Abrasion wear resistant polymeric substrate product

• US 5,190,807 A
• Filed: 10/18/1990
• Issued: 03/02/1993
• Est. Priority Date: 10/18/1990
• Status: Expired due to Term

• Current Assignee: Morgan Advanced Ceramics Inc.
• Original Assignee: Diamonex, Inc. (Morgan Advanced Materials PLC)
• Inventors: Finke, Steven J., Kimock, Fred M., Knapp, Bradley J.
• Primary Examiner(s): Robinson, Ellis P.
• Assistant Examiner(s): Turner, Archene A.
• Application Number:
  US07/600,210
• Time in Patent Office: 866 Days
• Field of Search: 428/408, 428/216, 428/336, 428/447, 428/426, 428/428, 428/698, 428/697, 428/701, 428/702, 428/446, 428/913, 428/469, 428/457
• US Class Current: 428/216
• CPC Class Codes: C23C 16/006 characterized by the colour of the layer
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: G02B 1/105 Protective coatings
• CPC Class Codes: G02B 1/111 using layers comprising organic materials
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

A substantially optically transparent coated substrate product with a highly adherent, abrasion-resistant diamond-like hard carbon coating is disclosed. The substrate product is comprised of a polymeric substrate, an adhesion-mediating polysiloxane polymer layer, one or more intermediate layers and an outer layer of diamond-like hard carbon. In another embodiment of the invention a thin metallic interlayer is disposed between a first interlayer layer and subsequent interlayers and/or diamond-like hard carbon. The invention also allows for the production of adherent thin film interference layer coatings (i.e. quarter wavelength stacks and anti-reflection coatings) using diamond-like hard carbon as the high refractive index layer and the interlayer(s) as the low refractive index layer or, alternatively, using diamond-like hard carbon as the low refractive index layer and the interlayer(s) as the high refractive index layer. The invention further discloses a method for fabricating the coated substrate product. The substrate product, exhibiting excellent resistance to abrasion and chemical attack, is particularly useful for commercial plastic articles such as optical lenses and sunglass lenses made of polycarbonate, CR-39®, or acrylic plastics.

Claims

1. A coated substrate product comprised of a substantially optically transparent polymeric substrate and a first composite layer, said first composite layer comprising a substantially optically transparent adhesion-mediating layer at least 3 microns thick bonded to and disposed towards said substrate of a polysiloxane polymer having a high elasticity and capable of forming a strong chemical bond to said polymeric substrate, a chemically vapor deposit first interlayer bonded to and disposed immediately adjacent to said adhesion-mediating layer of a substantially optically transparent material devoid of alkali metal atoms and fluorine, and a chemically vapor deposited first layer of substantially optically transparent diamond-like carbon bonded to and disposed immediately adjacent to said first interlayer and away from said substrate, said first interlayer being capable of forming a strong chemical bond to said adhesion-mediating layer and diamond-like carbon.

2. The product of claim 1 wherein said first diamond-like carbon layer is at least 200 Å

thick.

3. The product of claim 1 wherein said first interlayer comprises a substantially optically transparent material selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, tungsten nitride, molybdenum nitride, hafnium nitride, zirconium nitride, boron nitride, silicon oxide, silicon dioxide, yttrium oxide, germanium oxide, hafnium oxide, tantalum oxide, titanium oxide, zironium oxide, tungsten oxide, molybdenum oxide, boron oxide, silicon carbide, germanium carbide and mixtures thereof.

4. The product of claim 3 wherein said first interlayer is at least 10 Å

thick.

5. The product of claim 1 wherein said first interlayer comprises silicon dioxide at least 200 Å

thick.

6. The product of claim 1 wherein the thickness of at least one of said first interlayer and said first diamond-like carbon layer is selected to minimize the reflection of light at predetermined wavelengths.

7. The product of claim 1 wherein the thickness of at least one of said first interlayer and said first diamond-like carbon layer is selected to maximize the reflection of light at predetermined wavelengths.

8. The product of claim 1 wherein the thickness of said first interlayer and said first diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

9. The product of claim 1 wherein the compressive stress of said first interlayer is less than said first diamond-like carbon layer and greater than said adhesion-mediating layer.

10. The product of claim 1 wherein said first interlayer exhibits a tensile stress and said first diamond-like carbon layer exhibits a compressive stress.

11. The product of claim 1 including at least a second composite layer bonded to and disposed immediately adjacent to said first composite layer, said second composite layer comprising a second interlayer bonded to and disposed immediately adjacent to said first diamond-like carbon layer and away from said substrate and a second diamond-like carbon layer bonded to and disposed immediately adjacent to said second interlayer and away from said substrate.

12. The product of claim 11 wherein said second interlayer comprises a substantially optically transparent material selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, tungsten nitride, molybdenum nitride, hafnium nitride, zirconium nitride, boron nitride, silicon oxide, silicon dioxide, yttrium oxide, germanium oxide, tungsten oxide, molybdenum oxide, boron oxide, hafnium oxide, tantalum oxide, titanium oxide, zirconium oxide, silicon carbide, germanium carbide and mixtures thereof.

13. The product of claim 12 wherein the thickness of said second interlayer is at least 10 Å

thick.

14. The product of claim 11 wherein said second interlayer comprises silicon dioxide at lest 200 Å

thick.

15. The product of claim 11 wherein the thickness of said second diamond-like carbon layer is at least 200 Å

thick.

16. The product of claim 11 wherein the thickness of at least one of said first interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer is selected to minimize the reflection of light at predetermined wavelengths.

17. The product of claim 11 wherein the thickness of at least one of said first interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer is selected to maximize the reflection of light at predetermined wavelengths.

18. The product of claim 11 wherein the thickness of said first interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

19. The product of claim 11 wherein the thickness of said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

20. The product of claim 11 wherein the compressive stress of said second interlayer is less than said second diamond-like carbon layer.

21. The product of claim 11 wherein said second interlayer exhibits a tensile stress and said first diamond-like carbon layer and said second diamond-like carbon layer exhibit a compressive stress.

22. The product of claim 1 wherein said first composite layer includes a chemically vapor deposited third interlayer bonded to and disposed between said first interlayer and said first diamond-like carbon layer of a substantially optically transparent material capable of forming a strong chemical bond to said first interlayer and said first diamond-like carbon layer.

23. The product of claim 22 wherein said first interlayer comprises a substantially optically transparent material selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, tungsten nitride, molybdenum nitride, hafnium nitride, zirconium nitride, boron nitride, silicon dioxide, silicon oxide, yttrium oxide, germanium oxide, tungsten oxide, molybdenum oxide, boron oxide, hafnium oxide, silicon oxide, silicon dioxide, tantalum oxide, titanium oxide, zirconium oxide, silicon carbide, germanium carbide, aluminum oxide, cerium oxide, tin oxide, thorium oxide, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, francium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, radium oxide, barium fluoride, cerium fluoride, magnesium fluoride, thorium fluoride, calcium fluoride, neodymium fluoride, lead fluoride, sodium fluoride, lithium fluoride, zinc selenide, zinc sulfide and mixtures thereof.

24. The product of claim 22 wherein said third interlayer comprises a substantially optically transparent material selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, hafnium nitride, tungsten nitride, molybdenum nitride, zirconium nitride, boron nitride, silicon dioxide, silicon oxide, yttrium oxide, germanium oxide, hafnium oxide, tungsten oxide, molybdenum oxide, boron oxide, tantalum oxide, titanium oxide, zirconium oxide, silicon carbide, germanium carbide, and mixtures thereof.

25. The product of claim 24 wherein said third interlayer is at least 10 Å

thick.

26. The product of claim 22 wherein said third interlayer comprises silicon dioxide at least 200 Å

thick.

27. The product of claim 22 wherein said third interlayer comprises a substantially optically transparent metallic material capable of reflecting visible light selected from the group consisting of silicon, germanium, hafnium, molybdenum, tungsten, yttrium, tantalum, titanium and zirconium.

28. The product of claim 27 wherein said third interlayer is at least 25 Å

thick.

29. The product of claim 22 wherein said third interlayer comprises a substantially optically transparent metallic material capable of reflecting visible light selected from the group consisting of vanadium, niobium, chromium, manganese, rhenium, technetium, iron, cobalt, iridium, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, ruthenium, indium, aluminum, tin, osmium, thallium, lead, antimony, bismuth and polonium.

30. The product of claim 29 wherein said third interlayer is at least 25 Å

thick.

31. The product of claim 22 wherein the thickness of at least one of said first interlayer, said third interlayer and said first diamond-like carbon layer is selected to minimize the reflection of light at predetermined wavelengths.

32. The product of claim 22 wherein the thickness of at least one of said first interlayer, said third interlayer and said first diamond-like carbon layer is selected to maximize the reflection of light at predetermined wavelengths.

33. The product of claim 22 wherein the thickness of said first interlayer, said third interlayer and said first diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

34. The product of claim 22 wherein the thickness of said third interlayer and said first diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

35. The product of claim 22 wherein the compressive stress of said third interlayer is less than said first diamond-like carbon layer and greater than said adhesion-mediating layer.

36. The product of claim 22 wherein said third interlayer exhibits a tensile stress and said first diamond-like carbon layer exhibits a compressive stress.

37. The product of claim 22 including a fourth interlayer disposed between said third interlayer and said first diamond-like carbon layer of a substantially optically transparent material devoid of alkali metal atoms and fluorine and capable of forming a strong chemical bond with said third interlayer and said first diamond-like carbon layer.

38. The product of claim 37 wherein said fourth interlayer comprises a substantially optically transparent material selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, tungsten nitride, molybdenum nitride, hafnium nitride, zirconium nitride, boron nitride, silicon dioxide, silicon oxide, yttrium oxide, germanium oxide, hafnium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, boron oxide, titanium oxide, zirconium oxide, silicon carbide, germanium carbide and mixtures thereof.

39. The product of claim 38 wherein said fourth interlayer is at least 10 Å

thick.

40. The product of claim 37 wherein said fourth interlayer comprises silicon dioxide at least 200 Å

thick.

41. The product of claim 37 wherein the thickness of at least one of said first interlayer, said third interlayer, said fourth interlayer and said first diamond-like carbon layer is selected to minimize the reflection of light at predetermined wavelengths.

42. The product of claim 37 wherein the thickness of at least one of said first interlaYer, said third interlayer, said fourth interlayer and said first diamond-like carbon layer is selected to maximize the reflection of light at predetermined wavelengths.

43. The product of claim 37 wherein the thickness of said first interlayer, said third interlayer, said fourth interlayer and said first diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

44. The product of claim 37 wherein the thickness of said third interlayer, said fourth interlayer and said first diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

45. The product of claim 37 wherein the compressive stress of said fourth interlayer is less than said first diamond-like carbon layer and greater than said adhesion-mediating layer.

46. The product of claim 37 wherein said fourth interlayep exhibits a tensile stress and said first diamond-like carbon layer exhibits a compressive stress.

47. The product of claim 22 including at least one second composite layer bonded to and disposed immediately adjacent to said first composite layer.

48. The product of claim 47 wherein the thickness of at least one of said first interlayer, said third interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer is selected to minimize the reflection of light at predetermined wavelengths.

49. The product of claim 47 wherein the thickness of at least one of said first interlayer, said third interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer is selected to maximize the reflection of light at predetermined wavelengths.

50. The product of claim 47 wherein the thickness of said first interlayer, said third interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

51. The product of claim 47 wherein the thickness of said third interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

52. The product of claim 37 including at least one second composite layer bonded to and disposed immediately adjacent to said first composite layer.

53. The product of claim 52 wherein the thickness of at least one of said first interlayer, said third interlayer, said fourth interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer is selected to minimize the reflection of light at predetermined wavelengths.

54. The product of claim 52 wherein the thickness of at least one of said first interlayer, said third interlayer, said fourth interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer is selected to maximize the reflection of light at predetermined wavelengths.

55. The product of claim 52 wherein the thickness of said first interlayer, said third interlayer, said fourth interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.

56. The product of claim 52 wherein the thickness of said third interlayer, said fourth interlayer, said first diamond-like carbon layer, said second interlayer and said second diamond-like carbon layer corresponds to integer multiples of quarter wavelength optical thickness at predetermined wavelengths.