridium, rhodium, osmium or ruthenium.

37. A film according to claim 10 wherein said metal is gold or silver.

38. A film according to claim 10 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

39. A film according to claim 38 wherein said metal is palladium.

40. A film according to claim 39 wherein said polymer is a vinyl polymer.

48. An article consisting of a film according to claim 10 supported on a substrate.

49. An article according to claim 48 wherein said polymeric phase is activated to electroless deposition by exposure for up to 24 hours to UV radiation at about 7.5 milliwatts/square centimeter from a 254 nanometer wavelength mercury arc lamp at about 25 millimeters from said film surface or by exposure to heat in a 180°

C. oven for up to 5 minutes.

50. A film according to claim 49 having at least one other portion of its surface catalytically inert and activatable to electroless deposition by exposure to radiant energy or heat.

51. An article according to claim 50 wherein said polymer is a saturated and halogenated polymer, an unsaturated polymer or a vinyl polymer.

52. An article according to claim 51 wherein said metal is palladium, platinium, iridium, rhodium, osmium or ruthenium.

53. An article according to claim 51 wherein said metal is gold or silver.