Deposition products, composite materials and processes for the production thereof

• US 20040229034A1
• Filed: 04/23/2004
• Published: 11/18/2004
• Est. Priority Date: 05/16/2003
• Status: Active Grant

• Current Assignee: Argent Limited Partnership
• Original Assignee: Exciton Technologies Inc.
• Inventors: Djokic, Stojan
• Granted Patent: US 7,300,673 B2
• Time in Patent Office: Days
• US Class Current: 428/328
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/34 Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• CPC Class Codes: A01N 59/00 Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• CPC Class Codes: A01N 59/02 Sulfur; Selenium; Tellurium; Compounds thereof
• CPC Class Codes: A01N 59/16 Heavy metals; Compounds thereof
• CPC Class Codes: A61L 15/18 containing inorganic materials
• CPC Class Codes: A61L 15/46 Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
• CPC Class Codes: A61L 17/005 containing a biologically active substance, e.g. a medicament or a biocide
• CPC Class Codes: A61L 2300/104 Silver, e.g. silver sulfadiazine
• CPC Class Codes: A61L 2300/404 Biocides, antimicrobial agents, antiseptic agents
• CPC Class Codes: A61L 27/54 Biologically active materials, e.g. therapeutic substances A61L27/227 takes precedence
• CPC Class Codes: A61L 29/16 Biologically active materials, e.g. therapeutic substances A61L29/048 takes precedence
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence
• CPC Class Codes: B05D 1/18 performed by dipping
• CPC Class Codes: B05D 5/00 Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• CPC Class Codes: B05D 7/02 to macromolecular substances, e.g. rubber treatment or coating of shaped articles made of macromolecular substances C08J7/00
• CPC Class Codes: C23C 18/1646 Characteristics of the product obtained
• CPC Class Codes: C23C 18/42 Coating with noble metals
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/2949 Glass, ceramic or metal oxide in coating

Abstract

Methods for the production of deposition products including an oxidized metal species under both acidic and alkaline conditions, methods for the production of composite materials including a substrate and the deposition product, and products in the nature of deposition products and composite materials. The methods are particularly suited for depositing a very thin layer of a deposition product on a substrate and may be used to produce composite materials for use in many applications, including but not limited to electronics, materials engineering and medical applications. In a preferred embodiment, the metal is silver, the substrates are medical devices or components of medical devices and the deposition product includes an antimicrobially active oxidized silver species.

Claims

1. A method for producing a composite material comprising a substrate and a deposition product, wherein the deposition product is comprised of at least one oxidized species of a metal, the method comprising the following steps:

(a) first contacting the substrate with a first basic environment comprising ions of the metal in order to expose the substrate to the ions of the metal; and

(b) second contacting the substrate with a second basic environment in order to produce the composite material.

2. The method as claimed in claim 1 wherein the metal is comprised of silver.

3. The method as claimed in claim 2 wherein the first basic environment is comprised of a first basic solution comprising an amount of a silver diamino complex.

4. The method as claimed in claim 2 wherein the first basic environment is comprised of a first basic solution, wherein the first basic solution results from a mixture of a silver compound and ammonium hydroxide in an aqueous medium.

5. The method as claimed in claim 4 wherein the first basic solution is comprised of an amount of ammonium hydroxide which is selected such that a concentration of ammonium hydroxide in the first basic solution is between about 25 percent and about 35 percent ammonium hydroxide by volume of the first basic solution.

6. The method as claimed in claim 5 wherein the silver compound is selected from the group of silver compounds consisting of silver salts, silver oxides and mixtures thereof.

7. The method as claimed in claim 6 wherein the silver compound is comprised of silver nitrate.

8. The method as claimed in claim 7 wherein the first basic solution is comprised of an amount of silver nitrate which is selected such that a concentration of silver nitrate in the first basic solution is between about 1 gram per liter and about 20 grams per liter.

9. The method as claimed in claim 3 wherein the first basic solution has a pH in the range from about 8 to about 14.

10. The method as claimed in claim 4 wherein the first basic solution has a pH in the range from about 8 to about 14.

11. The method as claimed in claim 3 wherein the second basic environment is comprised of a second basic solution containing an amount of a strong alkali compound.

12. The method as claimed in claim 11 wherein the strong alkali compound is selected from the group of compounds consisting of sodium hydroxide, potassium hydroxide and mixtures thereof.

13. The method as claimed in claim 12 wherein the strong alkali compound is comprised of sodium hydroxide.

14. The method as claimed in claim 13 wherein the second basic solution is comprised of an amount of sodium hydroxide which is selected such that a concentration of sodium hydroxide in the first basic solution is between about 15 grams per liter and about 35 grams per liter.

15. The method as claimed in claim 11 wherein the first contacting step is performed for between about 1 minute and about 10 minutes.

16. The method as claimed in claim 11 wherein the second contacting step is performed for between about 1 minute and about 60 minutes.

17. The method as claimed in claim 11 wherein the second contacting step is performed at a temperature of between about 2 degrees Celsius and about 60 degrees Celsius.

18. The method as claimed in claim 11, further comprising the step of washing the composite material following the second contacting step.

19. The method as claimed in claim 11, further comprising the step, prior to the first contacting step, of etching the substrate by immersing the substrate in an etching solution.

20. The method as claimed in claim 19 wherein the etching solution is comprised of a mixture of an alcohol and an aqueous solution of a hydroxide compound.

21. The method as claimed in claim 20 wherein the hydroxide compound is selected from the group of hydroxide compounds consisting of sodium hydroxide, potassium hydroxide and mixtures thereof.

22. The method as claimed in claim 21 wherein the hydroxide compound is comprised of sodium hydroxide.

23. The method as claimed in claim 20 wherein the etching step is performed for between about 5 minutes and about 20 minutes.

24. The method as claimed in claim 11, further comprising the step of adding an amount of an oxidizing agent to the second basic solution during the second contacting step.

25. The method as claimed in claim 24 wherein the oxidizing agent is selected from the group of oxidizing agents consisting of persulfates, permanganates, peroxides and mixtures thereof.

26. The method as claimed in claim 25 wherein the oxidizing agent is comprised of a persulfate.

27. The method as claimed in claim 26 wherein the persulfate is selected from the group of persulfates consisting of potassium persulfate, sodium persulfate, ammonium persulfate and mixtures thereof.

28. The method as claimed in claim 27 wherein the persulfate is comprised of potassium persulfate.

29. The method as claimed in claim 27 wherein the second basic solution is comprised of an amount of persulfate which is selected such that a concentration of the persulfate in the second basic solution is between about 1 gram per liter and about 25 grams per liter.

30. The method as claimed in claim 11, further comprising the step of adding an amount of a residual silver compound to the second basic solution during the second contacting step.

31. The method as claimed in claim 30 wherein the residual silver compound is comprised of silver nitrate.

32. The method as claimed in claim 31 wherein the second basic solution is comprised of an amount of the residual silver compound which is selected such that a concentration of the residual silver compound in the second basic solution is between about 1 gram per liter and about 5 grams per liter.

33. The method as claimed in claim 11, further comprising the step of agitating the second basic solution during at least a portion of the second contacting step.

34. A method for producing a deposition product, wherein the deposition product is comprised of at least one oxidized species of a metal, the method comprising the following steps:

(a) providing a deposition solution comprising an amount of ions of the metal and an amount of an oxidizing agent; and

(b) producing the deposition product by facilitating a chemical reaction in the deposition solution between the ions of the metal and the oxidizing agent.

35. The method as claimed in claim 34 wherein the metal is comprised of silver and wherein the ions of the metal are comprised of silver ions.

36. The method as claimed in claim 35 wherein the deposition solution is comprised of an aqueous solution of a silver salt.

37. The method as claimed in claim 36 wherein the silver salt is comprised of silver nitrate.

38. The method as claimed in claim 36 wherein the oxidizing agent is selected from the group of oxidizing agents consisting of persulfates, permanganates, peroxides, hypochlorites and mixtures thereof.

39. The method as claimed in claim 38 wherein the oxidizing agent is comprised of a persulfate.

40. The method as claimed in claim 39 wherein the persulfate is selected from the group of persulfates consisting of potassium persulfate, sodium persulfate, ammonium persulfate and mixtures thereof.

41. The method as claimed in claim 40 wherein the persulfate is comprised of potassium persulfate.

42. The method as claimed in claim 39 wherein the amount of the oxidizing agent is selected to be a stoichiometrically appropriate amount relative to the amount of the ions of the metal.

43. The method as claimed in claim 40 wherein the amount of the silver ions is selected so that a concentration of the silver salt in the deposition solution is between about 1 gram per liter and about 20 grams per liter.

44. The method as claimed in claim 43 wherein the amount of the oxidizing agent is selected so that a concentration of the oxidizing agent in the deposition solution is between about 1 gram per liter and about 50 grams per liter.

45. The method as claimed in claim 40, further comprising the step of adding an amount of a source of anions to the deposition solution for combining with the ions of the metal in order to produce the deposition product.

46. The method as claimed in claim 45 wherein the source of anions is comprised of at least one acid.

47. The method as claimed in claim 46 wherein the acid is selected from the group of acids consisting of carbonic acid, nitric acid, perchloric acid, sulfuric acid, acetic acid, fluoroboric acid, citric acid, acetylsalicylic acid and mixtures thereof.

48. The method as claimed in claim 45 wherein the amount of the source of anions is selected to be a stoichiometrically appropriate amount relative to the amount of the ions of the metal.

49. The method as claimed in claim 40 wherein the deposition product producing step is comprised of maintaining the deposition solution at a temperature of between about 2 degrees Celsius and about 60 degrees Celsius.

50. The method as claimed in claim 40 wherein the deposition product producing step is comprised of maintaining the deposition solution at a temperature of between about 2 degrees Celsius and about 40 degrees Celsius.

51. The method as claimed in claim 40 wherein the deposition product producing step is comprised of maintaining the deposition solution at a temperature of between about 10 degrees Celsius and about 25 degrees Celsius.

52. The method as claimed in claim 40 wherein the deposition product producing step is comprised of agitating the deposition solution during at least a portion of the deposition product producing step.

53. The method as claimed in claim 40, further comprising the following steps:

(a) providing a substrate; and

(b) contacting the substrate with the deposition solution during the deposition product producing step, thereby producing a composite material comprising the substrate and the deposition product.

54. The method as claimed in claim 53 wherein the substrate contacting step is performed for at least about 1 minute.

55. The method as claimed in claim 54 wherein the substrate contacting step is performed for between about 1 minute and about 60 minutes.

56. The method as claimed in claim 55 wherein the substrate contacting step is performed for between about 1 minute and about 20 minutes.

57. The method as claimed in claim 56 wherein the substrate contacting step is performed for between about 2 minutes and about 10 minutes.

58. The method as claimed in claim 53, further comprising the step, following the substrate contacting step, of washing the composite material.

59. The method as claimed in claim 53, further comprising the step, prior to the substrate contacting step, of etching the substrate by immersing the substrate in an etching solution.

60. The method as claimed in claim 59 wherein the etching solution is comprised of a mixture of an alcohol and an aqueous solution of a hydroxide compound.

61. The method as claimed in claim 60 wherein the hydroxide compound is selected from the group of hydroxide compounds consisting of sodium hydroxide, potassium hydroxide and mixtures thereof.

62. The method as claimed in claim 60 wherein the hydroxide compound is comprised of sodium hydroxide.

63. The method as claimed in claim 60 wherein the etching step is performed for between about 5 minutes and about 20 minutes.

64. The method as claimed in claim 60, further comprising the step, following the etching step, of washing the substrate to remove residual alkali from the substrate.

65. The method as claimed in claim 53, further comprising the step, following the substrate contacting step, of immersing the composite material in boiling water.

66. The method as claimed in claim 65 wherein the immersing step is performed for at least about 1 minute.

67. The method as claimed in claim 53 wherein the silver salt is comprised of silver nitrate.

68. The method as claimed in claim 67 wherein the persulfate is selected from the group of persulfates consisting of potassium persulfate, ammonium persulfate and mixtures thereof.

69. The method as claimed in claim 68 wherein the substrate is a medical device.

70. The method as claimed in claim 69 wherein the amount of the silver ions is selected so that a concentration of the silver nitrate in the deposition solution is between about 1 gram per liter and about 20 grams per liter.

71. The method as claimed in claim 70 wherein the amount of the oxidizing agent is selected so that a concentration of the oxidizing agent in the deposition solution is between about 1 gram per liter and about 50 grams per liter.

72. The method as claimed in claim 69 wherein the substrate is comprised of a wound dressing.

73. The method as claimed in claim 72 wherein the substrate is comprised of a high density polyethylene material.

74. The method as claimed in claim 73 wherein the substrate is comprised of a skin adhesive layer, wherein the skin adhesive layer is comprised of a cross-linked silicon gel, and wherein the deposition product is deposited on the skin adhesive layer.

75. The method as claimed in claim 74 wherein the skin adhesive layer has adhesive properties and wherein the deposition product does not materially interfere with the adhesive properties of the skin adhesive layer.

76. A medical device comprising a composite material, wherein the composite material is comprised of a substrate and a deposition product and wherein the deposition product is comprised of an antimicrobially active oxidized silver species comprising a silver salt and a silver oxide.

77. The medical device as claimed in claim 76 wherein the oxidized silver species is comprised of a compound having the general formula Ag₇O₈X, where X is an anion.

78. The medical device as claimed in claim 77 wherein the oxidized silver species is further comprised of Ag₂SO₄.

79. The medical device as claimed in claim 77 wherein the oxidized silver species is further comprised of at least one silver oxide selected from the group of silver oxides consisting of monovalent silver oxide, bivalent silver oxide, trivalent silver oxide and mixtures thereof.

80. The medical device as claimed in claim 77 wherein X is derived from an acid.

81. The medical device as claimed in claim 77 wherein the oxidized silver species is comprised of a plurality of valent states of silver.

82. The medical device as claimed in claim 77 wherein X is selected from the group of anions consisting of HCO₃⁻

, CO₃²⁻

, NO₃⁻

, ClO₄⁻

, SO₄²⁻

, F⁻

, and mixtures thereof.

83. The medical device as claimed in claim 82 wherein X is comprised of NO₃⁻

.

84. The medical device as claimed in claim 76 wherein the medical device is comprised of a wound dressing.

85. The medical device as claimed in claim 84 wherein the substrate is comprised of a high density polyethylene material.

86. The medical device as claimed in claim 84 wherein the substrate is comprised of a cross-linked silicon gel.

87. The medical device as claimed in claim 84 wherein the substrate is comprised of a skin adhesive layer, wherein the skin adhesive layer is comprised of a cross-linked silicon gel, and wherein the deposition product is deposited on the skin adhesive layer.

88. The medical device as claimed in claim 87 wherein the oxidized silver species is comprised of a compound having the general formula Ag₇O₈X, where X is an anion.

89. The medical device as claimed in claim 88 wherein the oxidized silver species is further comprised of Ag₂SO₄.

90. The medical device as claimed in claim 88 wherein the oxidized silver species is further comprised of at least one silver oxide selected from the group of silver oxides consisting of monovalent silver oxide, bivalent silver oxide, trivalent silver oxide and mixtures thereof.

91. The medical device as claimed in claim 88 wherein X is derived from an acid.

92. The medical device as claimed in claim 88 wherein the oxidized silver species is comprised of a plurality of valent states of silver.

93. The medical device as claimed in claim 88 wherein X is selected from the group of anions consisting of HCO₃⁻

, CO₃²⁻

, NO₃⁻

, ClO₄⁻

, SO₄²⁻

, F⁻

, and mixtures thereof.

94. The medical device as claimed in claim 93 wherein X is comprised of NO₃⁻

.

95. The medical device as claimed in claim 87 wherein the skin adhesive layer has adhesive properties and wherein the deposition product does not materially interfere with the adhesive properties of the skin adhesive layer.