Durable high index nanocomposites for AR coatings

• US 7,264,872 B2
• Filed: 12/30/2004
• Issued: 09/04/2007
• Est. Priority Date: 12/30/2004
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Goenner, Emily S., Kolb, Brant U., Noyola, Joan M., Jones, Vivian W., Walker, Christopher B. Jr., Wang, Sharon
• Primary Examiner(s): LE, HOA T
• Application Number:
  US11/026,702
• Publication Number:
  US 20060147674A1
• Time in Patent Office: 978 Days
• Field of Search: 428/328, 428/702, 106/1.22, 106/1.25, 106/450, 977/834, 977/783, 977/902
• US Class Current: 428/328
• CPC Class Codes: C08J 2433/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: G02F 1/133502 Antiglare, refractive index matching layers
• CPC Class Codes: Y10S 977/783 Organic host/matrix, e.g. lipid
• CPC Class Codes: Y10S 977/834 Optical properties of nanomaterial, e.g. specified transparency, opacity, or index of refraction
• CPC Class Codes: Y10S 977/902 Specified use of nanostructure
• CPC Class Codes: Y10T 428/24355 Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof

Abstract

The present invention includes ultraviolet curable compositions preferably containing discrete, crystalline zirconia nanoparticles with reactive, or copolymerizable, surface modification, in a polymerizable monomer/oligomer resin mixture. It is believed that copolymerizable surface modification provides a functional group that enables the functionalized particle to co-polmerize with the reactive monomers, oligomers, and crosslinkers in the formulation. Relative to surface modification of the nanoparticles, acrylate functionality is preferred over methacrylate functionality. On the other hand, methacrylate functionality is preferred over non-reactive, or nonpolymerizable, functionality. As the nanocomposite cures, the resultant network is heavily crosslinked by selection of raw materials with substantial acrylate functionality.

Claims

1. A UV curable optical coating comprising:

a polymerizable mixture comprising monomer, oligomer, and mixtures thereof; and

surface modified inorganic nanoparticles comprising a majority of surface modified zirconia nanoparticles having an average cross-sectional diameter of about 10 to 30 nanometers and 10 wt-% to 33 wt-% of the total nanoparticles of inorganic nanoparticles having an average cross-sectional diameter of about 80 to 150 nanometers, wherein said optical coating has a refractive index of at least 1.6.

2. The coating of claim 1 wherein said inorganic nanoparticles are zirconia nanoparticles that are surface modified with 3:

1 acrylate silane;

nonionic silane.

3. The coating of claim 1 wherein said polymerizable mixture comprises one or more monomers having substantial acrylate and/or methacrylate functionality.

4. The coating of claim 1 wherein said majority of nanoparticles comprises about 67 to 90 wt % of the total weight of the nanoparticles.

5. The coating of claim 1 wherein said inorganic nanoparticles having an average cross-sectional diameter of about 10 to 30 nanometers comprise zirconia nanoparticles and the nanoparticles having an average cross-sectional diameter of about 80 to 150 nanometers comprise silica and represent about 10 to 33 wt % of the total nanoparticle weight.

6. A display system comprising the cured coating of claim 1.

7. The UV curable optical coating of claim 1 wherein the cured coating exhibits a 10 point mean roughness value of at least 30 nanometers.

8. The UV curable optical coating of claim 1 wherein the surface modified zirconia nanoparticles are acrylate silane surface modified.

9. The UV curable optical coating of claim 8 wherein said polymerizable mixture comprises one or more monomers having substantial acrylate functionality.

10. An antireflective coating comprising the cured coating of claim 1.

11. The coating of claim 1 wherein said inorganic nanoparticles having an average cross-sectional diameter of about 80 to 150 nanometers are selected from the group consisting of zirconia, silica, titanium, antimony, mixed metal oxides, and mixtures thereof.

12. A coated article comprising:

a polymeric substrate;

a hard coat layer coupled to the polymeric substrate;

a high refractive index optical layer coupled to the hard coat layer; and

an optional low refractive index optical layer coupled to the high refractive index optical layer, wherein said high refractive index optical layer comprises a bimodal system of functionalized zirconia nanoparticles comprising a majority of nanoparticles sized to about 10-30 nanometers and a minority of nanoparticles sized to about 80-150 nanoparticles.

13. The coated article of claim 12 wherein said bimodal system further comprises silica nanoparticles.

14. The coated article of claim 12 wherein said majority of nanoparticles consists of zirconia and said minority of nanoparticles consists of zirconia.

15. The coated article of claim 12 wherein said zirconia nanoparticles exhibit a 10 point mean average of at least 30 nanometers.

16. The coated article of claim 12 wherein said zirconia nanoparticles generally exist as discrete particles within the polymeric substrate.

17. The coated article of claim 12 wherein the high refractive index optical layer has refractive index of at least 1.6.

18. The coated article of claim 12 wherein the high refractive index optical layer comprises less than 70 weight percent of inorganic nanoparticles.

19. The coated article of claim 12 wherein said high refractive index optical layer exhibits a 10 point mean roughness value of at least 30 nanometers.

20. A display system comprising the coated article of claim 12.

21. An optical article comprising:

a polymeric substrate; and

a hard coat layer fixed to the polymeric substrate, said hard coat layer having a refractive index of at least 1.6;

wherein said hard coat layer comprises a bimodal system of functionalized inorganic nanoparticles comprising surface modified zirconia nanoparticles, wherein a majority of nanoparticles are sized to about 10-30 nanometers and 10 wt-% to 33 wt-% of the total nanoparticles are sized to about 80-150 nanoparticles.

22. The optical article of claim 21 further comprising a low refractive index optical layer coupled to the hard coat layer.

23. The optical article of claim 21 wherein said inorganic nanoparticles comprise ground zirconia nanoparticles.

24. The optical article of claim 21 wherein the hard coat layer exhibits a 10 point mean roughness value of at least 30 nanometers.

25. A display system comprising the optical article of claim 21.

26. A composition containing:

a polymerizable mixture comprising monomer, oligomer, and mixtures thereof; and

surface modified inorganic nanoparticles comprising surface modified zirconia nanoparticles defined by a polydispersity ranging from about 0.4 to about 0.8 and a z-average mean of about 20 to 80 dispersed within said mixture.

27. The composition of claim 26 wherein said nanoparticles are defined by a volume mean average of about 10 to 30 nm and an intensity average:

volume average ratio of about 1.5;

18.

28. The composition of claim 26 wherein said nanoparticles define a bimodal system comprised of functionalized zirconia nanoparticles comprising a majority of nanoparticles sized to about 10-30 nanometers and a minority of nanoparticles sized to about 80-150 nanoparticles.

29. The composition of claim 26 wherein the cured composition exhibits a 10 point mean roughness value of at least 30 nanometers.

30. The composition of claim 26 wherein the surface modified zirconia nanoparticles are acrylate silane surface modified.

31. The composition of claim 30 wherein said polymerizable mixture comprises one or more monomers having substantial acrylate functionality.

32. An optical article comprising:

a polymeric substrate; and

a hard coat layer fixed to the polymeric substrate, said hard coat layer having a refractive index of at least 1.6;

wherein said hard coat layer comprises the cured composition of claim 26.