Silane compositions and methods for bonding rubber to metals

• US 20050079364A1
• Filed: 10/08/2003
• Published: 04/14/2005
• Est. Priority Date: 10/08/2003
• Status: Abandoned Application

• Current Assignee: Aeromet Corporation, University of Cincinnati
• Original Assignee: Aeromet Corporation, University of Cincinnati
• Inventors: Sorenson, Max, van Ooij, William J., Stacy, Matthew B.
• Application Number:
  US10/681,422
• Publication Number:
  US 20050079364A1
• Time in Patent Office: Days
• US Class Current: 428/447
• CPC Class Codes: B60C 2009/0021 Coating rubbers for steel cords
• CPC Class Codes: B60C 9/0007 Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/28 sulfur-containing groups
• CPC Class Codes: C08L 2666/44 Silicon-containing compounds
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: C09J 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C09J 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09J151/08, C09J153/00
• CPC Class Codes: C09J 4/00 Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• CPC Class Codes: D07B 1/0666 the wires being characterised by an anti-corrosive or adhesion promoting coating
• CPC Class Codes: D07B 2201/2012 comprising polymers
• CPC Class Codes: D07B 2205/3017 Silicon carbides
• CPC Class Codes: D07B 2401/2095 Improving filler wetting respectively or filler adhesion
• CPC Class Codes: D07B 2501/2046 Tire cords
• CPC Class Codes: D07B 2801/18 Coating
• CPC Class Codes: Y10T 428/269 including synthetic resin or polymer layer or component
• CPC Class Codes: Y10T 428/2924 Composite
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane

Abstract

Compositions and methods for treating metal substrates and/or bonding metal substrates to polymeric materials, such as rubber, are provided. The compositions include at least one substantially hydrolyzed amino silane and at least one substantially hydrolyzed sulfur-containing silane. Optionally, the compositions include a nano-size particulate material. The compositions provide coatings on metal substrates for protecting the metal from corrosion and for adhering rubber-like polymeric compositions to the metal with polymer-to-metal vulcanization conditions less dependent on the coating thickness, and with use of less coating materials.

Claims

1. A method of treating a metal substrate, the method comprising:

applying a silane solution comprising a substantially hydrolyzed aminosilane and a substantially hydrolyzed sulfur-containing silane to at least a portion of a surface of the metal substrate; and

drying the solution on the metal substrate to form a coating having a thickness in the range from about 0.1 μ

m to about 1 μ

m thereon to treat the metal substrate.

2. The method of claim 1 further comprising, prior to applying the solution:

mixing an amino-silane and a sulfur-containing silane separately with an aqueous-based medium to substantially hydrolyze the amino-silane and the sulfur-containing silane; and

mixing the hydrolyzed amino-silane and the hydrolyzed sulfur-containing silane together to form the solution to be applied to the metal substrate.

3. The method of claim 2 wherein the amino-silane is a compound of the general formula I:

4. The method of claim 2 wherein the amino silane is selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

5. The method of claim 2 wherein the sulfur-containing silane is a compound of the general formula II

6. The method of claim 2 wherein the sulfur-containing silane is selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

7. The method of claim 1 wherein the solution comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane in a range from about 1:

4 to about 4;

1 by volume.

8. The method of claim 1 wherein the solution comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane of about 1:

1 by volume.

9. The method of claim 1 wherein the solution is applied in an amount sufficient to form the coating to a thickness in the range from about 0.2 μ

m to about 0.6 μ

m.

10. The method of claim 1 wherein applying the coating solution to the metal substrate comprises dipping the metal substrate in the solution.

11. The method of claim 1 wherein the solution applied to the metal substrate further comprises a nanosize particulate material.

12. The method of claim 11 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

13. The method of claim 11 wherein the nanosize particulate material has an average particle size of about 0.1 μ

m or less.

14. The method of claim 11 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight of the solution.

15. The method of claim 1 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm of the solution.

16. A method of treating a metal substrate, the method comprising:

mixing an amino-silane and a sulfur-containing silane separately with an aqueous-based medium to substantially hydrolyze the amino-silane and the sulfur-containing silane;

mixing the hydrolyzed amino-silane, the hydrolyzed sulfur-containing silane, and a nanosize particulate material, having an average particle size of about 0.1 μ

m or less, together to form a silane solution comprising a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane in a range from about 1;

4 to about 4;

1 by volume,

applying the solution to at least a portion of a surface of the metal substrate in an amount sufficient to form a coating to a thickness in the range from about 0.1 μ

m to about 1 μ

m; and

drying the solution on the metal substrate to form the coating thereon.

17. The method of claim 16 wherein the amino-silane is a compound of the general formula I

18. The method of claim 16 wherein the amino silane is selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

19. The method of claim 16 wherein the sulfur-containing silane is a compound of the general formula II

20. The method of claim 16 wherein the sulfur-containing silane is selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

21. The method of claim 16 wherein the solution applied to the metal comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane of about 1:

1 by volume.

22. The method of claim 16 wherein the solution is applied in an amount sufficient to form the coating to a thickness in the range from about 0.2 μ

m to about 0.6 μ

m.

23. The method of claim 16 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

24. The method of claim 16 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight of the solution.

25. The method of claim 16 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm of the solution.

26. A method of bonding a polymeric material to a metal substrate, the method comprising:

applying a silane solution comprising a substantially hydrolyzed amino-silane and a substantially hydrolyzed sulfur-containing silane to at least a portion of a surface of the metal substrate;

drying the silane solution on the metal substrate to form a coating having a thickness in the range from about 0.1 μ

m to about 1 μ

m thereon; and

applying an uncured polymeric material onto the surface of the metal substrate having the coating thereon and curing the polymeric material to bond the polymeric material to the coated metal substrate.

27. The method of claim 26 further comprising, prior to applying the solution:

mixing an amino-silane and a sulfur-containing silane separately with an aqueous-based medium to substantially hydrolyze the amino-silane and the sulfur-containing silane; and

mixing the hydrolyzed amino-silane and the hydrolyzed sulfur-containing silane together to form the solution to be applied to the metal substrate.

28. The method of claim 27 wherein the aqueous-based medium comprises water and alcohol.

29. The method of claim 27 wherein the amino-silane is a compound of the general formula I

30. The method of claim 27 wherein the amino silane is selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

31. The method of claim 27 wherein the sulfur-containing silane is a compound of the general formula II

32. The method of claim 27 wherein the sulfur-containing silane is selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

33. The method of claim 26 wherein the solution comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane in a range from about 1:

4 to about 4;

1 by volume.

34. The method of claim 26 wherein the solution comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane of about 1:

1 by volume.

35. The method of claim 26 wherein applying the solution to the metal substrate comprises dipping the metal substrate in the solution.

36. The method of claim 26 wherein the solution applied to the metal substrate further comprises a nanosize particulate material.

37. The method of claim 36 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

38. The method of claim 36 wherein the nanosize particulate material has an average particle size of about 0.1 μ

m or less.

39. The method of claim 36 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight of the solution.

40. The method of claim 36 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm of the solution.

41. The method of claim 26 wherein drying comprises heating the silane solution on the metal substrate to a temperature of at least about 60°

C.

42. The method of claim 26 wherein the coating formed has a thickness in the range from about 0.2 μ

m to about 0.6 μ

m.

43. The method of claim 26 wherein curing comprises applying heat and pressure to the polymeric material and coated metal substrate to form a bond therebetween.

44. The method of claim 26 wherein the polymeric material is rubber.

45. A bonded tire cord prepared by the method of claim 26.

46. A method of bonding a polymeric material to a metal substrate, the method comprising:

mixing an amino-silane and a sulfur-containing silane separately with an aqueous-based medium to substantially hydrolyze the amino-silane and the sulfur-containing silane;

mixing the hydrolyzed amino-silane, the hydrolyzed sulfur-containing silane, and a nanosize particulate material having an average particle size of about 0.1 μ

m or less, together to form a silane solution comprising a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane in a range from about 1;

4 to about 4;

1 by volume,

applying the solution to at least a portion of a surface of the metal substrate in an amount sufficient to form a coating to a thickness in the range from about 0.1 μ

m to about 1 μ

m; and

drying the solution on the metal substrate to form the coating thereon;

applying an uncured polymeric material onto the surface of the metal substrate having the solution applied thereon; and

curing the polymeric material with heat and pressure to bond the polymeric material to the metal substrate.

47. The method of claim 46 wherein the amino-silane is a compound of the general formula I

48. The method of claim 46 wherein the amino silane is selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

49. The method of claim 46 wherein the sulfur-containing silane is a compound of the general formula II

50. The method of claim 46 wherein the sulfur-containing silane is selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

51. The method of claim 46 wherein the solution applied to the metal comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane of about 1:

1 by volume.

52. The method of claim 46 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

53. The method of claim 46 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight of the solution.

54. The method of claim 46 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm of the solution.

55. The method of claim 46 wherein the coating formed has a thickness in the range from about 0.2 μ

m to about 0.6 μ

m.

56. The method of claim 46 wherein the polymeric material is rubber.

57. A bonded tire cord prepared by the method of claim 46.

58. A tire cord comprising rubber, a metal substrate, and an adhesive film therebetween bonding the rubber to the metal substrate, the adhesive film formed from a dried solution comprising a substantially hydrolyzed amino-silane and a substantially hydrolyzed sulfur-containing silane and having a thickness in the range from about 0.1 μ

m to about 1 μ

m.

59. The tire cord of claim 58 wherein the rubber is selected from the group consisting of natural rubber, sulfur-cured rubber, peroxide-cured rubber, EPDM, NBR, SBR, and combinations thereof.

60. The tire cord of claim 58 wherein the substrate comprises a metal selected from the group consisting of zinc, steel, titanium, nickle, copper, tin, aluminum, cobalt, alloys thereof, and combinations thereof,

61. The tire cord of claim 58 wherein the solution comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane of about about 1:

4 to about 4;

1 by volume.

62. The tire cord of claim 58 wherein the solution comprises a ratio of the hydrolyzed amino-silane to the hydrolyzed sulfur-containing silane of about 1:

1 by volume.

63. The tire cord of claim 58 wherein the amino-silane is a substantially hydrolyzed compound of the general formula I

64. The tire cord of claim 58 wherein the amino silane is a substantially hydrolyzed compound selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

65. The tire cord of claim 58 wherein the sulfur-containing silane is a substantially hydrolyzed compound of the general formula II

66. The tire cord of claim 58 wherein the sulfur-containing silane is a substantially hydrolyzed compound selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

67. The tire cord of claim 58 wherein the adhesive film has a thickness in the range from about 0.2 μ

m to about 0.6 μ

m.

68. The tire cord of claim 58 wherein the adhesive film further comprises a nanosize particulate material.

69. The tire cord of claim 68 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

70. The tire cord of claim 68 wherein the nanosize particulate material has an average particle size of about 0.1 μ

m or less.

71. The tire cord of claim 68 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight in the adhesive film.

72. The tire cord of claim 68 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm in the adhesive layer.

73. The tire cord of claim 58 wherein the rubber is substantially free of cobalt particles.

74. An metal treatment composition comprising a substantially hydrolyzed amino-silane, a substantially hydrolyzed sulfur-containing silane, and a nanosize particulate material.

75. The composition of claim 74 wherein the amino-silane is a substantially hydrolyzed compound of the general formula I

76. The composition of claim 74 wherein the amino silane is a substantially hydrolyzed compound selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

77. The composition of claim 74 wherein the sulfur-containing silane is a substantially hydrolyzed compound of the general formula II

78. The composition of claim 74 wherein the sulfur-containing silane is a substantially hydrolyzed compound selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

79. The composition of claim 74 wherein the hydrolyzed amino-silane and the hydrolyzed sulfur-containing silane are in a ratio in the range from about 1:

4 to about 4;

1 by volume.

80. The composition of claim 74 wherein the hydrolyzed amino-silane and the hydrolyzed sulfur-containing silane are in a ratio of about 1:

1 by volume.

81. The composition of claim 74 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

82. The composition of claim 74 wherein the nanosize particulate material has an average particle size of about 0.1 μ

m or less.

83. The composition of claim 74 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight in the composition.

84. The composition of claim 74 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm in the composition.

85. A metal substrate comprising a coating having a thickness in the range from about 0.1 μ

m to about 1 μ

m on at least a portion of the surface thereof, the coating comprising a substantially hydrolyzed amino-silane and a substantially hydrolyzed sulfur-containing silane.

86. The metal substrate of claim 85 wherein the amino-silane is a substantially hydrolyzed compound of the general formula I

87. The metal substrate of claim 85 wherein the amino silane is a substantially hydrolyzed compound selected from the group consisting of bis(trimethoxysilylpropyl)ethylene diamine, bis(trimethoxysilylpropyl) amine, N-methyl-aminopropyltriethoxysilane, and combinations thereof.

88. The metal substrate of claim 85 wherein the sulfur-containing silane is a substantially hydrolyzed compound of the general formula II

89. The metal substrate of claim 85 wherein the sulfur-containing silane is a substantially hydrolyzed compound selected from the group consisting of bis(trimethoxysilylpropyl) disulfide, bis(trimethoxysilylpropyl) tetrasulfide, and a combination thereof.

90. The metal substrate of claim 85 wherein the hydrolyzed amino-silane and the hydrolyzed sulfur-containing silane are in a ratio in the range from about 1:

4 to about 4;

1 by volume.

91. The metal substrate of claim 85 wherein the hydrolyzed amino-silane and the hydrolyzed sulfur-containing silane are in a ratio of about 1:

1 by volume.

92. The metal substrate of claim 85 wherein the coating further comprises a nanosize particulate material.

93. The metal substrate of claim 92 wherein the nanosize particulate material is selected from the group consisting of silica, zinc oxide, and combinations thereof.

94. The metal substrate of claim 92 wherein the nanosize particulate material has an average particle size of about 0.1 μ

m or less.

95. The metal substrate of claim 92 wherein the nanosize particulate material is silica and in a concentration range from about 10 ppm to about 1% by weight in the composition.

96. The metal substrate of claim 92 wherein the nanosize particulate material is silica and in a concentration range from about 50 ppm to about 1000 ppm in the composition.