Coating compositions having improved adhesion, coated substrates and methods related thereto

• US 20020086168A1
• Filed: 07/31/2001
• Published: 07/04/2002
• Est. Priority Date: 07/30/1999
• Status: Active Grant

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Anderson, Lawrence G., Sadvary, Richard J., Tyebjee, Shiryn
• Granted Patent: US 6,623,791 B2
• Time in Patent Office: Days
• US Class Current: 428/447
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08J 3/20 Compounding polymers with additives, e.g. colouring
• CPC Class Codes: C08K 2201/011 Nanostructured additives
• CPC Class Codes: C08K 3/01 characterized by their specific function
• CPC Class Codes: C08K 3/36 Silica
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 2666/28 Non-macromolecular organic substances
• CPC Class Codes: C08L 2666/54 Inorganic substances
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 7/00 Features of coating compositions, not provided for in group C09D5/00 driers C09F9/00; Processes for incorporating ingredients in coating compositions
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds
• CPC Class Codes: C09D 7/67 Particle size smaller than 100 nm
• CPC Class Codes: C09D 7/68 Particle size between 100-1000 nm
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Coating compositions are provided which include a polysiloxane comprising at least one reactive functional group, at least one material comprising at least one reactive functional group, and at least one boron-containing compound. Also provided are multi-layer composite coatings formed from a basecoat deposited from a pigmented coating composition and a topcoat applied over the basecoat, the topcoat deposited from the aforementioned coating composition. Methods for repairing a multi-layer composite coating and coated substrates are also provided. The compositions of the invention provide highly scratch resistant coatings, particularly highly scratch resistant color-plus-clear coatings, which have excellent intercoat adhesion to subsequently applied coating layers.

Claims

1. A coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof, wherein each component is different.

2. A coating composition according to claim 1, further comprising at least one functional group-containing film-forming polymer.

3. A coating composition according to claim 1, wherein each R², which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

4. A coating composition according to claim 1, wherein the polysiloxane (a) comprises at least two reactive functional groups.

5. A coating composition according to claim 1, wherein at least one R² group represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group.

6. A coating composition according to claim 5, wherein at least one R² group represents a group comprising at least two reactive functional groups selected from a hydroxyl group and a carbamate group.

7. A coating composition according to claim 1, wherein at least one R² group represents a group comprising an oxyalkylene group and at least two hydroxyl groups.

8. A coating composition according to claim 1, wherein the polysiloxane has the following structure (II) or (III):

9. A coating composition according to claim 8, wherein (n +m) ranges from 2 to 9.

10. A coating composition according to claim 9, wherein (n +m) ranges from 2 to 3.

11. A coating composition according to claim 8, wherein (n′

+m′

) ranges from 2 to 9.

12. A coating composition according to claim 11, wherein (n′

+m′

) ranges from 2 to 3.

13. A coating composition according to claim 8, wherein X represents a group which comprises at least one reactive functional group selected from at least one of a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

14. A coating composition according to claim 13, wherein X represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group.

15. A coating composition according to claim 13, wherein X represents a group comprising at least two hydroxyl groups.

16. A coating composition according to claim 1, wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount ranging from 0.01 to 90 weight percent based on total weight of resin solids of the components from which the composition is formed.

17. A coating composition according to claim 16, wherein the at least one polysiloxane (a) is present in an amount of at least 2 weight percent.

18. A coating composition according to claim 16, wherein the at least one polysiloxane (a) is present in an amount of at least 5 weight percent.

19. A coating composition according to claim 16, wherein the at least one polysiloxane (a) is present in an amount of at least 10 weight percent.

20. A coating composition according to claim 16, wherein the at least one polysiloxane (a) is present in an amount of at least 20 weight percent.

21. A coating composition according to claim 2, wherein the at least one reactive functional group-containing film-forming polymer is selected from at least one of polyether polymers, polyester polymers, acrylic polymers, silicon-based polymers, and polyurethane polymers.

22. A coating composition according to claim 2, wherein the film-forming polymer comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

23. A coating composition according to claim 2, wherein the film-forming polymer comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a carbamate group, and an epoxy group.

24. A coating composition according to claim 23, wherein the film-forming polymer comprises a n acrylic polymer having reactive functional groups selected from a hydroxyl group and a carbamate group.

25. A coating composition according to claim 2, wherein the at least one reactive functional group-containing film-forming polymer when added to the other components that form the composition, is present in the composition in an amount ranging from 2 to 80 weight percent based on total weight of resin solids of the components from which the composition is formed.

26. A coating composition according to claim 1, wherein the at least one reactant (b) is selected from at least one curing agent.

27. A coating composition according to claim 26, wherein the at least one curing agent is selected from at least one of an aminoplast resin, a polyisocyanate, a blocked isocyanate, a polyepoxide, a polyacid, and a polyol.

28. A coating composition according to claim 27, wherein the at least one curing agent comprises a polyisocyanate or a blocked isocyanate compound.

29. A coating composition according to claim 27, wherein the at least one curing agent comprises a mixture of a polyisocyanate and an aminoplast resin.

30. A coating composition according to claim 26, wherein the curing agent, when added to the other components that form the composition, is present in an amount ranging from 2 to 65 weight percent based on total weight of resin solids of the components from which the composition is formed.

31. A coating composition according to claim 1, wherein the boron-containing compound (c) is selected from at least one of boric acid, a boric acid ester, and mixtures thereof.

32. A coating composition according to claim 31, wherein the boron-containing compound comprises boric acid.

33. A coating composition according to claim 31, wherein said boron-containing compound comprises a boric acid ester selected from at least one of triisopropyl borate, trimethyl borate, triphenyl borate trimethoxyboroxine, polysiloxane borate, acrylic borate, and mixtures thereof and mixtures thereof.

34. A coating composition according to claim 31, wherein said boron-containing compound comprises a boric acid ester derivative selected from at least one of triethanolamineborate, triethanolamine borate, mannitol borate, n-propranol amine borate, trimetholpropane borate, glycerol borate, and mixtures thereof.

35. A coating composition according to claim 31, wherein the boron-containing compound comprises a reaction product formed from the following reactants:

(A) at least one polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4; and

(B) at least one boron-containing compound selected from at least one of boric acid, boric acid equivalents, and mixtures thereof.

36. A coating composition according to claim 35, wherein the polysiloxane (A) comprises at least two reactive functional groups.

37. A coating composition according to claim 35, wherein at least one R² group represents a group comprising at least one hydroxyl group.

38. A coating composition according to claim 35, wherein at least one R² group represents a group comprising at least two hydroxyl groups.

39. A coating composition according to claim 38, wherein at least one R² group represents a group comprising an oxyalkylene group and at least two hydroxyl groups.

40. A coating composition according to claim 35, wherein the polysiloxane (A) has the following structure (II) or (III):

41. A coating composition according to claim 40, wherein (n+m) ranges from 2 to 9.

42. A coating composition according to claim 41, wherein (n+m) ranges from 2 to 3.

43. A coating composition according to claim 40, wherein (n′

+m′

) ranges from 2 to 9.

44. A coating composition according to claim 43, wherein (n′

+m′

) ranges from 2 to 3.

45. A coating composition according to claim 40, wherein X represents a group which comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

46. A coating composition according to claim 40, wherein X represents a group comprising at least two hydroxyl groups.

47. A coating composition according to claim 1, wherein the at least one boron-containing compound (c), when added to the other components that form the composition, is present in the composition in an amount sufficient to provide an amount of boron ranging from 0.001 to 5 weight percent based on total weight of resin solids of the components from which the composition is formed.

48. A coating composition according to claim 1, wherein the components from which the coating composition is formed further comprise a plurality of particles which are different from components (a), (b) and (c).

49. A coating composition according to claim 48, wherein the plurality of particles are selected from inorganic particles, composite particles, and mixtures thereof.

50. A coating composition according to claim 48, wherein the particles are selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing.

51. A coating composition according to claim 50, wherein the particles comprise colloidal silica.

52. A coating composition according to claim 48, wherein the particles are surface treated.

53. A coating composition according to claim 48, wherein the particles have an average particle size of less than 100 microns prior to incorporation into the composition.

54. A coating composition according to claim 48, wherein the particles have an average particle size ranging from 1 to less than 1000 nanometers prior to incorporation into the composition.

55. A coating composition according to claim 54, wherein the particles have an average particle size ranging from 1 to 100 nanometers prior to incorporation into the composition.

56. A coating composition according to claim 55, wherein the particles have an average particle size ranging from 5 to 50 nanometers prior to incorporation into the composition.

57. A coating composition according to claim 48, wherein the particles, when added to the other components that form the composition, are present in the composition in an amount ranging from 0.01 to 75 weight percent based on total weight of the resin solids of the components from which the composition is formed.

58. A coating composition according to claim 57, wherein the particles are present in an amount of at least 0.1 weight percent.

59. A coating composition according to claim 58, wherein the particles are present in an amount of at least 0.5 weight percent.

60. A coating composition according to claim 58, wherein the particles are present in an amount of less than 20 weight percent.

61. A coating composition according to claim 59, wherein the particles are present in an amount of less than 10 weight percent.

73. A multi-layer composite coating according to claim 1, wherein the at least one polysiloxane (a), when added to the other components that form the composition, is present in the composition in an amount ranging from 0.01 to 90 weight percent based on total weight of resin solids of the components from which the composition is formed.

74. A multi-layer composite coating composition according to claim 2, wherein the at least one reactive functional group-containing film-forming polymer is selected from at least one of polyether polymers, polyester polymers, acrylic polymers, silicon-based polymers, and polyurethane polymers.

75. A multi-layer composite coating composition according to claim 2, wherein the film-forming polymer comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

76. A multi-layer composite coating according to claim 2, wherein the film-forming polymer comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a carbamate group, and an epoxy group.

77. A multi-layer composite coating according to claim 76, wherein the film-forming polymer comprises an acrylic polymer having reactive functional groups selected from a hydroxyl group and a carbamate group.

78. A multi-layer composite coating according to claim 2, wherein the at least one reactive functional group-containing film-forming polymer when added to the other components that form the composition, is present in the composition in an amount ranging from 2 to 80 weight percent based on total weight of resin solids of the components from which the composition is formed.

79. A multi-layer composite coating according to claim 1, wherein the at least one reactant (b) is selected from at least one curing agent.

80. A multi-layer composite coating according to claim 79, wherein the at least one curing agent is selected from at least one of an aminoplast resin, a polyisocyanate, a blocked isocyanate compound, a polyepoxide, a polyacid, and a polyol.

81. A multi-layer composite coating according to claim 80, wherein the at least one curing agent comprises a polyisocyanate and/or blocked isocyanate compound.

82. A multi-layer composite coating according to claim 80, wherein the at least one curing agent comprises a mixture of a polyisocyanate and an aminoplast resin.

83. A multi-layer composite coating according to claim 79, wherein the curing agent, when added to the other components that form the composition, is present in an amount ranging from 2 to 65 weight percent based on total weight of resin solids of the components from which the composition is formed.

84. A multi-layer composite coating according to claim 1, wherein the boron-containing compound (c) is selected from at least one of boric acid, boric acid ester, and mixtures thereof.

85. A multi-layer composite coating according to claim 84, wherein the boron-containing compound comprises boric acid.

86. A multi-layer composite coating according to claim 84, wherein said boron-containing compound comprises a boric acid ester selected from at least one of triisopropyl borate, trimethyl borate, triphenyl borate trimethoxyboroxine, polysiloxane borate, acrylic borate, and mixtures thereof.

87. A multi-layer composite coating according to claim 84, wherein the boron-containing compound comprises a reaction product of the following reactants:

(A) at least one polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4; and

(B) at least one boron-containing compound selected from at least one of boric acid, boric acid equivalents, and mixtures thereof.

88. A multi-layer composite coating according to claim 87, wherein at least one R² represents a group comprising at least one hydroxyl group.

89. A multi-layer composite coating according to claim 87, wherein at least one R² represents a group comprising at least two hydroxyl groups.

90. A multi-layer composite coating according to claim 87, wherein the polysiloxane (A) has the following structure (II) or (III):

91. A multi-layer composite coating according to claim 90, wherein X represents a group which comprises at least one reactive functional group selected from a hydroxyl group, a carboxyl group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

92. A multi-layer composite coating according to claim 90, wherein X represents a group comprising at least two hydroxyl groups.

93. A multi-layer composite coating according to claim 1, wherein the at least one boron-containing compound (c), when added to the other components that form the top coating composition, is present in the top coating composition in an amount sufficient to provide an amount of boron ranging from 0.001 to 5 weight percent based on total weight of resin solids of the components from which the top coating composition is formed.

94. A multi-layer composite coating according to claim 1, wherein the components from which the coating composition is formed further comprise a plurality of particles which are different from components (a), (b) and (c).

95. A multi-layer composite according to claim 94, wherein the plurality of particles are selected from inorganic particles, composite particles, and mixtures thereof.

96. A multi-layer composite coating according to claim 94, wherein the particles are selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing.

97. A multi-layer composite coating according to claim 96, wherein the particles comprise colloidal silica.

98. A multi-layer composite coating according to claim 94, wherein the particles have an average particle size ranging from 1 to less than 1000 nanometers prior to incorporation into the composition.

99. A multi-layer composite coating according to claim 98, wherein the particles have an average particle size ranging from 1 to 100 nanometers prior to incorporation into the composition.

100. A multi-layer composite coating according to claim 94, wherein the particles, when added to the other components that form the composition, are present in the composition in an amount ranging from 0.01 to 75 weight percent based on total weight of the resin solids of the components from which the composition is formed.

101. A multi-layer composite coating according to claim 100, wherein the particles are present in an amount of at least 0.1 weight percent.

102. A multi-layer composite coating according to claim 101, wherein the particles are present in an amount of less than 20 weight percent.

112. A coated substrate comprising a substrate and a cured coating over at least a portion of the substrate, the cured coating formed from the coating composition of claim 1.

113. A coated substrate comprising a substrate and a cured coating over at least a portion of the substrate, the cured coating formed from the coating composition of claim 2.

114. A coated substrate comprising a substrate and a cured multi-layer composite coating over at least a portion of the substrate, the cured multilayer composite coating comprising a base coat over at least a portion of the substrate formed from a film-forming base coating composition and a top coat over at least a portion of the base coat, the top coat formed from the coating composition of claim 1.

62. A coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2<

(m+n)<

4;

(b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;

(c) at least one boron-containing compound selected from boric acid and;

(d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof,

wherein each component is different.

63. A coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof;

(d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof; and

(e) at least one film-forming polymer selected from polyether polymers, polyester polymers, acrylic polymers and polyurethane polymers, said film-forming polymer having functional groups reactive with the functional groups of (a) and/or (b),

wherein each component is different.

64. A coating composition formed from components comprising:

(a) at least one polysiloxane having the following structure (II) or (III);

wherein;

m has a value of at least 1;

m′

ranges from 0 to 75;

n ranges from 0 to 75;

n′

ranges from 0 to 75;

each R, which may be identical or different, is selected from H, OH, monovalent hydrocarbon groups, monovalent siloxane groups, and mixtures of any of the foregoing; and

R^a comprises the following structure (IV);

—

R³—

X 

 

(IV)

wherein —

R³ is selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an alkenylene aryl group; and

X represents a group which comprises at least one reactive functional group selected from a hydroxyl group and a carbamate group.

(b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the at least one functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof;

(d) a plurality of inorganic particles selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing, and mixtures thereof; and

(e) at least one film-forming acrylic polymer having reactive functional groups selected from hydroyxl groups and carbamate groups,

wherein each component is different.

65. A multi-layer composite coating comprising a base coat deposited on a substrate from a film-forming base coating composition and a top coat deposited over at least a portion of the base coat, said top coat formed from a film-forming top coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof,

wherein each component is different.

66. A multi-layer composite coating according to claim 65, wherein the top coating composition further comprises at least one functional group-containing film-forming polymer.

67. A multi-layer composite coating according to claim 65, wherein each R², which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

68. A multi-layer composite coating according to claim 65, wherein at least one R² group represents a group comprising at least two reactive functional groups selected from a hydroxyl group and a carbamate group.

69. A multi-layer composite coating according to claim 66, wherein the polysiloxane (a) has the following structure (II) or (III):

70. A multi-layer composite coating according to claim 69, wherein X represents a group which comprises at least one reactive functional group selected from at least one of a hydroxyl group, a carboxyl group, an isocyanate group, a blocked isocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, a maleimide group, a fumarate group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

71. A multi-layer composite coating according to claim 70, wherein X represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group.

72. A multi-layer composite coating according to claim 70, wherein X represents a group comprising at least two hydroxyl groups.

103. A multi-layer composite coating comprising a base coat deposited on a substrate from a film-forming base coating composition, and a top coat deposited over at least a portion of the base coat, said top coat deposited from a film-forming top coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof; and

(d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof,

wherein each component is different.

104. A multi-layer composite coating comprising a base coat deposited on a substrate from a film-forming base coating composition and a top coat deposited over at least a portion of the base coat, said top coat deposited from a film-forming top coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof;

(d) a plurality of particles selected from inorganic particles, composite particles, and mixtures thereof; and

(e) at least one film-forming polymer selected from polyether polymers, polyester polymers, acrylic polymers silicon-based polymers, and polyurethane polymers, said film-forming polymer having functional groups reactive with the functional groups of (a) and/or (b), wherein each component is different.

105. A multi-layer composite coating comprising a base coat deposited on a substrate from a film-forming base coating composition and a top coat deposited over at least a portion of the base coat, said top coat deposited from a film-forming top coating composition formed from components comprising:

(a) at least one polysiloxane having the following structure (II) or (III);

wherein;

m has a value of at least 1;

m′

ranges from 0 to 75;

n ranges from 0 to 75;

n′

ranges from 0 to 75;

each R, which may be identical or different, is selected from H, OH, monovalent hydrocarbon groups, monovalent siloxane groups, and mixtures of any of the foregoing; and

R^a comprises the following structure (IV);

—

R³—

X 

 

(IV)

wherein —

R³ is selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an alkenylene aryl group; and

X represents a group which comprises at least one reactive functional group selected from a hydroxyl group and a carbamate group. (b) at least one reactant comprising at least one curing agent having at least one functional group reactive with the at least one functional group of the polysiloxane (a), the curing agent selected from at least one of a polyisocyanate, a blocked isocyanate, and an aminoplast resin;

(c) at least one boron-containing compound selected from boric acid, borate acid equivalents, and mixtures thereof;

(d) a plurality of inorganic particles selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing, and mixtures thereof; and

(e) at least one film-forming acrylic polymer having reactive functional groups selected from hydroyxl groups and carbamate groups,

wherein each component is different.

106. A method of repairing a multi-layer composite coating comprising a base coat formed on a substrate from a film-forming base coating composition and a first top coat deposited over at least a portion of the base coat, said first top coat formed from a first film-forming top coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(b) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and

(c) at least one boron-containing compound selected from boric acid, boric acid equivalents, and mixtures thereof,

wherein each component is different, the method comprising;

locating an area of the composite coating which is flawed,

applying a repair top coat film-forming composition to the flawed area after the flawed area has been prepared for repairing,

wherein the repair top coat film-forming composition comprises a film-forming composition which is the same or different from the first top coat film-forming composition.

107. A method according to claim 106, wherein the boron-contaiining compound (c) wherein the boron-containing compound comprises a reaction product formed from the following reactants:

(A) at least one polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4; and

(B) at least one boron-containing compound selected from at least one of boric acid, boric acid equivalents, and mixtures thereof.

108. A method according to claim 106, wherein the first film-forming top coating composition further comprises inorganic particles selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia and mixtures of any of the foregoing, and mixtures thereof.

109. A coating composition formed from components comprising:

(a) at least one polysiloxane comprising at least one reactive functional group, the polysiloxane comprising at least one of the following structural units (I);

R¹_nR²_mSiO_(4-n-m)/2 

 

(I)

wherein each R¹, which may be identical or different, represents H, OH, a monovalent hydrocarbon group or a monovalent siloxane group;

each R², which may be identical or different, represents a group comprising at least one reactive functional group, wherein m and n fulfill the requirements of 0<

n<

4, 0<

m<

4 and 2≦

(m+n)<

4;

(c) at least one reactant comprising at least one functional group that is reactive with the reactive functional group of the polysiloxane (a); and

(c) at least one compound selected from borates, aluminates, titanates, zirconates, silicates, siloxanes, silanes, and mixtures thereof,

wherein each component is different.

110. A coating composition according to claim 109, wherein the compound (c) comprises at least one of a borate and an aluminate.

111. A coating composition according to claim 110, wherein the compound (c) comprises aluminum alkoxide.