Method of forming antireflective coatings

• US 6,632,535 B1
• Filed: 06/08/2000
• Issued: 10/14/2003
• Est. Priority Date: 06/08/2000
• Status: Expired due to Term

• Current Assignee: Vision Dynamics LLC (New England Low Vision & Blindness)
• Original Assignee: Q2100, Inc.
• Inventors: Sun, Xiaodong, Buazza, Omar M.
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Keehan, Christopher M
• Application Number:
  US09/590,784
• Time in Patent Office: 1,223 Days
• Field of Search: 427/508, 427/512, 427/515, 427/558, 427/165, 427/169, 427/190, 427/204, 427/205, 427/387, 427/338.5, 427/389.7, 428/421, 428/447, 428/448, 428/688, 428/323
• US Class Current: 428/447
• CPC Class Codes: B29D 11/00442 Curing the lens material
• CPC Class Codes: B29D 11/0073 Optical laminates
• CPC Class Codes: B29D 11/00865 Applying coatings; tinting; colouring printing, marking or copying processes B41M; identification in general G09F3/00; producing decorative effects in general B44C; positioning or marking of lenses B24B13/0055
• CPC Class Codes: B29K 2995/003 Reflective
• CPC Class Codes: G02B 1/111 using layers comprising organic materials
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An antireflective coating may be formed on visible light transmitting materials. The antireflective coating may a stack of two coating layers. The first coating layer may be formed from a composition that includes a metal alkoxide. The first coating layer may be cured by the application of ultraviolet light or heat. The second coating layer may be formed from a second composition that includes an initiator and an ethylenically substituted monomer. The second composition may be cured by the application of ultraviolet light. The antireflective coatings may be applied to a plastic lens or a plastic lens mold.

Claims

1. A method for forming an at least partially antireflective coating on a visible light-transmitting substrate, comprising:

applying a first composition to at least one surface of the visible light-transmitting substrate to form a first coating layer, the first composition comprising a first metal alkoxide;

applying a second composition to the first coating layer, the second composition comprising, an ethylenically substituted monomer and a second metal alkoxide, wherein the second composition is curable by the application of ultraviolet light; and

directing ultraviolet light toward the second composition, wherein the ultraviolet light initiates curing of the second composition to form a second coating layer.

2. The method of claim 1, wherein the first composition is curable by the application of ultraviolet light.

3. The method of claim 1, further comprising directing ultraviolet light toward the first composition, wherein the ultraviolet light initiates curing of the first composition to form the first coating layer.

4. The method of claim 1, further comprising heating the first composition, wherein heating the first composition initiates curing of the first composition to form the first coating layer.

5. The method of claim 1, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the visible light-transmitting substrate.

6. The method of claim 1, wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

7. The method of claim 1, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the visible light-transmitting substrate, and wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

8. The method of claim 1, wherein the first and second metal alkoxides have the general formula M (Y)_p wherein M is titanium, aluminum, zirconium, boron, tin, indium, antimony, or zinc, Y is a C₁-C₁₀ alkoxy or acetylacetonate, and p is an integer equivalent to the valence of M.

9. The method of claim 1, wherein the first and second metal alkoxides have the general formula Ti(OR)₄, where R is a C₁-C₁₀ alkyl.

10. The method of claim 1, wherein the first and second metal alkoxides are titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, or titanium allylacetoacetate triisopropoxide.

11. The method of claim 1, wherein the first composition further comprises a photoinitiator.

12. The method of claim 1, wherein the first composition further comprises colloidal silica.

13. The method of claim 1, wherein the visible light-transmitting substrate is a plastic eyeglass lens.

14. The method of claim 1, wherein the visible light transmitting substrate is a glass lens.

15. The method of claim 1, wherein the first composition further comprises a coinitiator.

16. The method of claim 1, wherein the first composition further comprises an ethylenically substituted monomer.

17. The method of claim 1, wherein the first composition further comprises an organic solvent.

18. The method of claim 1, wherein the second composition further comprises a silane monomer.

19. The method of claim 1, wherein the second composition further comprises a fluoroacrylate.

20. The method of claim 1, wherein the second metal alkoxide is a titanium alkoxide.

21. The method of claim 1, wherein the second metal alkoxide is an aluminum alkoxide.

22. The method of claim 1, wherein the second composition further comprises a photoinitiator.

23. The method of claim 1, wherein the ethylenically substituted monomer comprises dipentaerythritol tetracrylate.

24. The method of claim 1, wherein the second composition further comprises an organic solvent.

25. The method of claim 1, further comprising forming a hardcoat layer on the surface of the visible light-transmitting substrate prior to applying the first composition to the surface of the visible light-transmitting substrate.

26. The method of claim 24, wherein forming a hardcoat layer on the surface of the visible light-transmitting substrate comprises:

applying an ultraviolet light curable hardcoat composition to the surface of the visible light-transmitting substrate; and

directing ultraviolet light toward the hardcoat composition, wherein the ultraviolet light initiates curing of the hardcoat composition to form the hardcoat layer.

27. The method of claim 1, wherein applying the hardcoat composition to the surface of the visible light-transmitting substrate comprises rotating the visible light-transmitting substrate while directing the hardcoat composition toward the visible light-transmitting substrate.

28. The method of claim 1, wherein applying the first composition comprises directing the first composition toward the visible light-transmitting substrate while rotating the visible light-transmitting substrate.

29. The method of claim 1, wherein applying the second composition comprises directing the second composition toward the visible light-transmitting substrate while rotating the visible light-transmitting substrate.

30. The method of claim 1, wherein ultraviolet light is directed toward the second composition for a time of less than about 90 seconds.

31. The method of claim 1, further comprising heating the visible light-transmitting substrate at a temperature of between about 40°

C. and about 140°

C. for a time of less than about 10 minutes.

32. The method of claim 1, wherein applying the first composition to the visible light-transmitting substrate comprises:

applying a first portion of the first composition to the visible light-transmitting substrate;

drying the first portion of the first composition;

applying a second portion of the first composition to the dried first portion; and

drying the second portion of the first composition.

33. The method of claim 1, wherein the ultraviolet light is produced by a germicidal lamp.

34. The method of claim 1, wherein the ultraviolet light is produced by a flash lamp.

35. The method of claim 1, further comprising forming a hardcoat layer upon the surface of the visible light transmitting substrate prior to forming the first coating layer.

36. The method of claim 1, wherein the first composition is applied to a front surface of the visible light-transmitting substrate.

37. The method of claim 1, wherein the first composition is applied to a back surface of the visible light-transmitting substrate.

38. The method of claim 1, wherein the first composition is applied to a front surface and a back surface of the visible light-transmitting substrate.

39. The method of claim 1, wherein a thickness of the first coating layer and the second coating layer, combined, is less than about 500 nm.

40. The method of claim 1, wherein the antireflective coating is formed in less than about 10 min.

41. A plastic eyeglass lens comprising an at least partially antireflective coating, formed by the method, comprising:

applying a first composition to at least one surface of a non-coated plastic eyeglass lens to form a first coating layer, the first composition comprising a first metal alkoxide;

applying a second composition to the first coating layer, the second composition comprising an ethylenically substituted monomer and a second metal alkoxide, wherein the second composition is curable by the application of ultraviolet light; and

directing ultraviolet light toward the second composition, wherein the ultraviolet light initiates curing of the second composition to form a second coating layer.

42. The method of claim 41, wherein the first composition is curable by the application of ultraviolet light.

43. The method of claim 41, further comprising directing ultraviolet light toward the first composition, wherein the ultraviolet light initiates curing of the first composition to form the first coating layer.

44. The method of claim 41, further comprising heating the first composition, wherein heating the first composition initiates curing of the first composition to form the first coating layer.

45. The method of claim 41, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the plastic eyeglass lens.

46. The method of claim 41, wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

47. The method of claim 41, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the plastic eyeglass lens, and wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

48. The method of claim 41, wherein the first and second metal alkoxides have the general formula M(Y)_p wherein M is titanium, aluminum, zirconium, boron, tin, indium, antimony, or zinc, Y is a C₁-C₁₀ alkoxy or acetylacetonate, and p is an integer equivalent to the valence of M.

49. The method of claim 41, wherein the first and second metal alkoxides have the general formula Ti(OR)₄, where R is a C₁-C₁₀ alkyl.

50. The method of claim 41, wherein the first and second metal alkoxides are titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, or titanium allylacetoacetate triisopropoxide.

51. The method of claim 41, wherein the first composition further comprises a photoinitiator.

52. The method of claim 41, wherein the first composition further comprises colloidal silica.

53. The method of claim 41, wherein the first composition further comprises a coinitiator.

54. The method of claim 41, wherein the first composition further comprises an ethylenically substituted monomer.

55. The method of claim 41, wherein the first composition further comprises an organic solvent.

56. The method of claim 41, wherein the second composition further comprises a silane monomer.

57. The method of claim 41, wherein the second composition further comprises a fluoroacrylate.

58. The method of claim 41, wherein the second metal alkoxide is a titanium alkoxide.

59. The method of claim 41, wherein the second metal alkoxide is an aluminum alkoxide.

60. The method of claim 41, wherein the second composition further comprises a photoinitiator.

61. The method of claim 41, wherein the ethylenically substituted monomer comprises dipentaerythritol tetracrylate.

62. The method of claim 41, wherein the second composition further comprises an organic solvent.

63. The method of claim 41, further comprising forming a hardcoat layer on the surface of the plastic eyeglass lens prior to applying the first composition to the surface of the plastic eyeglass lens.

64. The method of claim 63, wherein forming a hardcoat layer on the surface of the plastic eyeglass lens comprises:

applying an ultraviolet light curable hardcoat composition to the surface of the plastic eyeglass lens; and

directing ultraviolet light toward the hardcoat composition, wherein the ultraviolet light initiates curing of the hardcoat composition to form the hardcoat layer.

65. The method of claim 41, wherein applying the hardcoat composition to the surface of the plastic eyeglass lens comprises rotating the plastic eyeglass lens while directing the hardcoat composition toward the plastic eyeglass lens.

66. The method of claim 41, wherein applying the first composition comprises directing the first composition toward the plastic eyeglass lens while rotating the plastic eyeglass lens.

67. The method of claim 41, wherein applying the second composition comprises directing the second composition toward the plastic eyeglass lens while rotating the plastic eyeglass lens.

68. The method of claim 41, wherein ultraviolet light is directed toward the second composition for a time of less than about 90 seconds.

69. The method of claim 41, further comprising heating the plastic eyeglass lens at a temperature of between about 40°

C. and about 140°

C. for a time of less than about 10 minutes.

70. The method of claim 41, wherein applying the first composition to the plastic eyeglass lens substrate comprises:

applying a first portion of the first composition to the plastic eyeglass lens;

drying the first portion of the first composition;

applying a second portion of the first composition to the dried first portion; and

drying the second portion of the first composition.

71. The method of claim 41, wherein the ultraviolet light is produced by a germicidal lamp.

72. The method of claim 41, wherein the ultraviolet light is produced by a flash lamp.

73. The method of claim 41, further comprising forming a hardcoat layer upon the surface of the plastic eyeglass lens prior to forming the first coating layer.

74. The method of claim 41, wherein the first composition is applied to a front surface of the plastic eyeglass lens.

75. The method of claim 41, wherein the first composition is applied to a back surface of the plastic eyeglass lens.

76. The method of claim 41, wherein the first composition is applied to a front surface and a back surface of the plastic eyeglass lens.

77. The method of claim 41, wherein a thickness of the first coating layer and the second coating layer, combined, is less than about 500 nm.

78. The method of claim 41, wherein the antireflective coating is formed in less than about 10 min.

79. A method for forming an at least partially antireflective coating on a lens, comprising:

applying a first composition to at least one surface of the lens to form a first coating layer, the first composition comprising a first metal alkoxide;

applying a silicon containing composition to the first composition to form a silicon layer, the silicon containing composition comprising colloidal silicon or a silane monomer;

applying a second composition to the silicon layer, the second composition comprising an an ethylenically substituted monomer and a second metal alkoxide, wherein the second composition is curable by the application of ultraviolet light; and

directing ultraviolet light toward the second composition, wherein the ultraviolet light initiates curing of the second composition to form a second coating layer.

80. The method of claim 79, wherein the first composition is curable by the application of ultraviolet light.

81. The method of claim 79, further comprising directing ultraviolet light toward the first composition, wherein the ultraviolet light initiates curing of the first composition to form the first coating layer.

82. The method of claim 79, further comprising heating the first composition, wherein heating the first composition initiates curing of the first composition to form the first coating layer.

83. The method of claim 79, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the lens.

84. The method of claim 79, wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

85. The method of claim 79, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the lens, and wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

86. The method of claim 79, wherein the first and second metal alkoxides have the general formula M (Y)_p wherein M is titanium, aluminum, zirconium, boron, tin, indium, antimony, or zinc, Y is a C₁-C₁₀ alkoxy or acetylacetonate, and p is an integer equivalent to the valence of M.

87. The method of claim 79, wherein the first and second metal alkoxides have the general formula Ti(OR)₄, where R is a C₁-C₁₀ alkyl.

88. The method of claim 79, wherein the first and second metal alkoxides are titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, or titanium allylacetoacetate triisopropoxide.

89. The method of claim 79, wherein the first composition further comprises a photoinitiator.

90. The method of claim 79, wherein the lens is a plastic eyeglass lens.

91. The method of claim 79, wherein the lens is a glass lens.

92. The method of claim 79, wherein the first composition further comprises a coinitiator.

93. The method of claim 79, wherein the first composition further comprises an ethylenically substituted monomer.

94. The method of claim 79, wherein the first composition further comprises an organic solvent.

95. The method of claim 79, wherein the second composition further comprises a fluoroacrylate.

96. The method of claim 79, wherein the second metal alkoxide is a titanium alkoxide.

97. The method of claim 79, wherein the second metal alkoxide is an aluminum alkoxide.

98. The method of claim 79, wherein the second composition further comprises a photoinitiator.

99. The method of claim 79, wherein the ethylenically substituted monomer comprises dipentaerythritol tetracrylate.

100. The method of claim 79, wherein the second composition further comprises an organic solvent.

101. The method of claim 79, further comprising forming a hardcoat layer on the surface of the lens prior to applying the first composition to the surface of the lens.

102. The method of claim 100, wherein forming a hardcoat layer on the surface of the lens comprises:

applying an ultraviolet light curable hardcoat composition to the surface of the lens; and

directing ultraviolet light toward the hardcoat composition, wherein the ultraviolet light initiates curing of the hardcoat composition to form the hardcoat layer.

103. The method of claim 79, wherein applying the hardcoat composition to the surface of the lens comprises rotating the lens while directing the hardcoat composition toward the lens.

104. The method of claim 79, wherein applying the first composition comprises directing the first composition toward the lens while rotating the lens.

105. The method of claim 79, wherein applying the second composition comprises directing the second composition toward the lens while rotating the lens.

106. The method of claim 79, wherein ultraviolet light is directed toward the second composition for a time of less than about 90 seconds.

107. The method of claim 79, further comprising heating the lens at a temperature of between about 40°

C. and about 140°

C. for a time of less than about 10 minutes.

108. The method of claim 79, wherein applying the first composition to the lens comprises:

applying a first portion of the first composition to the lens;

drying the first portion of the first composition;

applying a second portion of the first composition to the dried first portion; and

drying the second portion of the first composition.

109. The method of claim 79, wherein the ultraviolet light is produced by a germicidal lamp.

110. The method of claim 79, wherein the ultraviolet light is produced by a flash lamp.

111. The method of claim 79, further comprising forming a hardcoat layer upon the surface of the lens prior to forming the first coating layer.

112. The method of claim 79, wherein the first composition is applied to a front surface of the lens.

113. The method of claim 79, wherein the first composition is applied to a back surface of the lens.

114. The method of claim 79, wherein the first composition is applied to a front surface and a back surface of the lens.

115. The method of claim 79, wherein a thickness of the first coating layer and the second coating layer, combined, is less than about 500 nm.

116. The method of claim 79, wherein the antireflective coating is formed in less than about 10 min.

117. A plastic eyeglass lens comprising an at least partially antireflective coating, formed by the method, comprising:

applying a first composition to at least one surface of a non-coated plastic eyeglass lens to form a first coating layer, the first composition comprising a first metal alkoxide;

applying a silicon containing composition to the first composition to form a silicon layer, the silicon containing composition comprising colloidal silicon or a silane monomer;

applying a second composition to the first coating layer, the second composition comprising an ethylenically substituted monomer and a second metal alkoxide, wherein the second composition is curable by the application of ultraviolet light; and

directing ultraviolet light toward the second composition, wherein the ultraviolet light initiates curing of the second composition to form a second coating layer.

118. The method of claim 117, wherein the first composition is curable by the application of ultraviolet light.

119. The method of claim 117, further comprising directing ultraviolet light toward the first composition, wherein the ultraviolet light initiates curing of the first composition to form the first coating layer.

120. The method of claim 117, further comprising heating the first composition, wherein heating the first composition initiates curing of the first composition to form the first coating layer.

121. The method of claim 117, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the plastic eyeglass lens.

122. The method of claim 117, wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

123. The method of claim 117, wherein the first coating layer has an index of refraction that is greater than an index of refraction of the plastic eyeglass lens, and wherein the second coating layer has an index of refraction that is less than an index of refraction of the first coating layer.

124. The method of claim 117, wherein the first and second metal alkoxides have the general formula M (Y)_p wherein M is titanium, aluminum, zirconium, boron, tin, indium, antimony, or zinc, Y is a C₁-C₁₀ alkoxy or acetylacetonate, and p is an integer equivalent to the valence of M.

125. The method of claim 117, wherein the first and second metal alkoxides have the general formula Ti(OR)₄ where R is a C₁-C₁₀ alkyl.

126. The method of claim 117, wherein the first and second metal alkoxides are titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, or titanium allylacetoacetate triisopropoxide.

127. The method of claim 117, wherein the first composition further comprises a photoinitiator.

128. The method of claim 117, wherein the first composition further comprises a coinitiator.

129. The method of claim 117, wherein the first composition further comprises an ethylenically substituted monomer.

130. The method of claim 117, wherein the first composition further comprises an organic solvent.

131. The method of claim 117, wherein the second composition further comprises a fluoroacrylate.

132. The method of claim 117, wherein the second metal alkoxide is a titanium alkoxide.

133. The method of claim 117, wherein the second metal alkoxide is an aluminum alkoxide.

134. The method of claim 117, wherein the second composition further comprises a photoinitiator.

135. The method of claim 117, wherein the ethylenically substituted monomer comprises dipentaerythritol tetracrylate.

136. The method of claim 117, wherein the second composition further comprises an organic solvent.

137. The method of claim 117, further comprising forming a hardcoat layer on the surface of the lens prior to applying the first composition to the surface of the plastic eyeglass lens.

138. The method of claim 137, wherein forming a hardcoat layer on the surface of the plastic eyeglass lens comprises:

applying an ultraviolet light curable hardcoat composition to the surface of the plastic eyeglass lens; and

directing ultraviolet light toward the hardcoat composition, wherein the ultraviolet light initiates curing of the hardcoat composition to form the hardcoat layer.

139. The method of claim 117, wherein applying the hardcoat composition to the surface of the plastic eyeglass lens comprises rotating the lens while directing the hardcoat composition toward the plastic eyeglass lens.

140. The method of claim 117, wherein applying the first composition comprises directing the first composition toward the plastic eyeglass lens while rotating the plastic eyeglass lens.

141. The method of claim 117, wherein applying the second composition comprises directing the second composition toward the plastic eyeglass lens while rotating the plastic eyeglass lens.

142. The method of claim 117, wherein ultraviolet light is directed toward the second composition for a time of less than about 90 seconds.

143. The method of claim 117, further comprising heating the plastic eyeglass lens at a temperature of between about 40°

C. and about 140°

C. for a time of less than about 10 minutes.

144. The method of claim 117, wherein applying the first composition to the plastic eyeglass lens comprises:

applying a first portion of the first composition to the plastic eyeglass lens;

drying the first portion of the first composition;

applying a second portion of the first composition to the dried first portion; and

drying the second portion of the first composition.

145. The method of claim 117, wherein the ultraviolet light is produced by a germicidal lamp.

146. The method of claim 117, wherein the ultraviolet light is produced by a flash lamp.

147. The method of claim 117, further comprising forming a hardcoat layer upon the surface of the plastic eyeglass lens prior to forming the first coating layer.

148. The method of claim 117, wherein the first composition is applied to a front surface of the plastic eyeglass lens.

149. The method of claim 117, wherein the first composition is applied to a back surface of the plastic eyeglass lens.

150. The method of claim 117, wherein the first composition is applied to a front surface and a back surface of the plastic eyeglass lens.

151. The method of claim 117, wherein a thickness of the first coating layer and the second coating layer, combined, is less than about 500 nm.

152. The method of claim 117, wherein the antireflective coating is formed in less than about 10 min.