Selective catalytic activation of non-conductive substrates

• US 20050241949A1
• Filed: 04/30/2004
• Published: 11/03/2005
• Est. Priority Date: 04/30/2004
• Status: Active Grant

• Current Assignee: Macdermid Acumen Incorporated (Element Solutions Inc)
• Original Assignee: Macdermid Incorporated (Element Solutions Inc)
• Inventors: Crouse, Kenneth
• Granted Patent: US 7,255,782 B2
• Time in Patent Office: Days
• US Class Current: 205/118
• CPC Class Codes: C23C 18/1608 from pretreatment step, i.e. selective pre-treatment
• CPC Class Codes: C23C 18/1653 Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• CPC Class Codes: C23C 18/1658 with two steps starting with metal deposition followed by addition of reducing agent
• CPC Class Codes: C23C 18/208 with use of metal first
• CPC Class Codes: C23C 18/30 Activating or accelerating or sensitising with palladium or other noble metal
• CPC Class Codes: H05K 2203/0709 Catalytic ink or adhesive for electroless plating catalyst filler H05K2201/0236
• CPC Class Codes: H05K 2203/1157 Using means for chemical reduction
• CPC Class Codes: H05K 3/182 characterised by the patterning method

Abstract

A process of providing a pattern of a metal on a non-conductive substrate to create loop antennae for wireless articles and for creating circuitry for smart cards, such as phone cards is provided. The method comprises the steps of catalyzing the non-conductive substrate by applying a catalytic ink, reducing a source of catalytic metal ions in the catalytic ink to its associated metal, depositing electroless metal on the pattern of catalytic ink on the surface of the substrate; and plating electrolytic metal on the electroless metal layer to produce the desired pattern of metal on the non-conductive substrate. The catalytic ink typically comprises one or more solvents, a source of catalytic metal ions, a crosslinking agent, one or more copolymers, a polyurethane polymer, and, optionally, one or more fillers.

Claims

1. A method of providing a pattern of a metal on a non-conductive substrate, the method comprising the steps of:

a) applying a catalytic ink in a desired pattern on a surface of the non-conductive substrate, wherein the catalytic ink comprises;

i) a solvent;

ii) a source of catalytic metal ions;

iii) a crosslinking agent;

iv) a copolymer; and

v) a polyurethane polymer;

b) reducing the source of catalytic metal ions to its associated metal with a suitable reducing agent;

c) depositing electroless metal on the pattern of catalytic ink; and

d) plating electrolytic metal on top of the electroless metal layer to a desired thickness to produce the pattern of metal on the non-conductive substrate.

2. The method according to claim 1, wherein the catalytic ink is applied by screen printing, gravure, lithography or flexography.

3. The method according to claim 1, wherein the solvent is selected from the group consisting of aromatic and aliphatic hydrocarbons, glycerol, ketones, esters, glycol ethers, and esters of glycol ethers.

4. The method according to claim 3, wherein the solvent is selected from the group consisting of toluene, xylene, glycerol, methyl ethyl ketone, cyclohexanone, butyl acetate, dioctyl phthalate, butyl glycolate, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol acetate, propylene glycol monomethyl ether-acetate, acetone, isophorone, methyl propyl ketone, methyl amyl ketone, diacetone-alcohol, and combinations of the foregoing.

5. The method according to claim 4, wherein the solvent is cyclohexanone.

6. The method according to claim 1, wherein the catalytic metal ions are selected from the group consisting of palladium, gold, silver, platinum, copper, and combinations of the foregoing.

7. The method according to claim 6, wherein the catalytic metal ions comprise palladium.

8. The method according to claim 7, wherein the source of palladium is selected from the group consisting of palladium dichloride and palladium acetate.

9. The method according to claim 8, wherein the source of palladium is a solution of about 10% to about 20% palladium dichloride in water with hydrochloric acid.

10. The method according to claim 8, wherein the source of palladium is a solution of about 0.1% to about 2% palladium acetate in cyclohexanone.

11. The method according to claim 1, wherein the crosslinking agent is a polyisocyanate.

12. The method according to claim 1, wherein the copolymer comprises vinyl chloride and hydroxylpropyl acrylate.

13. The method according to claim 1, wherein the catalytic ink comprises one or more fillers selected from the group consisting of talc, oxides of manganese, titanium, magnesium, aluminum, bismuth, copper, nickel, tin, zinc, and silicon, silicates, bentonites, chalk, carbon black, and combinations of the foregoing.

14. The method according to claim 13, wherein the one or more fillers comprise talc and fumed silica.

15. The method according to claim 1, wherein the non-conductive substrate is selected from the group consisting of polyimides, polyethylene terephthalate, polyesters, acrylonitrile-butadiene-styrene, polyvinylidine chloride, paper and polycarbonates.

16. The method according to claim 15, wherein the non-conductive substrate is polyethylene terephthalate.

17. The method according to claim 1, wherein the source of catalytic metal ions is reduced to its associated metal with a reducing agent selected from the group consisting of sodium borohydride, hydrazine, hydrazine hydrate, hydrazine sulfate, and dihydrazine sulfate.

18. The method according to claim 17, wherein the reducing agent is sodium borohydride.

19. The method according to claim 1, wherein the electroless metal is selected from the group consisting of electroless copper, electroless nickel, and combinations thereof.

20. The method according to claim 1, wherein the electrolytic metal is plated using an acid copper plating bath.

21. A copper radio frequency identification antenna made by the process of claim 1.

22. A method of providing a pattern of a metal on a non-conductive substrate, the method comprising the steps of:

a) applying a catalytic ink in a solid pattern with an outline of the desired pattern on a surface of the non-conductive substrate, wherein the catalytic ink comprises;

i) one or more solvents;

ii) a source of catalytic metal ions;

iii) a polyisocyanate;

iv) a copolymer, wherein the copolymer is capable of crosslinking with the polyisocyanate; and

v) a polyurethane polymer;

b) reducing the source of catalytic metal ions to its associated metal with a suitable reducing agent;

c) depositing electroless metal on the pattern of catalytic ink on the surface of the substrate;

d) plating electrolytic metal on the electroless metal layer to a desired thickness to produce the desired pattern of metal on the non-conductive substrate

e) printing a UV etch resist with the desired pattern; and

f) etching away the plated metal between the resist to define the desired circuit.

23. The method according to claim 22, wherein the catalytic ink is applied by screen printing, gravure, lithography, or flexography.

24. The method according to claim 22, wherein the solvent is selected from the group consisting of aromatic and aliphatic hydrocarbons, glycerol, ketones, esters, glycol ethers, and esters of glycol ethers.

25. The method according to claim 24, wherein the solvent is selected from the group consisting of toluene, xylene, glycerol, methyl ethyl ketone, cyclohexanone, butyl acetate, dioctyl phthalate, butyl glycolate, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol acetate, propylene glycol monomethyl ether-acetate, acetone, isophorone, methyl propyl ketone, methyl amyl ketone, diacetone-alcohol and combinations of the foregoing.

26. The method according to claim 25, wherein the solvent is cyclohexanone.

27. The method according to claim 22, wherein the catalytic metal ions are selected from the group consisting of palladium, gold, silver, platinum, copper, and combinations of the foregoing.

28. The method according to claim 27, wherein the catalytic metal ions comprise palladium.

29. The method according to claim 28, wherein the source of palladium is selected from the group consisting of palladium dichloride and palladium acetate.

30. The method according to claim 29, wherein the source of palladium is a solution of about 10% to about 20% palladium dichloride in water with hydrochloric acid.

31. The method according to claim 29, wherein the source of palladium is a solution of about 0.1% to about 2% palladium acetate in cyclohexanone.

32. The method according to claim 22, wherein the crosslinking agent is a polyisocyanate.

33. The method according to claim 22, wherein the copolymer comprises vinyl chloride and hydroxylpropyl acrylate.

34. The method according to claim 22, wherein the catalytic ink comprises one or more fillers selected from the group consisting of talc, oxides of manganese, titanium, magnesium, aluminum, bismuth, copper, nickel, tin, zinc, and silicon, silicates, bentonites, chalk, carbon black, and combinations of the foregoing.

35. The method according to claim 34, wherein the one or more fillers comprise talc and fumed silica.

36. The method according to claim 22, wherein the non-conductive substrate is selected from the group consisting of polyimides, polyethylene terephthalate, polyesters, acrylonitrile-butadiene-styrene, polyvinylidine chloride, and polycarbonates.

37. The method according to claim 36, wherein the non-conductive substrate is polyethylene terephthalate.

38. The method according to claim 22, wherein the source of catalytic metal ions is reduced to its associated metal with a reducing agent selected from the group consisting of sodium borohydride, hydrazine, hydrazine hydrate, hydrazine sulfate, and dihydrazine sulfate.

39. The method according to claim 38, wherein the reducing agent is sodium borohydride.

40. The method according to claim 22, wherein the electroless metal is selected from the group consisting of electroless copper, electroless nickel, and combinations thereof.

41. The method according to claim 22, wherein the electrolytic metal is plated using an acid copper plating bath.

42. A copper radio frequency identification antenna made by the process of claim 22.

43. A method of providing a desired pattern of metal on a non-conductive substrate comprising the steps of:

a) applying a catalytic ink on a surface of the non-conductive substrate, wherein the catalytic ink comprises;

i) a solvent;

ii) a source of catalytic metal ions;

iii) a crosslinking agent;

iv) a copolymer; and

v) a polyurethane polymer;

b) reducing the source of catalytic metal ions to its associated metal using a suitable reducing agent;

c) printing resist in a desired pattern on the catalytic ink on the non-conductive substrate;

d) depositing electroless metal on the non-conductive substrate in the areas not covered by the printed resist on the catalytic ink; and

e) plating electrolytic metal on top of the electroless metal deposit.

44. The method according to claim 43, wherein the catalytic ink is applied by screen printing, gravure, lithography, or flexography.

45. The method according to claim 43, wherein the solvent is selected from the group consisting of aromatic and aliphatic hydrocarbons, glycerol, ketones, esters, glycol ethers, and esters of glycol ethers.

46. The method according to claim 45, wherein the solvent is selected from the group consisting of toluene, xylene, glycerol, methyl ethyl ketone, cyclohexanone, butyl acetate, dioctyl phthalate, butyl glycolate, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol acetate, propylene glycol monomethyl ether-acetate, acetone, isophorone, methyl propyl ketone, methyl amyl ketone, diacetone-alcohol and combinations of the foregoing.

47. The method according to claim 46, wherein the solvent is cyclohexanone.

48. The method according to claim 43, wherein the catalytic metal ions are selected from the group consisting of palladium, gold, silver, platinum, copper, and combinations of the foregoing.

49. The method according to claim 48, wherein the catalytic metal ions comprise palladium.

50. The method according to claim 49, wherein the source of palladium is selected from the group consisting of palladium dichloride and palladium acetate.

51. The method according to claim 50, wherein the source of palladium is a solution of about 10% to about 20% palladium dichloride in water with hydrochloric acid.

52. The method according to claim 50, wherein the source of palladium is a solution of about 0.1% to about 2% palladium acetate in cyclohexanone.

53. The method according to claim 43, wherein the crosslinking agent is a polyisocyanate.

54. The method according to claim 43, wherein the copolymer comprises vinyl chloride and hydroxylpropyl acrylate.

55. The method according to claim 43, wherein the catalytic ink comprises one or more fillers selected from the group consisting of talc, oxides of manganese, titanium, magnesium, aluminum, bismuth, copper, nickel, tin, zinc, and silicon, silicates, bentonites, chalk, carbon black, and combinations of the foregoing.

56. The method according to claim 55, wherein the one or more fillers comprise talc and fumed silica.

57. The method according to claim 43, wherein the non-conductive substrate is selected from the group consisting of polyimides, polyethylene terephthalate, polyesters, acrylonitrile-butadiene-styrene, polyvinylidine chloride, and polycarbonates.

58. The method according to claim 57, wherein the non-conductive substrate is polyethylene terephthalate.

59. The method according to claim 43, wherein the source of catalytic metal ions is reduced to its associated metal with a reducing agent selected from the group consisting of sodium borohydride, hydrazine, hydrazine hydrate, hydrazine sulfate, and dihydrazine sulfate.

60. The method according to claim 59, wherein the reducing agent is sodium borohydride.

61. The method according to claim 43, wherein the electroless metal is selected from the group consisting of electroless copper, electroless nickel, and combinations thereof.

62. The method according to claim 43, wherein the electrolytic metal is plated using an acid copper plating bath.

63. A phone card made by the process of claim 43.