Coated articles with a surface-modifying layer and methods of making the same
A fluorine-free fingerprint-hiding coating made from alkyl silane oligomers or polymers addresses the durability and adhesion issues of existing coatings by dispersing fingerprint oils effectively, maintaining hydrophobicity, and withstanding abrasion.
Patent Information
- Application Number
- PCT/US2024/057255
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-07-09
- Filing Date
- 2024-11-25
- Publication Date
- 2025-06-05
AI Technical Summary
Existing fingerprint-hiding coatings on glass, glass-ceramic, and ceramic materials suffer from limited durability and adhesion, especially when used in combination with other treatments like anti-reflective coatings.
A fluorine-free surface-modifying layer, specifically a fingerprint-hiding coating, is developed using an oligomer or polymer of alkyl silanes. This coating exhibits low polar surface energy and high dispersive surface energy, making it oleophilic and effective in dispersing fingerprint oils, thereby reducing visibility and color shift.
The coating demonstrates excellent abrasion resistance, maintaining its hydrophobic and oleophilic properties even after extensive abrasion tests. It also shows good adhesion to the substrate and can be used in conjunction with other treatments without compromising durability.
Smart Images

Figure US2024057255_05062025_PF_FP_ABST
Abstract
Description
ATTORNEY DOCKET NO. SP23-219WO COATED ARTICLES WITH A SURFACE-MODIFYING LAYER ANDMETHODS OF MAKING THE SAMECLAIM OF PRIORITY
[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S.Provisional Application Serial No. 63 / 603,156 filed on November 28, 2023, and U.S. Provisional Application Serial No.63 / 669,001 filed on July 9, 2024, the contents of which are relied upon and incorporated herein by reference in their entirety. FIELD
[0002] The present disclosure relates generally to coated articles with a surface-modifying layer (e.g., fingerprint-hiding coating) and methods of making the same and, more particularly, to coated articles comprising a surface-modifying layer (e.g., fingerprint-hiding coating) that is fluorine-free and methods of making coated articles. BACKGROUND
[0003] Glass, glass-ceramic, and ceramic materials are commonly used in variousconsumer electronic products including display devices, for example, liquid crystal displays (LCDs), electrophoretic displays (EPD), organic light-emitting diode displays (OLEDs), plasma display panels (PDPs), or the like. For example, chemically strengthened glass is favored for many touch-screen products, including cell phones, music players, e-book readers, notepads, tablets, laptop computers, automatic teller machines, and other similar devices. Many of these glass, glass-ceramic, and ceramic materials are also employed in displays and display devices of consumer electronic products that do not have touch-screen capability but are prone to direct human contact, including desktop computers, laptop computers, elevator screens, equipment displays, and others. Glass, glass-ceramic, and ceramic materials are often treated to provide aesthetic and functional characteristics based on the end-use application of the material. For example, anti-reflective, anti-glare, anti-fingerprint, and fingerprint-hiding treatments are common treatments used on materials used in touch-screen products.
[0004] The durability of some types of treatments, such as an anti-fingerprint coatingor a fingerprint-hiding coating, can be limited, especially when used in combination with other treatments, for example an anti-reflective coating. It is known to use fluorinated silanes, for example fluoroethersilanes, which can bind to the surface as a monolayer or multilayer, to form coatings with a thickness from 2 nm to 5 nm. Once this nanoscale coating is abraded away, the surface no longer exhibits repellant properties. Attempts to improve the durability and adhesionATTORNEY DOCKET NO. SP23-219WO of an ETC coating include roughening the underlying surface that the ETC coating is disposed on.
[0005] Consequently, there is a need for a new surface-modifying layer (e.g.,fingerprint-hiding coating) that can be used with glass, glass-ceramic, and / or ceramic articles with improved abrasion resistance and / or that can be used in conjunction with other treatments, for example, an anti-reflective coating. This need and others are addressed by the present disclosure. SUMMARY
[0006] The above need and other needs are addressed by the present disclosure whichprovides a surface-modifying layer (e.g., fingerprint-hiding coating) or a coated article containing the same that can reduce a visibility and / or color shift associated with disposing a fingerprint thereon. Providing a low polar surface energy and / or a high dispersive surface energy a can enable oils (e.g., fingerprint oil) to be dispersed across the fingerprint-hiding surface (e.g., oleophilic), which can decrease a visibility and / or a color shift associated with fingerprints. For example, providing an alkyl silane can enable a low polar surface energy and high dispersive surface energy of the fingerprint-hiding coating, which can enable the fingerprint-hiding coating to be oleophilic. Providing a high diiodomethane contact angle (e.g., about 60° or more) and / or a low hexadecane contact angle (e.g., 20° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oil to be dispersed across the surface-modifying layer (e.g., fingerprint-hiding coating) rather than beading up into pronounced droplets. Providing a low oleic acid contact angle (e.g., about 40° or less or 35° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oil to be dispersed across the surface-modifying layer (e.g., fingerprint- hiding coating) rather than beading up into pronounced droplets. Providing a high water contact angle (e.g., about 90° or more or about 100° or more) can enhance the removal of aqueous material (e.g., water droplets, sweat droplets) from the surface-modifying layer (e.g., fingerprint-hiding coating). Consequently, the fingerprint-hiding coating can be hydrophobic and oleophilic.
[0007] Providing a surface-modifying layer (e.g., fingerprint-hiding coating) inaccordance with the aspects of the disclosure can exhibit good abrasion resistance (e.g., an abraded water contact angle of about 80° or more or 90° or more after 2,000 cycles and / or 3,500 cycles in a Steel Wool Abrasion Test, a cheesecloth-abraded water contact angle of about 80° or more or 90° or more after 200,000 cycles in a Cheesecloth Abrasion Test, or a rubber- abraded water contact angle of about 80° or more or 90° or more after 3,000 cycles in a RubberATTORNEY DOCKET NO. SP23-219WO Abrasion Test), for example, maintaining a hydrophobic and / or oleophilic character. The surface-modifying layer (e.g., fingerprint-hiding coating) can exhibit good adhesion to the surface that is disposed on, for example, a surface of a substrate or an optical stack. Providing a thickness of the surface-modifying layer (e.g., fingerprint-hiding coating) from about 1 nm to 75 nm (e.g., from about 2 nm to 5 nm) can provide good durability fingerprint-hiding coating while minimizing the amount of material required to achieve the above-mentioned effects.
[0008] As discussed herein, the properties of the present disclosure are different fromthe corresponding properties of Comparative Examples discussed herein in a statistically significant way that demonstrates that the surface-modifying layer (e.g., fingerprint-hiding coating) of the present disclosure does a better job of “hiding” visual effects associated with an applied fingerprint than the Comparative Examples. Providing a fluorine-free fingerprint- hiding coating can be cheaper to produce and / or more environmentally friendly.
[0009] The surface-modifying layer (e.g., fingerprint-hiding coating) can comprise anoligomer of one or more alkyl silanes, a polymer of one or more alkyl silanes, or both. As used herein, the term “polymer” may generally refer to oligomers, polymers, or combinations thereof. The alkyl silane can be a bis-silane or a tris-silane, which can produce a polymer or copolymer with disiloxane bonds between at least a pair of monomers.
[0010] In aspects, the surface-modifying layer (e.g., fingerprint-hiding coating) can bebonded to and / or disposed on a planarization layer 123. The planarization layer can comprisea silica or an at least partial silica-like network. Providing a silica or a partial silica-like network can enable the planarization layer to be stiff (e.g., elastic modulus of about 9 GPa or more) while allowing the surface-modifying layer (e.g., fingerprint-hiding coating) to remain flexible enough to withstand abrasion.
[0011] The substrate can comprise a glass-based, glass-ceramic, and / or ceramic-basedmaterial, which can provide good dimensional stability, good impact resistance, and / or good puncture resistance. The glass-based, glass-ceramic, and / or ceramic-based substrate can comprise one or more compressive stress regions, which can further provide increased impact resistance and / or increased puncture resistance.
[0012] Some example aspects of the disclosure are described below with theunderstanding that any of the features of the various aspects may be used alone or in combination with one another.
[0013] Aspect 1. A coated article comprising:a substrate comprising a first major surface; andATTORNEY DOCKET NO. SP23-219WO a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein the fingerprint- hiding coating is fluorine-free, wherein the fingerprint-hiding coating exhibits: a water contact angle from 90° to 120°; an oleic acid contact angle of 40° or less; and a coefficient of friction of the exterior surface is 0.25 or less.
[0014] Aspect 2. The coated article of aspect 1, wherein the fingerprint-hiding coatingcomprises an alkyl silane at the exterior surface, wherein: the alkyl silane is bonded to the substrate by a silane group, the alkyl silane is bonded to another part of the fingerprint-hiding coating by a silane group, or both; the silane group of the alkyl silane is at a free end of the alkyl silane; or both.
[0015] Aspect 3. The coated article of aspect 2, wherein the fingerprint-hiding coatingcomprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both.
[0016] Aspect 4. The coated article of aspect 3, wherein the oligomer of the alkyl silane,the polymer of the alkyl silane, or both comprises at least one of: a dialkyl siloxane block; a dimethylsiloxane block bonding monomers of the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, together; or a disiloxane group bonding monomers of the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, together.
[0017] Aspect 5. The coated article of any one of aspects 2-4, wherein the alkyl silaneis substantially free of chlorine.
[0018] Aspect 6. The coated article of any one of aspects 1-5, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 or more, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
[0019] Aspect 7. The coated article of aspect 6, wherein, in the structure, at least oneof: n is 1, and q is from 1 to 100; orATTORNEY DOCKET NO. SP23-219WO n is 1, m is 8, p is 8, and q is from 1 to 100.
[0020] Aspect 8. The coated article of aspect 6, wherein, in the structure, at least oneof: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
[0021] Aspect 9. The coated article of any one of aspects 6-8, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34.
[0022] Aspect 10. The coated article of aspect 9, wherein R’ is CH3, and m is 8.
[0023] Aspect 11. The coated article of aspect 9 or aspect 10, wherein the condensationproduct further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[0024] Aspect 12. The coated article of aspect 11, wherein a ratio of the monomericunits comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:10.
[0025] Aspect 13. The coated article of any one of aspects 6-12, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[0026] Aspect 14. The coated article of aspect 13, wherein a ratio of the monomericunits comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[0027] Aspect 15. The coated article of aspect 2, wherein the fingerprint-hiding coatingcomprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein theATTORNEY DOCKET NO. SP23-219WO oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
[0028] Aspect 16. The coated article of aspect 15, wherein, in the structure, at least one:n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[0029] Aspect 17. The coated article of aspect 15, wherein, in the structure, at least one:n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
[0030] Aspect 18. The coated article of aspect 15 wherein, in the structure, at least oneof: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
[0031] Aspect 19. The coated article of any one of aspects 15-17 wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3and OH, and m is from 3 to 34.
[0032] Aspect 20. The coated article of aspect 18, wherein R is OCH3, and m is 8.
[0033] Aspect 21. The coated article of aspect 18, wherein R is OCH3, and m is 6.
[0034] Aspect 22. The coated article of any one of aspects 18-21, wherein thecondensation product further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[0035] Aspect 23. The coated article of aspect 21, wherein a ratio of the monomericunits comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {ATTORNEY DOCKET NO. SP23-219WO {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof is from 10:1 to 1:10.
[0036] Aspect 24. The coated article of any one of aspects 21-23, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[0037] Aspect 25. The coated article of aspect 24, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[0038] Aspect 26. The coated article of aspect 24, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.
[0039] Aspect 27. The coated article of any one of aspects 21-23, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[0040] Aspect 28. The coated article of aspect 27, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[0041] Aspect 29. The coated article of aspect 27, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.
[0042] Aspect 30. The coated article of any one of aspects 1-29, wherein thefingerprint-hiding coating exhibits the oleic acid contact angle of 30° or less.
[0043] Aspect 31. The coated article of any one of aspects 1-30, wherein thefingerprint-hiding coating exhibits at least one of: a voltage of about 15 Volts or less in a Tribocharging test; or a voltage difference between a peripheral contact region and a center contact region of about 5 Volts or less in the Tribocharging test.ATTORNEY DOCKET NO. SP23-219WO
[0044] Aspect 32. The coated article of any one of aspects 1-31, wherein when asimulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits at least one of: an effective diameter of droplets of the simulated fingerprint of 10 µm or more; a mean height of droplets of the simulated fingerprint on the exterior surface of 0.15 µm or less; or a spherical cap radius of droplets of the simulated fingerprint of 40 µm or more.
[0045] Aspect 33. The coated article of any one of aspects 1-32, wherein when asimulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits: a core material value Vmc of a droplet of the simulated fingerprint of 0.10 µm3 / µm2or more between areal material ratios of 10% and 90%.
[0046] Aspect 34. The coated article of aspect 33, wherein the fingerprint-hidingcoating exhibits at least one of: a ratio of a volume of the droplet to an area of the droplet is 0.78 µm3 / µm2or less; a ratio of a height of the droplet to the area of the droplet is 0.005 µm / µm2or less; a total area of the simulated fingerprint over the exterior surface of 150,000 µm2or more; a haze of 8% or less with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; a center of a sphere modeled on the droplet of the simulated fingerprint is located greater than 30 µm from the exterior surface of the fingerprint-hiding coating; a mean gray level is 150 or less as measured in a Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; or a normalized gray level is 2.0 or less as measured in a Normalized Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test.
[0047] Aspect 35. The coated article of any one of aspects 1-34, wherein thefingerprint-hiding coating comprises at least one of: a polar surface energy of from 2 milliNewtons per meter to 6 milliNewtons per meter; or a total surface energy of from 25 milliNewtons per meter to 35 milliNewtons per meter.ATTORNEY DOCKET NO. SP23-219WO
[0048] Aspect 36. The coated article of any one of aspects 1-35, wherein thefingerprint-hiding coating comprises a thickness from 1 nanometer to 75 nanometers.
[0049] Aspect 37. The coated article of any one of aspects 1-36, wherein the exteriorsurface of the fingerprint-hiding coating comprises from 0.5 atom% to 2 atom% of a non- fluorine halogen.
[0050] Aspect 38. The coated article of any one of aspects 1-37, wherein the exteriorsurface of the fingerprint-hiding coating is free of a transition metal-containing compound.
[0051] Aspect 39. The coated article of any one of aspects 1-38, wherein thefingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
[0052] Aspect 40. The coated article of any one of aspects 1-39, further comprising aplanarization layer positioned between the substrate and the fingerprint-hiding coating, the fingerprint-hiding coating disposed on the planarization layer, the planarization layer exhibiting at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silicon in the planarization layer is about 0.2 or more.
[0053] Aspect 41. The coated article of aspect 40, wherein the planarization layercomprises a refractive index ranging from 1.37 to 1.55.
[0054] Aspect 42. The coated article of any one of aspects 40-41, wherein theplanarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
[0055] Aspect 43. The coated article of any one of aspects 40-42, wherein theplanarization layer exhibits at least one of: an abraded water contact angle of about 80° or more after being abraded for 2,000 cycles in a Steel Wool Abrasion test; a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.ATTORNEY DOCKET NO. SP23-219WO
[0056] Aspect 44. The coated article of any one of aspects 1-43, further comprising atleast one of: an anti-reflective coating positioned between the fingerprint-hiding coating and the substrate; or a gradient coating comprising a refractive index gradient positioned between the fingerprint-hiding coating and the substrate.
[0057] Aspect 45. The coated article of any one of aspects 1-44, further comprising anoptical stack positioned between the fingerprint-hiding coating and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
[0058] Aspect 46. The coated article of aspect 45, wherein the optical stack has a stackthickness from about 10 nanometers to about 10 micrometers.
[0059] Aspect 47. The coated article of aspect 46, wherein the stack thickness of theoptical stack is from about 50 nanometers to about 5 micrometers.
[0060] Aspect 48. The coated article of any one of aspects 46-47, wherein the stackthickness of the optical stack is from about 50 nanometers to about 500 nanometers.
[0061] Aspect 49. The coated article of any one of aspects 45-48, wherein the opticalstack comprises a scratch resistant layer, and the scratch resistant layer has a scratch-resistant thickness from 0.05 micrometers to 3 micrometers.
[0062] Aspect 50. The coated article of any one of aspects 45-49, wherein the coatedarticle including the optical stack and the fingerprint-hiding coating exhibits a hardness of 8 GigaPascals or greater measured by a Berkovich Indenter Hardness test.
[0063] Aspect 51. The coated article of any one of aspects 45-50, wherein the opticalstack comprises one or more of a silicon-containing oxide, a silicon-containing nitride, a silicon-containing oxynitride, and Nb2O5.
[0064] Aspect 52. The coated article of any one of aspects 45-51, wherein the opticalstack comprises two or more layers with different refractive indices including at least a first low refractive index (RI) layer and a second high refractive index (RI) layer, wherein the absolute value of a difference between the first low RI layer and the second high RI layer is 0.2 or more, and further wherein the optical stack comprises one or more of a silicon-containing oxide, a silicon-containing nitride, a silicon-containing oxynitride, and Nb2O5.
[0065] Aspect 53. The coated article of any one of aspects 1-52, wherein the substrateis a textured substrate.ATTORNEY DOCKET NO. SP23-219WO
[0066] Aspect 54. The coated article of aspect 53, wherein the coated article furthercomprises an anti-reflective coating or a gradient coating positioned between the fingerprint- hiding coating and the textured substrate.
[0067] Aspect 55. The coated article of aspect 54, wherein a thickness of the anti-reflective coating is from about 200 nanometers to about 3 micrometers.
[0068] Aspect 56. The coated article of any one of aspects 1-52, wherein the substrateis a polymer substrate.
[0069] Aspect 57. A coated article comprising:a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 or more, q is 1 or more, R is selected from agroup consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
[0070] Aspect 58. The coated article of aspect 57, wherein R” is CH3.
[0071] Aspect 59. The coated article of any one of aspects 57-58, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[0072] Aspect 60. The coated article of any one of aspects 57-59, wherein, in thestructure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
[0073] Aspect 61. A coated article comprising:a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein:ATTORNEY DOCKET NO. SP23-219WO the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34.
[0074] Aspect 62. The coated article of aspect 61, wherein R’ is CH3.
[0075] Aspect 63. The coated article of aspect 61, wherein R’ is CH3, and m is 8.
[0076] Aspect 64. The coated article of any one of aspects 61-63, wherein thecondensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[0077] Aspect 65. The coated article of aspect 64, wherein a ratio of the monomericunits comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof is from 10:1 to 1:10.
[0078] Aspect 66. The coated article of any one of aspects 61-65, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof .
[0079] Aspect 67. The coated article of aspect 66, wherein a ratio of the monomericunits comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[0080] Aspect 68. The coated article of any one of aspects 57-67, wherein thefingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
[0081] Aspect 69. The coated article of any one of aspects 57-68, further comprisingan optical stack positioned between the fingerprint-hiding coating and the substrate, whereinATTORNEY DOCKET NO. SP23-219WO the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
[0082] Aspect 70. The coated article of any one of aspects 57-69 wherein the substrateis a textured substrate.
[0083] Aspect 71. The coated article of aspect 70, wherein the coated article furthercomprises an anti-reflective coating or a gradient coating positioned between the fingerprint- hiding coating and the textured substrate.
[0084] Aspect 72. The coated article of any one of aspects 57-68, wherein the substrateis a polymer substrate.
[0085] Aspect 73. A coated article comprising:a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
[0086] Aspect 74. The coated article of aspect 73, wherein the alkyl silane is chlorine-free.
[0087] Aspect 75. The coated article of aspect 73 or aspect 74, wherein R’ is OCH3.
[0088] Aspect 76. The coated article of any one of aspects 73-75, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[0089] Aspect 77. The coated article of any one of aspects 73-75, in the structure, atleast one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
[0090] Aspect 78. The coated article of any one of aspects 73-75 wherein, in thestructure, at least one of:ATTORNEY DOCKET NO. SP23-219WO n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
[0091] Aspect 79. A coated article comprising:a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.
[0092] Aspect 80. The coated article of aspect 79, wherein R is OCH3, and m is 8.
[0093] Aspect 81. The coated article of aspect 80, wherein R is OCH3, and m is 6.
[0094] Aspect 82. The coated article of any one of aspects 79-81, wherein thecondensation product further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[0095] Aspect 83. The coated article of aspect 82, wherein a ratio of the monomericunits comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:10.
[0096] Aspect 84. The coated article of aspect 82, wherein a ratio of the monomericunits comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof,is from 1:1 to 1:10.
[0097] Aspect 85. The coated article of any one of aspects 79-84, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product ofATTORNEY DOCKET NO. SP23-219WO monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[0098] Aspect 86. The coated article of aspect 85, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[0099] Aspect 87. The coated article of aspect 85, a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.
[00100] Aspect 88. The coated article of any one of aspects 79-84, wherein theoligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00101] Aspect 89. The coated article of aspect 88, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00102] Aspect 90. The coated article of aspect 89, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00103] Aspect 91. The coated article of any one of aspects 79-90, wherein thefingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
[00104] Aspect 92. The coated article of any one of aspects 79-91, further comprisingan optical stack positioned between the fingerprint-hiding coating and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
[00105] Aspect 93. The coated article of any one of aspects 79-92 wherein the substrateis a textured substrate.
[00106] Aspect 94. The coated article of aspect 93, wherein the coated article furthercomprises an anti-reflective coating or a gradient coating positioned between the fingerprint- hiding coating and the textured substrate.ATTORNEY DOCKET NO. SP23-219WO
[00107] Aspect 95. The coated article of any one of aspects 79-94, wherein the substrateis a polymer substrate.
[00108] Aspect 96. A coated article comprising:a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 or more, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
[00109] Aspect 97. The coated article of aspect 96, wherein the planarization layercomprises at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silica of about 0.2 or more.
[00110] Aspect 98. The coated article of any one of aspects 96-97, wherein theplanarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
[00111] Aspect 99. The coated article of any one of aspects 96-98, wherein R” is CH3.
[0112] Aspect 100. The coated article of any one of aspects 96-99, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[00113] Aspect 101. The coated article of any one of aspects 96-99, wherein, in thestructure, at least one of: n is 2, and q is from 1 to 100;ATTORNEY DOCKET NO. SP23-219WO n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
[00114] Aspect 102. A coated article comprising:a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34.
[00115] Aspect 103. The coated article of aspect 102, wherein the planarization layercomprises at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silica of about 0.2 or more.
[00116] Aspect 104. The coated article of any one of aspects 102-103, wherein theplanarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
[00117] Aspect 105. The coated article of any one of aspects 102-104, wherein R’ isCH3, and m is 8.
[00118] Aspect 106. The coated article of any one of aspects 102-105, wherein thecondensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate..ATTORNEY DOCKET NO. SP23-219WO
[00119] Aspect 107. The coated article of aspect 106, wherein a ratio of the monomericunits comprising {OSi(R’)2[CH2]mSi(R’)2} to the monomeric units comprising {R”Si(OCH3)3} is from 10:1 to 1:10.
[00120] Aspect 108. The coated article of any one of aspects 102-107, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof .
[00121] Aspect 109. The coated article of aspect 108, wherein a ratio of the monomericunits comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00122] Aspect 110. The coated article of aspect 108, wherein a ratio of the monomericunits comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:10.
[00123] Aspect 111. The coated article of any one of aspects 102-110, wherein theplanarization layer exhibits at least one of: an abraded water contact angle of about 80° or more after being abraded for 2,000 cycles in a Steel Wool Abrasion test; a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
[00124] Aspect 112. The coated article of any one of aspects 102-111, furthercomprising an optical stack positioned between the planarization layer and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
[00125] Aspect 113. The coated article of any one of aspects 102-112, wherein thesubstrate is a textured substrate.ATTORNEY DOCKET NO. SP23-219WO
[00126] Aspect 114. The coated article of aspect 113, wherein the coated article furthercomprises an anti-reflective coating or a gradient coating positioned between the planarization layer and the textured substrate.
[00127] Aspect 115. The coated article of any one of aspects 102-114, wherein thesubstrate is a polymer substrate.
[00128] Aspect 116. A coated article comprising:a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
[00129] Aspect 117. The coated article of aspect 116, wherein the planarization layercomprises at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silica of about 0.2 or more.
[00130] Aspect 118. The coated article of any one of aspects 116-117, wherein theplanarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
[00131] Aspect 119. The coated article of any one of aspects 116-118, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; orATTORNEY DOCKET NO. SP23-219WO n is 1, m is 8, p is 8, and q is from 1 to 100.
[00132] Aspect 120. The coated article of any one of aspects 116-119, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
[00133] Aspect 121. The coated article of any one of aspects 116-118, wherein, in thestructure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
[00134] Aspect 122. A coated article comprising:a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.
[00135] Aspect 123. The coated article of aspect 122, wherein R is OCH3, and m is 8.
[0136] Aspect 124. The coated article of aspect 122, wherein R is OCH3, and m is 6.
[0137] Aspect 125. The coated article of any one of aspects 122-124 , wherein thecondensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, orATTORNEY DOCKET NO. SP23-219WO combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[00138] Aspect 126. The coated article of aspect 125, wherein a ratio of the monomericunits comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof,is from 10:1 to 1:10.
[00139] Aspect 127. The coated article of aspect 125, wherein a ratio of the monomericunits comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:10.
[00140] Aspect 128. The coated article of any one of aspects 125-127, wherein theoligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00141] Aspect 129. The coated article of aspect 128, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00142] Aspect 130. The coated article of aspect 128, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:10.
[00143] Aspect 131. The coated article of any one of aspects 125-127, wherein theoligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00144] Aspect 132. The coated article of aspect 131, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00145] Aspect 133. The coated article of aspect 131, wherein a ratio of the monomericunits comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:10.
[00146] Aspect 134. A method of forming a coated article comprising:disposing an alkyl silane on a first major surface of a substrate, the alkyl silane comprising a C3-C34 alkyl group, and the alkyl silane comprising at least two reactiveATTORNEY DOCKET NO. SP23-219WO groups independently selected from a silane, a non-fluorine halogen, or combinations thereof; and reacting the alkyl silane to form a fingerprint-hiding coating on the first major surface of the substrate, wherein the fingerprint-hiding coating exhibits: a water contact angle from 90° to 120°; an oleic acid contact angle of 40° or less; and a coefficient of friction of the exterior surface is 0.25 or less.
[00147] Aspect 135. The method of aspect 134, wherein the disposing comprises spraycoating the alkyl silane on the first major surface.
[00148] Aspect 136. The method of any one of aspects 134-135, wherein the reactingcomprises heating the alkyl silane at a temperature of about 80°C to about 250°C for a period of time from about 10 minutes to about 8 hours.
[00149] Aspect 137. The method of any one of aspects 134-135, wherein the reactingcomprises disposing the alkyl silane on the planarization layer at a temperature from about 20°C to about 40°C for a period of time from about 1 hour to about 24 hours.
[00150] Aspect 138. The method of any one of aspects 134-137, wherein two of the atleast two reactive groups are located at opposite ends of the alkyl silane.
[00151] Aspect 139. The method of any one of aspects 134-138, wherein the alkylsilane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, or combinations thereof.
[00152] Aspect 140. The method of any one of aspects 134-139, wherein the alkylsilane comprises an alkyl chlorodimethylsilane and an alkyl trimethoxysilane.
[0153]
[00154] Aspect 141. The method of aspect 140, wherein the alkyl trimethoxysilane isoctadecyl trimethoxysilane.
[00155] Aspect 142. The method of any one of aspects 139-141, wherein an amount ofthe alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00156] Aspect 143. The method of aspect 142, wherein the amount of the alkyltrimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.ATTORNEY DOCKET NO. SP23-219WO
[00157] Aspect 144. The method of any one of aspects 134-143, wherein the alkylsilane comprises 1,8-bis(chlorodimethylsilyl)ocatane, chloropropyltrimethoxysilane, octadecyl trimethoxysilane, or combinations thereof.
[00158] Aspect 145. The method of any one of aspects 134-143, wherein the alkylsilane comprises 1,8- bis(trimethoxysilyl)octane, 1,6-bis(trimethoxysilyl)hexane, octadecyl trimethoxysilane, or combinations thereof.
[00159] Aspect 146. The method of any one of aspects 134-145, wherein the alkylsilane is chlorine-free.
[00160] Aspect 147. The method of any one of aspects 134-146, wherein the alkylsilane comprises an alkyl trimethoxysilyl and an alkyl trimethoxysilane.
[00161] Aspect 148. The method of aspect 147, wherein the alkyl trimethoxysilane isoctadecyl trimethoxysilane.
[00162] Aspect 149. The method of any one of aspects 147-148, wherein an amount ofthe alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00163] Aspect 150. The method of aspect 149, wherein the amount of the alkyltrimethoxysilane as a wt% of the total amount of the alkyl silane is from about 10% to about 50%.
[00164] Aspect 151. The method of any one of aspects 134-150 or 253-259 inclusive,wherein the alkyl silane further comprises a dimethylsilane with silanes at both ends of the dimethylsilane.
[00165] Aspect 152. The method of aspect 151, wherein the dimethylsilane is dichloro-tetramethyl-disoloxane.
[00166] Aspect 153. The method of any one of aspects 151-152, wherein an amount ofthe dimethylsilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00167] Aspect 154. The method of aspect 153, wherein the amount of thedimethylsilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
[00168] Aspect 155. The method of any one of aspects 134-146, wherein the alkylsilane consists of a single alkyl silane compound.
[00169] Aspect 156. The method of any one of aspects 134-155, wherein the disposingthe alkyl silane comprises disposing a solution containing the alkyl silane, wherein a pH of the solution is from 6 to 8.ATTORNEY DOCKET NO. SP23-219WO
[00170] Aspect 157. The method of any one of aspects 134-156, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both.
[00171] Aspect 158. The method of any one of aspects 134-157, wherein thefingerprint-hiding coating further comprises: the alkyl silane is bonded to the substrate by a silane group, the alkyl silane is bonded to another part of the coated article by a silane group, or both; a silane group of the alkyl silane is at a free end of the alkyl silane; or both.
[00172] Aspect 159. The method of any one of aspects 157-158, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a dialkyl siloxane block.
[00173] Aspect 160. The method of any one of aspects 157-159, wherein monomericunits comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a disiloxane group.
[00174] Aspect 161. The method of any one of aspects 157-160, wherein monomericunits comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a dimethylsiloxane block.
[00175] Aspect 162. The method of any one of aspects 157-161, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3andCH2CH3, n is 1 or more, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
[00176] Aspect 163. The method of aspect 162, wherein R” is CH3.
[0177] Aspect 164. The method of any one of aspects 162-163, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[00178] Aspect 165. The method of any one of aspects 162-163, wherein, in thestructure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; orATTORNEY DOCKET NO. SP23-219WO n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
[00179] Aspect 166. The method of any one of aspects 157-161, wherein thefingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3and CH2CH3, and m is from 3 to 34.
[00180] Aspect 167. The method of aspect 166, wherein R’ is CH3.
[0181] Aspect 168. The method of aspect 166, wherein R’ is CH3, and m is 8.
[0182] Aspect 169. The method of any of aspects 166-168 wherein the condensationproduct further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, , wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[00183] Aspect 170. The method of aspect 169, wherein a ratio of the monomeric unitscomprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof. is from 10:1 to 1:10.
[00184] Aspect 171. The method of any of aspects 169-170 wherein the oligomer ofthe alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00185] Aspect 172. The method of aspect 171, wherein a ratio of the monomeric unitscomprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00186] Aspect 173. The method of any one of aspects 157-161, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
[00187] Aspect 174. The method of aspect 173, wherein the alkyl silane is chlorine-free.ATTORNEY DOCKET NO. SP23-219WO
[00188] Aspect 175. The method of any of aspects 173-174, wherein R’ is OCH3.
[0189] Aspect 176. The method of any of aspects 173-175, wherein, in the structure,at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[00190] Aspect 177. The method of any of aspects 173-175, wherein, in the structure,at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
[00191] Aspect 178. The method of any of aspects 173-175, wherein, in the structure,at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
[00192] Aspect 179. The method of any one of aspects 157-161, wherein thefingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3and OH, and m is from 3 to 34.
[00193] Aspect 180. The method of aspect 179, wherein R is OCH3, and m is 8.
[0194] Aspect 181. The method of aspect 179, wherein R is OCH3, and m is 6.
[0195] Aspect 182. The method of any one of aspects 179-181, wherein thecondensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, , wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[00196] Aspect 183. The method of aspect 182, wherein a ratio of the monomeric unitscomprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO
[00197] Aspect 184. The method of aspect 182, wherein a ratio of the monomeric unitscomprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:10.
[00198] Aspect 185. The method of any one of aspects 179-184, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00199] Aspect 186. The method of aspect 185, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00200] 187. The method of aspect 185, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.
[00201] Aspect 188. The method of any one of aspects 179-184, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00202] Aspect 189. The method of aspect 188, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10
[00203] Aspect 190. The method of aspect 188, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:10.
[00204] Aspect 191. A method of forming a coated article comprising:evaporating a functionalized polyhedral oligomeric silsesquioxane onto a first major surface of a substrate; impinging an ion beam at the first major surface of the substrate, the impinging occurs in a chamber comprising a chamber pressure ranging from about 10-4Pascal to about 1 Pascal, the ion beam is generated using a discharge current from about 0.25 Amps to about 1 Amp to form a planarization layer; and then reacting material of the planarization layer with a alkyl silane to form a fingerprint- hiding coating, the alkyl silane comprising 3 or more carbons, wherein the silaneATTORNEY DOCKET NO. SP23-219WO comprises at least two reactive groups independently selected from a silane, a non- fluorine halogen, or combinations thereof, wherein the fingerprint-hiding coating exhibits: a water contact angle from 90° to 120°; an oleic acid contact angle of 40° or less; and a coefficient of friction of the exterior surface is 0.25 or less.
[00205] Aspect 192. The method of aspect 191, wherein the functionalized polyhedraloligomeric silsesquioxane is at least partially functionalized by at least one of: an alkene comprising from 2 to 8 carbons, an alkane comprising from 1 to 8 carbons, or combinations thereof.
[00206] Aspect 193. The method of any one of aspects 191-192, wherein theevaporating the functionalized polyhedral oligomeric silsesquioxane and the impinging occur simultaneously.
[00207] Aspect 194. The method of any one of aspects 191-193, wherein the reactingcomprises evaporating the alkyl silane at a temperature of about 80°C to about 250°C for a period of time from about 10 minutes to about 8 hours.
[00208] Aspect 195. The method of any one of aspects 191-194, wherein the reactingcomprises disposing the alkyl silane on the planarization layer at a temperature from about 20°C to about 40°C for a period of time from about 1 hour to about 24 hours.
[00209] Aspect 196. The method of any one of aspects 191-195, wherein two of the atleast two reactive groups are located at opposite ends of the alkyl silane.
[00210] Aspect 197. The method of any one of aspects 191-196, wherein the alkylsilane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, or combinations thereof.
[00211] Aspect 198. The method of any one of aspects 191-197, wherein the alkylsilane comprises an alkyl chlorodimethylsilane and an alkyl trimethoxysilane.
[00212] Aspect 199. The method of aspect 199, wherein the alkyl trimethoxysilane isoctadecyl trimethoxysilane.
[00213] Aspect 200. The method of any one of aspects 198-199, wherein an amount ofthe alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.ATTORNEY DOCKET NO. SP23-219WO
[00214] Aspect 201. The method of aspect 200, wherein the amount of the alkyltrimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
[00215] Aspect 202. The method of any one of aspects 191-201, wherein the alkylsilane comprises 1,8-bis(chlorodimethylsilyl)ocatane, chloropropyltrimethoxysilane, octadecyl trimethoxysilane, or combinations thereof.
[00216] Aspect 203. The method of any one of aspects 191-201, wherein the alkylsilane comprises 1,8- bis(trimethoxysilyl)octane, 1,6-bis(trimethoxysilyl)hexane, octadecyl trimethoxysilane, or combinations thereof.
[00217] Aspect 204. The method of any one of aspects 191-201, wherein the alkylsilane is chlorine-free.
[00218] Aspect 205. The method of any one of aspects 134-204, wherein the alkylsilane comprises an alkyl trimethoxysilyl and an alkyl trimethoxysilane.
[00219] Aspect 206. The method of aspect 205, wherein the alkyl trimethoxysilane isoctadecyl trimethoxysilane.
[00220] Aspect 207. The method of any one of aspects 205-206, wherein an amount ofthe alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00221] Aspect 208. The method of aspect 207, wherein the amount of the alkyltrimethoxysilane as a wt% of the total amount of the alkyl silane is from about 10% to about 50%.
[00222] Aspect 209. The method of any one of aspects 191-208, wherein the alkylsilane further comprises a dimethylsilane with silanes at both ends of the dimethylsilane.
[00223] Aspect 210. The method of aspect 209, wherein the dimethylsilane is dichloro-tetramethyl-disoloxane.
[00224] Aspect 211. The method of any one of aspects 209-210, wherein an amount ofthe dimethylsilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00225] Aspect 212. The method of aspect 211, wherein the amount of thedimethylsilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
[00226] Aspect 213. The method of any one of aspects 191-204, wherein the alkylsilane consists of a single alkyl silane compound.ATTORNEY DOCKET NO. SP23-219WO
[00227] Aspect 214. The method of any one of aspects 191-213, wherein the disposingthe alkyl silane comprises disposing a solution containing the alkyl silane, wherein a pH of the solution is from 6 to 8.
[00228] Aspect 215. The method of any one of aspects 191-214, wherein theplanarization layer exhibiting at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silicon in the planarization layer is about 0.2 or more.
[00229] Aspect 216. The method of any one of aspects 191-215, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both.
[00230] Aspect 217. The method of any one of aspects 119-216, wherein thefingerprint-hiding coating further comprises: the alkyl silane is bonded to the planarization layer by a silane group; a silane group of the alkyl silane is at a free end of the alkyl silane; or both.
[00231] Aspect 218. The method of any one of aspects 216-217, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a dialkyl siloxane block.
[00232] Aspect 219. The method of any one of aspects 216-218, wherein monomericunits comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a disiloxane group.
[00233] Aspect 220. The method of any one of aspects 216-219, wherein monomericunits comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a dimethylsiloxane block.
[00234] Aspect 221. The method of any one of aspects 216-220, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3 andCH2CH3, n is 1 or more, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
[00235] Aspect 222. The method of aspect 221, wherein R” is CH3.ATTORNEY DOCKET NO. SP23-219WO
[00236] Aspect 223. The method of any one of aspects 221-222, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[00237] Aspect 224. The method of any one of aspects 221-222, wherein, in thestructure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
[00238] Aspect 225. The method of any one of aspects 216-220, wherein thefingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34.
[00239] Aspect 226. The method of aspect 225, wherein R’ is CH3.
[0240] Aspect 227. The method of aspect 225, wherein R’ is CH3, and m is 8.
[0241] Aspect 228. The method of any of aspects 225-227, wherein the condensationproduct further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[00242] Aspect 229. The method of aspect 228, wherein a ratio of the monomeric unitscomprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:10.
[00243] Aspect 230. The method of any of aspects 228-229, wherein the oligomer ofthe alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof
[00244] Aspect 231. The method of aspect 230, wherein a ratio of the monomeric unitscomprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO
[00245] Aspect 232. The method of any one of aspects 216-220, wherein thefingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
[00246] Aspect 233. The method of aspect 232, wherein the alkyl silane is chlorine-free.
[00247] Aspect 234. The method of any of aspects 232-233, wherein R’ is OCH3.
[0248] Aspect 235. The method of any one of aspects 232-234, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
[00249] Aspect 236. The method of any one of aspects 232-234, wherein, in thestructure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
[00250] Aspect 237. The method of any one of aspects 232-234, wherein, in thestructure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
[00251] Aspect 238. The method of any one of aspects 216-220, wherein thefingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.
[00252] Aspect 239. The method of aspect 238, wherein R is OCH3, and m is 8.
[0253] Aspect 240. The method of aspect 238, wherein R is OCH3, and m is 6.ATTORNEY DOCKET NO. SP23-219WO
[00254] Aspect 241. The method of any one of aspects 238-240, wherein thecondensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
[00255] Aspect 242. The method of aspect 241, wherein a ratio of the monomeric unitscomprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:10.
[00256] Aspect 243. The method of aspect 241, wherein a ratio of the monomeric unitscomprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:10.
[00257] Aspect 244. The method of any one of aspects 238-243, wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00258] Aspect 245. The method of aspect 244, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00259] Aspect 246. The method of aspect 244, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.
[00260] Aspect 247. The method of any one of aspects 238-243 wherein the oligomerof the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
[00261] Aspect 248. The method of aspect 247, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.
[00262] Aspect 249. The method of aspect 247, wherein a ratio of the monomeric unitscomprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO
[00263] Aspect 250. The coated article of any one of aspects 6-14, wherein R is selectedfrom a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
[00264] Aspect 251. The coated article of any one of aspects 57-60, wherein R isselected from a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
[00265] Aspect 252. The coated article of any one of aspects 96-101, wherein R isselected from a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
[00266] Aspect 253. The method of any one of aspects 134-138, wherein the alkylsilane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, an alkyl dimethylmethoxysilane, an alkyl dimethylethoxysilane or combinations thereof.
[00267] Aspect 254. The method of any one of aspects 134-139, wherein the alkylsilane comprises an alkyl dimethylmethoxysilane and an alkyl trimethoxysilane.
[00268] Aspect 255. The method of any one of aspects 253-254, wherein the alkyltrimethoxysilane is octadecyl trimethoxysilane.
[00269] Aspect 256. The method of any one of aspects 253-255, wherein an amount ofthe alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00270] Asperct 257. The method of aspect 256, wherein the amount of the alkyltrimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
[00271] Aspect 258. The method of any one of aspects 134-143 or 253-257 inclusive,wherein the alkyl silane comprises 1,8-bis(dimethylmethoxysilyl)octane, octadecyl trimethoxysilane, or combinations thereof.
[00272] Aspect 259. The method of any one of aspects 253-258, wherein the alkylsilane is chlorine-free.
[00273] Aspect 260. The method of any one of aspects 191-196, wherein the alkylsilane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, an alkyl dimethylmethoxysilane, an alkyl dimethylethoxysilane or combinations thereof.
[00274] Aspect 261. The method of any one of aspects 191-196 wherein the alkyl silanecomprises an alkyl dimethylmethoxysilane and an alkyl trimethoxysilane.ATTORNEY DOCKET NO. SP23-219WO
[00275] Aspect 262. The method of any one of aspects 260-261, wherein the alkyltrimethoxysilane is octadecyl trimethoxysilane.
[00276] Aspect 263. The method of any one of aspects 261-262, wherein an amount ofthe alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
[00277] Aspect 264. The method of aspect 263, wherein the amount of the alkyltrimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
[00278] Aspect 265. The method of any one of aspects 191-201 or 260-264 inclusive,wherein the alkyl silane comprises 1,8-bis(dimethylmethoxysilyl)octane, octadecyl trimethoxysilane, or combinations thereof.
[00279] Aspect 266. The method of any one of aspects 221-231, wherein R is selectedfrom a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
[00280] Aspect 267. The method of any one of aspects 221-231, wherein R is selectedfrom a methoxy group, an ethoxy group, or combinations thereof.
[00281] Aspect 268. The method of any one of aspects 221-231, wherein R is amethoxy group.
[00282] Aspect 269. The coated article of any one of aspect 1-5, wherein thefingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3andCH2CH3, n is 1 or more, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof..
[00283] Aspect 270. The coated article of any one of aspects 1-5 or 269 inclusive,wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34, and monomeric units comprising {R4Si(OCH3)2}, {R4Si(OCH3)}, {R4Si}, { R4Si(OCH3)2(OH)}, {R4Si(OCH3)(OH)2}, { R4Si(OH)3}, or combinations thereof, wherein R4is a (C5-C38) alkyl; optionally, wherein at least a portion of the monomeric units are linked to the substrate; and wherein a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R4Si(OCH3)2}, {R4Si(OCH3)},ATTORNEY DOCKET NO. SP23-219WO {R4Si}, { R4Si(OCH3)2(OH)}, {R4Si(OCH3)(OH)2}, { R4Si(OH)3}, or combinations thereof, is 10:1 to 1:10.
[00284] Aspect 271. The coated article of any one of aspects 1-6 or 269-270 inclusive,wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof; and wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2}to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is 10:1 to 1:10.
[00285] Aspect 272. The coated article of any one of aspects 1-271, wherein thefingerprint-hiding coating exhibits at least one of: a voltage of about 15 Volts or less in a Tribocharging test; or a voltage difference between a peripheral contact region and a center contact region of about 5 Volts or less in the Tribocharging test.
[00286] Aspect 273. The coated article of any one of aspects 1-272, wherein when asimulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits at least one of: an effective diameter of droplets of the simulated fingerprint of 10 µm or more; a mean height of droplets of the simulated fingerprint on the exterior surface of 0.15 µm or less; or a spherical cap radius of droplets of the simulated fingerprint of 40 µm or more.
[00287] Aspect 274. The coated article of any one of aspects 1-273, wherein when asimulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits: a core material value Vmc of a droplet of the simulated fingerprint of 0.10 µm3 / µm2or more between areal material ratios of 10% and 90%.
[00288] Aspect 275. The coated article of aspect 274, wherein the fingerprint-hidingcoating exhibits at least one of: a ratio of a volume of the droplet to an area of the droplet is 0.78 µm3 / µm2or less; a ratio of a height of the droplet to the area of the droplet is 0.005 µm / µm2or less; a total area of the simulated fingerprint over the exterior surface of 150,000 µm2or more; a haze of 8% or less with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; a center of a sphere modeled on the droplet of the simulated fingerprint is located greater than 30 µm from the exterior surface of the fingerprint- hiding coating; a mean gray level is 150 or less as measured in a Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; or a normalized gray level is 2.0 or less as measured in a Normalized GrayATTORNEY DOCKET NO. SP23-219WO Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test.
[00289] Aspect 276. The coated article of any one of aspects 1-275, wherein thefingerprint-hiding coating comprises a thickness from 1 nanometer to 75 nanometers.
[00290] Aspect 277. The coated article of any one of aspects 1-276, wherein thefingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
[00291] Aspect 278. The coated article of any one of aspects 1-277, furthercomprising a planarization layer positioned between the substrate and the fingerprint-hiding coating, the fingerprint-hiding coating disposed on the planarization layer, the planarization layer exhibiting at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a molar ratio of hydrogen to silicon in the planarization layer is about 0.2 or more;or a refractive index ranging from 1.37 to 1.55.
[00292] Aspect 279. The coated article of aspect 278, wherein the planarization layerexhibits at least one of: an abraded water contact angle of about 80° or more after being abraded for 2,000 cycles in a Steel Wool Abrasion test; a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
[00293] Aspect 280. The coated article of any one of aspects 1-279, furthercomprising at least one of: an anti-reflective coating positioned between the fingerprint-hiding coating and the substrate; or a gradient coating comprising a refractive index gradient positioned between the fingerprint-hiding coating and the substrate.
[00294] Aspect 281. The coated article of any one of aspects 1-280, wherein thesubstrate is a metal, glass, glass ceramic, or polymer substrate.
[00295] Aspect 282. The coated article of any one of aspects 1-281, wherein thefingerprint-hiding coating is substantially free of halogens.
[00296] Aspect 283. A coated article comprising: a substrate comprising a first majorsurface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint- hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint- hiding coating is fluorine-free, the fingerprint-hiding coating is substantially free of halogens and comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, whereinATTORNEY DOCKET NO. SP23-219WO the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
[00297] Aspect 284. A coated article comprising: a substrate comprising a first majorsurface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating is substantially free of halogens and comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selectedfrom CH3 and CH2CH3, n is 1 or more, q is 1 or more, R is selected from a group consisting ofa hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof. BRIEF DESCRIPTION OF THE DRAWINGS
[00298] The above and other features and advantages of aspects of the presentdisclosure are better understood when the following detailed description is read with reference to the accompanying drawings, in which:
[0299] FIGS. 1, 2A, 2B, and 2C are schematic views of exemplary coated articles according to aspects;
[00300] FIG. 3 is a schematic plan view of an example consumer electronic deviceaccording to aspects;
[0301] FIG. 4 is a schematic perspective view of the example consumer electronicdevice of FIG. 3;
[0302] FIG. 5 schematically illustrates a functionalized polyhedral oligomeric silsesquioxane (POSS) compound;
[00303] FIG. 6 schematically illustrates a reaction of polysilazane (PHPS);ATTORNEY DOCKET NO. SP23-219WO
[00304] FIGS. 7-8 are flow charts illustrating example methods of making coatedarticles in accordance with aspects of the disclosure;
[00305] FIG. 9 schematically illustrates a step(s) in methods of making a coated articlecomprising evaporating a functionalized POSS and impinging an ion beam on a first major surface of a substrate;
[0306] FIG. 10 schematically illustrates a step in methods of making a coated article comprising reacting material at the first major surface with an alkyl silane;
[0307] FIG. 11 schematically illustrates a step in methods of making a coated article comprising disposing a solution over a first major surface of a substrate;
[0308] FIG. 12 schematically illustrates a step in methods of making a coated article comprising heating the solution on the first major surface;
[0309] FIG. 13 schematically illustrates a step in methods of making a coated article comprising spraying an alkyl silane and reacting the alkyl silane;
[00310] FIG. 14 schematically illustrates simulated fingerprints applied to Examples1-2 and Comparative Examples XX-YY;
[00311] FIG. 15 schematically illustrates the results of cleaning simulated fingerprintsapplied to Example 1 and Comparative Examples YY-ZZ;
[00312] FIG. 16 schematically illustrates (a) simulated fingerprints applied toExamples 1-2 and Comparative Examples XX-YY and (b) a distribution of droplet sizes associated with the simulated fingerprint as measured by white light interferometry with the vertical axis (i.e., y-axis) and horizontal axis (i.e., x-axis) corresponding to physical locations in µm;
[0313] FIGS.17A-17H shows chemical structure for alkyl silane compounds used to form Examples 1-2, Comparative Example EEE, Comparative Example XX, and Examples 46- 71;
[0314] FIG. 18A shows a polymeric structure of a surface-modifying layer in accordance with aspects of the disclosure;
[0315] FIG. 18B shows a polymeric structure of a surface-modifying layer in accordance with aspects of the disclosure;
[0316] FIG. 18C shows a polymeric structure of a surface-modifying layer in accordance with aspects of the disclosure;
[0317] FIG. 19A-19C shows spatial plots of water contact angle for Examples 1-2 and Comparative Example XX, respectively, with the vertical axis (i.e., y-axis) and horizontal axis (i.e., x-axis) corresponding to physical locations in millimeters;ATTORNEY DOCKET NO. SP23-219WO
[0318] FIG. 20 shows mean gray level on the vertical axis (i.e., y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY;
[0319] FIG.21 shows haze in % on the vertical axis (i.e., y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY;
[0320] FIG. 22 shows mean height of droplets of the artificial fingerprint in µm on the vertical axis (i.e., y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY;
[0321] FIG. 23 shows an average ratio of mean height to area of droplets of the artificial fingerprint (in µm / µm2or µm-1) on the vertical axis (i.e., y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY;
[0322] FIG. 24 shows a mean spherical cap radius of droplets of the artificial fingerprint in µm on the vertical axis (i.e., y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX- YY;
[0323] FIG.25 shows a total area of the droplets of the artificial fingerprint in µm2on the vertical axis (i.e., y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY;
[0324] FIG. 26 shows an average ratio of a volume of a droplet of the artificial fingerprint to an area of the droplet (in µm3 / µm2or µm) on the vertical axis (i.e. y-axis) as a function of oleic acid contact angle in degrees on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY; and
[0325] FIG.27 shows haze in % on the vertical axis (i.e., y-axis) as a function of mean gray level on the horizontal axis (i.e., x-axis) for Examples 1-2 and Comparative Examples XX-YY;
[0326] FIG. 28 schematically illustrates simulated fingerprints applied to Examples 3-8 and Comparative Examples DD-GG;
[0327] FIG. 29 schematically illustrates the Tribocharging Test;
[00328] FIG. 30 schematically illustrates voltages as contours with the vertical axis(i.e., y-axis) and horizontal axis (i.e., x-axis) corresponding to physical locations inside region2911 of FIG. 29;ATTORNEY DOCKET NO. SP23-219WO
[0329] FIG. 31 schematically illustrates tribocharging voltages for Example 8 and Comparative Examples AA and XX-YY where the vertical axis (i.e., y-axis) corresponds to voltage in Volts;
[00330] FIGS. 32-33 schematically illustrate triobcharging voltages in terms of Voltson the vertical axis (i.e., y-axis) as a function of time in seconds after the Tribocharging Test is complete on the horizontal axis (i.e., x-axis);
[0331] FIG. 34 schematically illustrates molar ratios of hydrogen to silicon (vertical axis – y-axis) as measured by dynamic secondary-ion mass spectrometry (D-SIMS) for Examples 35-44 and Comparative Examples JJ-KK; and
[0332] FIGS. 35, 36A, 36B, and 36C are schematic views of exemplary coated articles according to aspects;
[0333] FIG. 37 shows static water contact angle in degrees on the vertical axis (i.e., y-axis) as a function of rubber abrasion test cycles on the horizontal axis (i.e., x-axis) for Example 46-53;
[00334] FIG. 38 schematically illustrates simulated fingerprints applied to Examples46-63;
[0335] FIG. 39 shows normalized gray level on the vertical axis (i.e., y-axis) as a function of 1,8-bis(chlorodimethylsilyl)octane (BISCO) precursor volume percent relative to a total amount of BISCO and octadecyl trimethoxysilane on the horizontal axis (i.e., x-axis) for Examples 46-53;
[00336] FIG. 40 schematically illustrates simulated fingerprints applied to Examples54-57;
[0337] FIG. 41 shows static water contact angle in degrees on the vertical axis (i.e., y-axis) as a function of rubber abrasion test cycles on the horizontal axis (i.e., x-axis) to Examples 54-57;
[00338] FIG. 42 schematically illustrates simulated fingerprints applied to Examples58-61;
[0339] FIG. 43 shows static water contact angle in degrees on the vertical axis (i.e., y-axis) as a function of rubber abrasion test cycles on the horizontal axis (i.e., x-axis) for Examples 58-61;
[0340] FIG. 44 shows normalized gray level of a human fingerprint on the vertical axis (i.e., y-axis) as a function of the number of wipes on the horizontal axis (i.e., x-axis) for Example 54 before and after capping treatment;ATTORNEY DOCKET NO. SP23-219WO
[0341] FIG. 45 schematically depicts a positive ion Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) spectrum with intensity on the vertical axis (i.e., y-axis) as a function of mass-to-charge ratio (m / z) for Example 46;
[0342] FIG. 46 schematically depicts a positive ion Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) spectra with intensity on the vertical axis (i.e., y-axis) as a function of mass-to-charge ratio (m / z) for polydimethylsiloxane (PDMS);
[0343] FIG. 47 schematically depicts a positive ionTime-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) spectrum with intensity on the vertical axis (i.e., y-axis) as a function of mass-to-charge ratio (m / z) for Example 54;
[0344] FIG. 48 schematically depicts a Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) spectrum with intensity on the vertical axis (i.e., y-axis) as a function of mass-to-charge ratio (m / z) for octadecyl trimethoxysilane (OTS).
[0345] FIG. 49 schematically depicts TOF-SIMS spatial plots at various mass-to- charge ratios (m / z) of Example 49 (BISCO:OTS of 50:50);
[0346] FIG. 50 schematically depicts TOF-SIMS spatial plots of green / blue overlay for C2H5+and Si2C4H13O+of Examples 49- 51 (BISCO:OTS of 50:50, 40:60, and 30:70);
[0347] FIG. 51 schematically depicts TOF-SIMS spatial plots at regions of interest for BISCO and OTS of Example 49 (BISCO:OTS of 50:50);
[0348] FIG.52 schematically depicts positive ion Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) spectra with intensity on the vertical axis (i.e., y-axis) as a functionof mass-to-charge ratio (m / z) for the BISCO region of interest of FIG. 51, the OTS region ofinterest of FIG. 51, a pure BISCO reference, and a pure OTS reference; and
[0349] FIG. 53 shows an intensity of a Si2C4H13O+ / C2H5+ratio on the vertical axis(i.e., y-axis), as measured in FIG. 52 for the BISCO region of interest of FIG. 51, the OTSregion of interest of FIG. 51, the pure BISCO reference, and the pure OTS reference;
[0350] FIG. 54 shows static water contact angle in degrees on the vertical axis (i.e., y-axis) as a function of rubber abrasion test cycles on the horizontal axis (i.e., x-axis) for Examples 62-63;
[0351] FIG. 55 shows static water contact angle in degrees on the vertical axis (i.e., y-axis) as a function of rubber abrasion test cycles on the horizontal axis (i.e., x-axis) for Examples 64-65;
[0352] FIG. 56 shows static water contact angle in degrees on the vertical axis (i.e., y-axis) as a function of rubber abrasion test cycles on the horizontal axis (i.e., x-axis) for Examples 66 and 68;ATTORNEY DOCKET NO. SP23-219WO
[00353] FIG. 57 schematically illustrates simulated fingerprints applied to Examples66-67; and
[00354] FIG. 58 schematically illustrates simulated fingerprints applied to Examples50, 56, 62, 64, and 67.
[00355] Throughout the disclosure, the drawings are used to emphasize certain aspects.As such, it should not be assumed that the relative size of different regions, portions, and substrates shown in the drawings are proportional to its actual relative size, unless explicitly indicated otherwise. DETAILED DESCRIPTION
[00356] Aspects will now be described more fully hereinafter with reference to theaccompanying drawings in which example aspects are shown. Whenever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts.
[00357] FIGS. 1, 2A-2C, 35, and 36A-36C illustrate views of a coated article 101,201, 211, 221, 3501, 3601, 3611, or 3621 comprising a surface-modifying layer 113 (e.g.,fingerprint-hiding coating) disposed over a substrate 103 in accordance with aspects of thedisclosure. In aspects, as shown in FIGS. 35 and 36A-36C, the surface-modifying layer 113(e.g., fingerprint-hiding coating) can be disposed on a planarization layer 123, where theplanarization layer 123 is positioned between the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) and the substrate 103. Unless otherwise noted, a discussion offeatures of aspects of one surface-modifying layer 113 (e.g., fingerprint-hiding coating) orcoated article can apply equally to corresponding features of any aspects of the disclosure. For example, identical part numbers throughout the disclosure can indicate that, in some aspects, the identified features are identical to one another and that the discussion of the identified feature of one aspect, unless otherwise noted, can apply equally to the identified feature of any of the other aspects of the disclosure.
[00358] As shown in FIGS. 1, 2A-2C, 35, and 36A-36C, the substrate 103 comprisesa first major surface 105 and a second major surface 107 opposite the first major surface 105.As shown, the first major surface 105 can extend along a first plane 104, and / or the secondmajor surface 107 can extend along a second plane 106. In aspects, as shown, the second plane106 can be parallel to the first plane 104. As used herein, a substrate thickness 109 is definedbetween the first major surface 105 and the second major surface 107 as a distance betweenthe first plane 104 and the second plane 106. In aspects, the substrate thickness 109 can beabout 10 micrometers (µm) or more, about 25 µm or more, about 40 µm or more, about 60 µmATTORNEY DOCKET NO. SP23-219WO or more, about 70 µm or more, about 80 µm or more, about 90 µm or more, about 100 µm or more, about 125 µm or more, about 150 µm or more, about 200 µm or more, about 300 µm or more, about 5 millimeters (mm) or less, about 3 mm or less, about 2 mm or less, about 1 mm or less, about 800 µm or less, about 500 µm or less, about 300 µm or less, about 200 µm orless, about 180 µm or less, or about 160 µm or less. In aspects, the substrate thickness 109 canrange from about 10 µm to about 5 mm, from about 25 µm to about 3 mm, from about 40 µm to about 3 mm, from about 60 µm to about 2 mm, from about 70 µm to about 2 mm, from about 70 µm to about 1 mm, from about 70 µm to about 800 µm, from about 80 µm to about 500 µm, from about 90 µm 500 µm, from about 100 µm to about 200 µm, from about 125 µm to about 200 µm, from about 150 µm to about 200 µm, from about 150 µm to about 160 µm, or anyrange or subrange therebetween. Alternatively, the substrate thickness 109 can be from about1 millimeter (mm) to about 5 mm, from about 1 mm to about 3 mm, or any range or subrange therebetween.
[00359] The substrate 103 can comprise a glass-based material, a glass-ceramicmaterial, and / or a ceramic-based material having a pencil hardness of 8H or more, for example, 9H or more. As used herein, pencil hardness is measured using ASTM D 3363-20 with standard lead graded pencils. Providing a glass-based substrate, a glass-ceramic substrate, and / or a ceramic-based substrate can enhance puncture resistance and / or impact resistance. As used herein, “glass-based” includes both glasses and glass-ceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase. A glass-based material(e.g., glass-based substrate) may comprise an amorphous material (e.g., glass) and optionallyone or more crystalline materials (e.g., ceramic). Exemplary glass-based materials may be an alkali-free glass and / or comprise a low content of alkali metals (e.g., R2O of about 10 mol% or less, wherein R2O comprises Li2O Na2O, and K2O). As used herein, “ceramic-based” includes both ceramics and glass-ceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase. In aspects, ceramic-based materials can comprise one or more oxides, nitrides, oxynitrides, carbides, borides, and / or silicides. Throughout thedisclosure, an elastic modulus (e.g., Young’s modulus) of the substrate 103 is measured usingISO 527-1:2019. In aspects, the substrate 103 can comprise an elastic modulus ranging fromabout 10 GPa to about 100 GPa, from about 40 GPa to about 100 GPa, from about 60 GPa to about 100 GPa, from about 60 GPa to about 80 GPa, from about 80 GPa to about 100 GPa, orany range or subrange therebetween. In aspects, the substrate 103 may comprise a polymersubstrate.ATTORNEY DOCKET NO. SP23-219WO
[00360] In aspects, the substrate 103 can be optically transparent. As used herein,“optically transparent” or “optically clear” means an average transmittance of 70% or more in the wavelength range of 400 nm to 750 nm through a 1.0 mm thick piece of a material. In aspects, an “optically transparent material” or an “optically clear material” may have an average transmittance of 75% or more, 80% or more, 85% or more, or 90% or more, 91% or more, 92% or more, 94% or more, 96% or more in the wavelength range of 400 nm to 750 nm through a 1.0 mm thick piece of the material. The average transmittance in the wavelength range of 400 nm to 700 nm is calculated by measuring the transmittance of whole number wavelengths from about 400 nm to about 700 nm and averaging the measurements.
[00361] In some aspects, the substrate 103, in addition to being transparent, can also becolored transparent, opaque, colored opaque, translucent, or colored translucent. As used herein “opaque” and “translucent” can mean as follows: opacity is the measure of impenetrability to visible light. An opaque object is neither transparent (allowing all light to pass through) nor translucent (allowing some light to pass through). When light strikes an interface between two substances, in general some may be reflected, some absorbed, some scattered, and the rest transmitted. An opaque substance transmits very little light, and therefore reflects, scatters, or absorbs most of it. Opacity depends on the frequency of the light being considered. For instance, some kinds of glass, while transparent in the visual range, are largely opaque to ultraviolet light. Further, the colored transparent, colored opaque, and colored translucent can be anyone of a variety of colors including, for example, black, white, green, yellow, pink, red, blue, orange, purple, brown etc..
[00362] In aspects, the coated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621comprising a glass-based substrate, a glass-ceramic substrate, and / or a ceramic-based substrate can comprise one or more compressive stress regions. In aspects, a compressive stress region may be created by chemically strengthening. Chemically strengthening may comprise an ion exchange process, where ions in a surface layer are replaced by–or exchanged with–larger ions having the same valence or oxidation state. Methods of chemically strengthening will be discussed later. Without wishing to be bound by theory, chemically strengthening the substrate103 can enable good impact resistance, good puncture resistance, and / or enable small bendradii, for example, with the compressive stress from the chemical strengthening counteracting bend-induced tensile stress on the outermost surface of the substrate. A compressive stressregion may extend into a portion of the first portion and / or the second portion for a depth calledthe depth of compression (DOC). As used herein, depth of compression means the depth at which the stress in the chemically strengthened substrates and / or portions described hereinATTORNEY DOCKET NO. SP23-219WO changes from compressive stress to tensile stress. Depth of compression may be measured by a surface stress meter or a scattered light polariscope (SCALP, wherein values reported herein were made using SCALP-5 made by Glasstress Co., Estonia) depending on the ion exchange treatment and the thickness of the article being measured. Where the stress in the substrate and / or portion is generated by exchanging potassium ions into the substrate, a surface stress meter, for example, the FSM-6000 (Orihara Industrial Co., Ltd. (Japan)), is used to measure depth of compression. Unless specified otherwise, compressive stress (including surface CS) is measured by surface stress meter (FSM) using commercially available instruments, for example the FSM-6000, manufactured by Orihara. Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. Unless specified otherwise, SOC is measured according to Procedure C (Glass Disc Method) described in ASTM standard C770-16, entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety. Where the stress is generated by exchanging sodium ions into the substrate, and the article being measured is thicker than about 400 µm, SCALP is used to measure the depth of compression and central tension (CT). Where the stress in the substrate and / or portion is generated by exchanging both potassium and sodium ions into the substrate and / or portion, and the article being measured is thicker than about 400 µm, the depth of compression and CT are measured by SCALP. Without wishing to be bound by theory, the exchange depth of sodium may indicate the depth of compression while the exchange depth of potassium ions may indicate a change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile). The refracted near-field (RNF; the RNF method is described in U.S. Patent No. 8,854,623, entitled “Systems and methods for measuring a profile characteristic of a glass sample”, which is incorporated herein by reference in its entirety) method also may be used to derive a graphical representation of the stress profile. When the RNF method is utilized to derive a graphical representation of the stress profile, the maximum central tension value provided by SCALP is utilized in the RNF method. The graphical representation of the stress profile derived by RNF is force balanced and calibrated to the maximum central tension value provided by a SCALP measurement. As used herein, “depth of layer” (DOL) means the depth that the ions have exchanged into the substrate and / or portion (e.g., sodium, potassium). Throughout the disclosure, DOL is measured in accordance with ASTM C-1422. Without wishing to be bound by theory, a DOL is usually greater than or equal to the corresponding DOC. Through the disclosure, when the maximum central tension cannot be measured directly by SCALP (as when the article being measured is thinner thanATTORNEY DOCKET NO. SP23-219WO about 400 µm) the maximum central tension can be approximated by a product of a maximum compressive stress and a depth of compression divided by the difference between the thickness of the substrate and twice the depth of compression, wherein the compressive stress and depth of compression are measured by FSM.
[00363] In aspects, the substrate 103 may comprise a first compressive stress region atthe first major surface 105 that can extend to a first depth of compression from the first majorsurface 105. In aspects, the substrate 103 may comprise a second compressive stress region atthe second major surface 107 that can extend to a second depth of compression from the secondmajor surface 107. In aspects, the first depth of compression and / or the second depth ofcompression as a percentage of the substrate thickness 109 can be about 5% or more, about10% or more, about 12% or more, about 15% or more, about 17% or more, about 30% or less, about 25% or less, about 22% or less, about 20% or less, about 17% or less, or about 15% or less. In aspects, the first depth of compression and / or the second depth of compression as apercentage of the substrate thickness 109 can range from about 5% to about 30%, from about10% to about 25%, from about 10% to about 22%, from about 12% to about 20%, from about 12% to about 17%, from about 15% to about 17%, or any range or subrange therebetween. In aspects, the first depth of compression and / or the second depth of compression can be about 1 µm or more, about 10 µm or more, about 15 µm or more, about 20 µm or more, about 25 µm or more, about 30 µm or more, about 200 µm or less, about 150 µm or less, about 100 µm or less, about 60 µm or less, about 45 µm or less, about 30 µm or less, or about 20 µm or less. In aspects, the first depth of compression and / or the second depth of compression can range from about 1 µm to about 200 µm, from about 1 µm to about 150 µm, from about 10 µm to about100 µm, from about 15 µm to about 600 µm, from about 20 µm to about 45 µm, from about 20µm to about 30 µm, or any range or subrange therebetween. By providing a first depth of compression and / or a second depth of compression from about 1% to about 30% of the first thickness, good impact and / or puncture resistance can be enabled.
[00364] In aspects, the first compressive stress region can comprise a maximum firstcompressive stress, and / or the second compressive stress region can comprise a maximum second compressive stress. In further aspects, the maximum first compressive stress and / or the maximum second compressive stress can be about 100 MegaPascals (MPa) or more, about 300 MPa or more, 400 MPa or more, about 500 MPa or more, about 600 MPa or more, about 700 MPa or more, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 800 MPa or less. In further aspects, the maximum first compressive stress and / or the maximum second compressive stress can range from about 100 MPa to about 1,500 MPa, fromATTORNEY DOCKET NO. SP23-219WO about 100 MPa to about 1,200 MPa, from about 300 MPa to about 1,200 MPa, from about 300 MPa to about 1,000 MPa, from about 400 MPa to about 1,000 MPa, from about 500 MPa to about 1,000 MPa, from about 600 MPa to about 900 MPa, from about 700 MPa to about 800 MPa, or any range or subrange therebetween. By providing a maximum first compressive stress and / or a maximum second compressive stress from about 100 MPa to about 1,500 MPa, good impact and / or puncture resistance can be enabled.
[00365] In aspects, the substrate 103 may comprise a tensile stress region. The tensilestress region can be positioned between the first compressive stress region and the second compressive stress region. In aspects, the tensile stress region can comprise a maximum tensile stress. In further aspects, the maximum first stress can be about 10 MPa or more, about 20 MPa or more, about 30 MPa or more, about 100 MPa or less, about 80 MPa or less, or about 60 MPa or less. In further aspects, the maximum tensile stress can range from about 10 MPa to about 100 MPa, from about 10 MPa to about 80 MPa, from about 10 MPa to about 60 MPa, from about 20 MPa to about 100 MPa, from about 20 MPa to about 80 MPa, from about 20 MPa to about 60 MPa, from about 30 MPa to about 100 MPa, from about 30 MPa to about 80 MPa, from about 30 MPa to about 60 MPa, or any range or subrange therebetween. Providing a maximum tensile stress from about 10 MPa to about 100 MPa can enable good impact and / or puncture resistance.
[00366] As used herein, if a first layer and / or component is described as “disposedover” a second layer and / or component, other layers may or may not be present between the first layer and / or component and the second layer and / or component. Furthermore, as used herein, “disposed over” does not refer to a relative position with reference to gravity. For example, a first layer and / or component can be considered “disposed over” a second layer and / or component, for example, when the first layer and / or component is positioned underneath, above, or to one side of a second layer and / or component. As used herein, a first layer and / or component described as “bonded to” a second layer and / or component means that the layers and / or components are bonded to each other, either by direct contact and / or bonding between the two layers and / or components or via an adhesive layer. As used herein, a first layer and / or component described as “contacting” or “in contact with” a second layer and / or components refers to direct contact and includes the situations where the layers and / or components are bonded to each other. As used herein, a first layer and / or component described as “disposed on” a second layer and / or component means that the layers do not have any other layers therebetween other than an optional layer of a coupling agent or are bonded together.ATTORNEY DOCKET NO. SP23-219WO Consequently, a first layer disposed over a second layer may further be disposed on, in contact with, and / or bonded to the second layer.
[00367] In aspects, as shown in FIGS. 2A-2C and 36A-36C, the coated article 201,211, 221, 3601, 3611, or 3621 can comprise an optical stack 203 comprising a third majorsurface 205 disposed on the first major surface 105 of the substrate 103. As shown, the opticalstack 203 can comprise a fourth major surface 207 opposite the third major surface 205 with astack thickness 209 defined therebetween. In aspects, the stack thickness 209 can be about 10nanometers (nm) or more, about 50 nm or more, about 100 nm or more, about 300 nm or more, about 500 nm or more, about 700 nm or more, about 1 µm or more, about 10 µm or less, about5 µm or less, about 2 µm or less, or about 1 µm or less. aspects, the stack thickness 209 canrange from about 10 nm to about 10 µm, from about 50 nm to about 5 µm, from about 100 nm to about 2 µm, from about 300 nm to about 1 µm, from about 500 nm to about 1 µm, or anyrange or subrange therebetween. In exemplary aspects, the stack thickness 209 can range from10 nm to 10 µm, from 50 nm to 5 µm, or from 50 nm to 500 nm.
[00368] In further aspects, the optical stack 203 can comprise an anti-reflective (AR)coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, and / or an edge filter coating. For example, the anti-reflective coatingof the optical stack 203 can be positioned between the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) and the substrate 103. In even further aspects, the optical stack 203(e.g., anti-reflective coating) can comprise two or more layers with differing refractive index values, for example, with a first low refractive index (RI) from about 1.3 to about 1.6 and a second high refractive index (RI) from about 1.6 to about 3.0. In still further aspects, the twoor more layers of the optical stack 203 can form an alternative set of layers, for example, 2 setsor more, 3 sets or more, 5 sets or more, or 10 sets or more, for example, from 2 to 15 periods, from 2 to 10 periods, from 2 to 12 periods, from 3 to 8 periods, from 3 to 6 periods, or any range or subrange therebetween.
[00369] In aspects, as shown in FIGS. 2B and 36B, the coated article 211 comprisesoptical stack 203a comprising a plurality of a silicon-containing oxide, a silicon-containingnitride, and / or a silicon-containing oxynitride layers. For example, the optical stack 203a canbe an anti-reflective coating. As shown, the optical stack 203a can comprise one or moreperiods 213 comprising two or more layers with different refractive indices, for example, a firstlow RI layer 215a and a second high RI layer 217a. For example, the optical stack 203a shownin FIG. 2B has 2 periods 213 comprising first low RI layers 215a and 215b (L)and a secondhigh RI layers 217a and 217b (H) that alternate in the following sequence of layers: L / H / L / H,ATTORNEY DOCKET NO. SP23-219WO although H / L / H / L could be provided in other aspects. An absolute value of a differencebetween the first low RI layer 215a and a second high RI layer 217a can be about 0.01 or more,about 0.05 or more, about 0.1 or more, or even 0.2 or more. Exemplary materials for the firstlow RI layer 215a include SiO2, Al2O3, GeO2, SiO2, AlOxNy, SiOxNy, SiuAlvOxNy, MgO, andMgAl2O4. Exemplary materials for the second high RI layer 217a include SiuAlvOxNy, AlN,oxygen-doped SiNx, SiNx, Si3N4, AlOxNy, SiOxNy, Ta2O5, Nb2O5, HfO2, TiO2, ZrO2, Y2O3, ZrO2, Al2O3, and diamond-like carbon. The oxygen content of the materials for the high RIlayer(s) 217a and 217b may be minimized, especially in SiNx or AlNx materials. The foregoingmaterials may be hydrogenated up to about 30% by weight. As used herein, it is to be understood that the subscripts (e.g., “u,” “v”, “x,” “y,” and “z”) range from greater than 0 to 1, where the subscripts sum to 1 to represent an “atomic fraction formula.” See, for example: (i) Charles Kittel, Introduction to Solid State Physics, seventh edition, John Wiley & Sons, Inc., NY, 1996, pp. 611-627; (ii) Smart and Moore, Solid State Chemistry, An introduction, Chapman & Hall University and Professional Division, London, 1992, pp. 136-151; and (iii) James F. Shackelford, Introduction to Materials Science for Engineers, Sixth Edition, Pearson Prentice Hall, New Jersey, 2005, pp. 404-418.The balance of the material (i.e., 1 minus the sum of the subscripts) is the first atom (e.g., SiNx with x = 0.57 actually corresponds to Si0.43N0.57,which is the same as Si3N4). Also, the sum of all subscripts is greater than 0.
[00370] In aspects, the optical stack 203a can include the antireflective structure,antireflective coating, or outer optical film described in U.S. Patent No. 10,948,629, issued March 16, 2021, U.S. Published Application No.2022 / 0011468, and / or WIPO Publication WO 2022 / 125846, which are incorporated by reference in their entirety. In aspects, as shown inFIG. 2B, the optical stack 203a can comprise a capping layer 219. In further aspects, thecapping layer 219 can comprise a low refractive index material, which can be the same materialas the first low RI layer 215a. In further aspects, the capping layer 219 can comprise a silicon-containing oxide (e.g., silicon dioxide), a silicon-containing nitride (e.g., an oxide-doped silicon nitride, silicon nitride, etc.), and a silicon-containing oxynitride (e.g., silicon oxynitride). An exemplary aspect of the capping layer is silicon dioxide (SiO2). In aspects, asshown, the layer of the optical stack 203 closest to the substrate 103 can be a low index layer(i.e., first low RI layer 215a) and the layer closest to the surface-modifying layer 113 (FIG.2B) or the planarization layer 123 (FIG. 36B) can be a low index layer (e.g., capping layer219). An exemplary combination of materials for the optical stack is SiO2 for the first low RI layer, silicon nitride (e.g., Si3N4, SiNx) or silicon oxynitride (SiOxNy) for the second high RI layer, and silicon dioxide (SiO2) for the capping layer.ATTORNEY DOCKET NO. SP23-219WO
[00371] In aspects, the coated article 211 can comprise a stack thickness 209acorresponding to a physical thickness of the optical stack 203a in a range from about 50 nm toless than 500 nm, from about 75 nm to about 490 nm, from about 100 nm to about 180 nm, from about 125 nm to about 475 nm, from about 150 nm to about 450 nm, from about 175 nm to about 425 nm, from about 200 nm to about 400 nm, from about 225 nm to about 375 nm, from about 250 nm to about 350 nm, from about 250 nm to about 340 nm, or any range or subrange therebetween. As used herein, the term “optical thickness” is determined by (n*d), where "n" refers to the RI of the sub-layer and "d" refers to the physical thickness of the layer.In aspects, at least one layer in the optical stack 203a can have an optical thickness from about2 nm to about 200 nm, from about 10 nm to about 100 nm, from about 15 nm to about 90 nm, from about 50 nm to about 80 nm, or any range or subrange therebetween. In further aspects,the first low RI layers 215a and 215b in periods 213 in the optical stack 203 can be within ormore of the ranges mentioned in the previous sentence. In aspects, a combined physicalthickness of the second high RI layers 217a and 217b can be about 90 nm or more, about 100nm or more, about 120 nm or more, about 130 nm or more, about 150 nm or more, or less than500 nm. For example, the combined physical thickness of the second high RI layers 217a and217b can range from about 90 nm to less than 500 nm, from about 100 nm to about 300 nm, from about 120 nm to about 200 nm, or any range or subrange therebetween. In aspects, thecombined physical thickness of the second high RI layers 217a and 217b as a percentage ofthe physical thickness of the stack thickness 209a can be about 30% or more, about 35% ormore, about 40% or more, or about 45% or more, for example, ranging from about 35% to about 75%, from about 40% to about 65%, from about 45% to about 55%, or any range or subrange therebetween.
[00372] In aspects, the optical stack 203a of the coated article 211 can comprise aresidual stress of less than about +50 MPa (tensile) to about -1000 MPa (compression). In some implementations of the article 100, the anti-reflective coating is characterized by a residual stress from about -50 MPa to about -1000 MPa (compression), or from about -75 MPa to about -800 MPa (compression). Unless otherwise noted, residual stress in the anti-reflective coatingis obtained by measuring the curvature of the substrate 103 before and after deposition of theanti-reflective coating, and then calculating residual film stress according to the Stoney equation according to principles known and understood by those with ordinary skill in the field of the disclosure.
[00373] In aspects, the optical stack 203a and / or the coated article 211 may exhibit avisible photopic average reflectance of about 1% or less, about 0.9% or less, about 0.8% orATTORNEY DOCKET NO. SP23-219WO less, about 0.7% or less, about 0.6% or less, about 0.5% or less, about 0.4% or less, about 0.3% or less, or about 0.2% or less, over the optical wavelength regime. These photopic average reflectance values may be exhibited at incident illumination angles in the range from about 0° to about 20°, from about 0°to about 40°, or from about 0° to about 60°. As used herein, “photopic average reflectance” mimics the response of the human eye by weighting the reflectance versus wavelength spectrum according to the human eye’s sensitivity. Photopic average reflectance may also be referred to as the luminance, or tristimulus Y value of reflected light, according to known conventions, for example CIE color space conventions. The photopicaverage reflectance is defined as the spectral reflectance, multiplied by theilluminant spectrum, , and the CIE’s color matching function, , related to the eye’sspectral response:
[00374] Further, the article exhibits a CIE a* value, in reflectance, from about -10 to+2 and a CIE b* value, in reflectance, from -10 to +2, the CIE a* and CIE b* values each measured on the optical film structure at a normal incident illumination angle. In aspects, theoptical stack 203a and / or the coated article 211 can exhibit a photopic average lighttransmission of about 90% or greater, 92% or greater, 94% or greater, 96% or greater, or 98%or greater, over the optical wavelength regime. In some embodiments, the optical stack 203aand / or the coated article 211 exhibits an average light transmission of about 87% or greater,88% or greater, 89% or greater, 90% or greater, 91% or greater, 92% or greater, 93% or greater, 94% or greater, or 95% or greater, over the optical wavelength regime in the infrared spectrum from 800 nm to 1000 nm, from 900 nm to 1000 nm, or from 930 nm to 950 nm. In aspects, theoptical stack 203a and / or the coated article 211 can exhibit a hardness of 8 GPa or greatermeasured at an indentation depth of about 100 nm or a maximum hardness of 9 GPa or greater measured over an indentation depth range from about 100 nm to about 500 nm, the hardness and the maximum hardness measured by a Berkovich Indenter Hardness Test (as defined below).
[00375] In aspects, as shown in FIGS. 2B and 36B, the coated article 211 comprisesoptical stack 203a comprising an optical film 231, a scratch-resistant layer 233, and an optionalcapping layer 229. In aspects, the optical stack 203b can include the scratch resistant coating,anti-reflective coating, and / or optical film structure described in U.S. Patent No. 9,328,016, issued May 3, 2016, U.S. Patent No. 9,684,097, issued June 20, 2017, U.S. Patent No.ATTORNEY DOCKET NO. SP23-219WO 9,703,011, issued July 11, 2017, U.S. Patent No. 9,079,802, issued July 14, 2015, U.S. Patent No.9,726,786, issued August 8, 2017, U.S. Patent No.10,416,352, issued September 17, 2019,which are incorporated by reference in their entirety. For example, the optical stack 203b canbe an anti-reflective coating and / or a scratch-resistant coating.
[00376] In further aspects, as shown in FIGS. 2C and 36C, the optical film 231 of theoptical stack 203b can comprise one or more periods 223 comprising two or more layers withdifferent refractive indices, for example, a first low RI layer 225 and a second high RI layer227. For example, the optical stack 203b shown in FIG. 2C has 3 periods 223 forming theoptical film 231 with alternating first low RI layers 225 and second high RI layers 227. In evenfurther aspects, the optical film 231 can comprise any number of periods, for example, withinone or more of the ranges discussed above for the optical stack 203a. An absolute value of adifference between the first low RI layers 225 and the second high RI layers 227 can be about0.01 or more, about 0.05 or more, about 0.1 or more, or even 0.2 or more. In further aspects,the first low RI layers 225 can comprise any of the materials discussed above for the first lowRI layer 215a, for example, silicon dioxide (SiO2). In further aspects, the second high RI layers227 can comprise any of the materials discussed above for the second high RI layer 217a, forexample, SiOxNy. In further aspects, a layer of the first low RI sub-layers 225 and / or the secondhigh RI sub-layers 227 can comprise an optical thickness (n*d) in the range from about 2 nmto about 200 nm, from about 10 nm to about 100 nm, from about 15 nm to about 100 nm, or any range or subrange therebetween. In even further aspects, all of the layers in the optical film231 or all of the second high RI layers in the optical film 231 can have an optical thicknesswithin one or more of the ranges mentioned in the previous sentence. In further aspects, a layerof the first low RI sub-layers 225 and / or the second high RI sub-layers 227 can comprise aphysical thickness from about 10 nm to about 800 nm, from about 10 nm to about 500 nm, from about 10 nm to about 300 nm, from about 10 nm to about 200 nm, from about 20 nm toabout 100 nm, or any range or subrange therebetween. In further aspects, the optical stack 203and / or any one or of the layers or sections therein (e.g., optical film 231, a scratch-resistantlayer 233, an optional capping layer 229) may exhibit an extinction coefficient (at a wavelengthof about 400 nm) of about 10-4or less.
[00377] In further aspects, as shown in FIGS. 2C and 36C, the scratch-resistant layer233 can include an inorganic carbide, nitride, oxide, diamond-like material, or combination ofthese. Examples of suitable materials for the scratch-resistant layer 233 include metal oxides,metal nitrides, metal oxynitride, metal carbides, metal oxycarbides, and / or combinations thereof combination thereof. Exemplary metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn,ATTORNEY DOCKET NO. SP23-219WO Hf, Ta and W. Specific examples of materials that may be utilized in the scratch-resistant layer 233 may include Al2O3, AlN, AlOxNy, Si3N4, SiOxNy, SiuAlvOxNy, diamond, diamond-like carbon, SixCy, SixOyCz, ZrO2, TiOxNy, or combinations thereof. In even further aspects, thescratch-resistant layer 233 can comprise the same material as the second high RI layers 227,for example, SiOxNy. In even further aspects, a physical thickness of the scratch-resistant layer and / or the optical stack can be from about 0.05 µm to about 3 µm, from about 0.1 µm to about 3 µm, from about 0.2 µm to about 3 µm, from about 0.3 µm to about 2.2 µm, from about 0.5 µm to about 2.1 µm, from about 1 µm to about 2.1 µm, from about 1.8 µm to about 2.1 µm, or any range or subrange therebetween. In exemplary aspects, a physical thickness of the scratch- resistant layer can be from 0.05 µm to 3 µm, from 0.3 µm to 2.2 µm, or from 1 µm to 2.1 µm.The scratch-resistant layer 233 and / or the optical stack 203b may exhibit a hardness of about8 GPa or greater, about 10 GPa or greater, about 13 GPa or greater, or about 17 GPa or greater, as measured by the Berkovich Indenter Hardness Test (as described below).
[00378] Although not shown, it is to be understood that the scratch-resistant layer canbe sandwiched by portions of the optical film. For example, 3 or more periods can be positioned between the scratch-resistant layer and the substrate while 2 or more periods can be positioned between the scratch-resistant layer and the surface-modifying layer (e.g., fingerprint-hiding coating).
[00379] In further aspects, as shown in FIGS. 2C or 36C, the optical stack 203b cancomprise capping layer 229 disposed over (e.g., disposed on) the scratch-resistant layer. Ineven further aspects, the capping layer 229 can include a low refractive index material, such asSiO2, Al2O3, GeO2, SiO2, AlOxNy, SiOxNy, SiuAlvOxNy, MgO, MgF2, BaF2, CaF2, DyF3, YbF3,YF3, or CeF3. In further aspects, the capping layer 229 can comprise the same material as thefirst high RI layers 225, for example, SiO2. In further aspects, a thickness of the capping layer229 can be from about 10 nm to about 120 nm, from about 20 nm to about 115 nm, from about 50 nm to about 110 nm, from about 80 nm to about 110 nm, from about 90 nm to about 105nm, or any range or subrange therebetween. The capping layer 229 may exhibit an intrinsichardness in the range from about 7 GPa to about 10 GPa, as measured by the Berkovich Indenter Hardness Test (as measured on the surface of a layer of the same material of the capping layer, formed in the same manner, but having a thickness of about 1 micrometer or greater).
[00380] In further aspects, a stack thickness 209b corresponding to a physical thicknessof the optical stack 203b can range from about 0.2 µm to about 3 µm, from about 0.5 µm toabout 3 µm, from about 1 µm to about 3 µm, from about 1.2 µm to about 3 µm, from about 1.5ATTORNEY DOCKET NO. SP23-219WO µm to about 3 µm from about 2 µm to about 2.6 µm, or any range or subrange therebetween.In further aspects, the optical stack 203b can exhibit an average light reflectance of about 0.5%or less, about 0.25% or less, about 0.1% or less, or even 0.05% or less over the opticalwavelength regime. In further aspects, the optical stack 203b can exhibit an averagetransmittance or average reflectance having an average oscillation amplitude of about 5 percentage points or less over the optical wavelength regime. In further aspects, the opticalstack 203b may exhibit an average light transmission of 80% or greater, 82% or greater, 85%or greater, 90% or greater, 90.5% or greater, 91% or greater, 91.5% or greater, 92% or greater, 92.5% or greater, 93% or greater, 93.5% or greater, 94% or greater, 94.5% or greater, or 95% or greater.
[00381] The optical stack 203, 203a, or 203b may be formed using various depositionmethods, for example, vacuum deposition techniques, chemical vapor deposition (e.g., plasma enhanced chemical vapor deposition (PECVD), low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or nonreactive sputtering or laser ablation), thermal or e-beam evaporation and / or atomic layer deposition. Liquid-based methods may also be used, for example, printing, spraying, or slot coating. Where vacuumdeposition is utilized, inline processes may be used to form the optical stack 203, 203a, or 203bin one deposition run. In aspects, the vacuum deposition can be made by a linear PECVDsource. In aspects, the optical stack 203, 203a, or 203b can be prepared using a sputteringprocess (e.g., a reactive sputtering process), chemical vapor deposition (CVD) process, plasma- enhanced chemical vapor deposition process, or some combination of these processes. Inaspects, the optical stack 203a or 203b comprising low RI layer(s) 215a, 215b, or 225 andhigh RI layer(s) 217a, 217b, or 227 can be prepared according to a reactive sputtering process.According to some embodiments, optical stack 203a or 203b (including low RI layer 215a,215b, or 225, high RI layer 217a, 217b, or 227 and capping layer 219 or 229) can be fabricatedusing a metal-mode, reactive sputtering in a rotary drum coater. The reactive sputtering process conditions were defined through careful experimentation to achieve the desired combinations of hardness, refractive index, optical transparency, low color, and controlled film stress.
[00382] In further aspects, the optical stack 203 can comprise a gradient coatingcomprising a refractive index gradient. For example, the gradient coating of the optical stack203 can be positioned between the surface-modifying layer 113 (FIG. 2A) or the planarizationlayer 123 (FIG. 36A) and the substrate 103. In even further aspects, the refractive indexgradient can span a range of refractive index values of about 0.2 or more, about 0.3 or more,ATTORNEY DOCKET NO. SP23-219WO about 0.4 or more, about 1 or less, about 0.8 or less, about 0.6 or less, or about 0.5 or less, for example, from about 0.2 to about 1, from about 0.3 to about 0.8, from about 0.4 to about 0.6, or any range or subrange therebetween. In even further aspects, the gradient coating can comprise a concentration gradient of one or more of oxygen, nitrogen, and / or silicon. It should be understood, however, that other functional coatings may be provided in the optical stack203 to achieve predetermined optical properties of the coated article 201, 211, 221, 3501, 3601,3611, or 3621.
[00383] According to one or more aspects, an anti-reflective coating can be used incombination with an anti-glare (AG) surface. Anti-glare surface treatments can impact the performance of anti-reflective coatings. Thus, selection of the proper anti-glare surface can be important for optimal performance, particularly in difficult use environments, such as vehicle interiors. In such environments, it may be beneficial for anti-glare surfaces on a cover glass to have the minimum sparkle and provide the appropriate anti-glare effect and tactile while meeting a required Contrast Ratio (CR) under sunlight. For example, a sample can be prepared with a chemically-etched Ultra-Low Sparkle (ULS) AG surface on a glass substrate made of Corning® Gorilla® Glass with an anti-reflective coating according to embodiments of this disclosure, and an easy-to-clean (ETC) coating to provide stable color appearance with wide- viewing angles to facilitate on sunlight viewability.
[00384] Anti-glare surfaces can be prepared on a Corning® Gorilla® Glass substrateby using a chemical etching method that enables ultra-low sparkle performance suitable for high resolution display up to 300 pixels per inch (PPI). Anti-glare glass optical properties can be analyzed, including with and without contributions from specular reflection (i.e., specular component excluded (SCE) or specular component included (SCI)), transmission haze, gloss, distinctness of image (DOI), and sparkle. Further information regarding these properties and how these measurement are made can be found in (1) C. Li and T. Ishikawa, Effective Surface Treatment on the Cover Glass for Auto-Interior Applications, SID Symposium Digest of Technical Papers Volume 1, Issue 36.4, pp. 467 (2016); (2) J. Gollier, G.A. Piech, S.D. Hart, J.A. West, H. Hovagimian, E.M. Kosik Williams, A. Stillwell and J. Ferwerda, Display Sparkle Measurement and Human Response, SID Symposium Digest of Technical Papers Volume 44, Issue 1 (2013); and (3) J. Ferwerda, A. Stillwell, H. Hovagimian and E.M. Kosik Williams, Perception of sparkle in anti-glare display screen, Journal of the SID, Vol 22, Issue 2 (2014), the contents of which are incorporated herein by reference.
[00385] The balance of the five metrics of SCE / SCI (see previous paragraph),transmission haze, gloss, distinctness of image (DOI), and sparkle is important for maximizingATTORNEY DOCKET NO. SP23-219WO the benefits of an anti-glare for display readability, tactility on the glass surface, and the aesthetic appearance of high-performance touch displays in applications such as vehicle interiors. Sparkle is a micro-scattering interaction of the anti-glare surface with LCD pixels to create bright spots degrading image quality, especially at high resolution. The sparkle effect can be characterized using the method of the Pixel Power Deviation with reference (PPDr) to examine the sparkle effect on different resolution displays. For example, ultra-low sparkle anti- glare glass with less than 1% PPDr will have invisible sparkle effect on a display of less than 300 pixels-per-inch (PPI). However, up to 4% PPDr may be acceptable depending on the contents of display, based on the preference of the end-user. In vehicular or automotive interior settings, about 120 PPI to about 300 PPI is acceptable, and displays over 300 PPI have diminishing value.
[00386] In aspects, the substrate 103 and / or an anti-glare surface of the optical stack203, 203a, and / or 203b can comprise a textured surface, for example, having particulates, amechanically roughened surface, and / or a chemically roughened surface. In further aspects, the anti-glare and / or textured surface can be formed by treating the corresponding surface with an anti-glare treatment. Exemplary aspects of anti-glare treatments include chemical or physical surface treatment to form irregularities and / or etching the surface (e.g., with hydrofluoric acid) to create an etched region exhibiting anti-glare properties.
[00387] Throughout the disclosure, hardness of the optical stack is measured using the“Berkovich Indenter Hardness Test.” As used herein, the “Berkovich Indenter Hardness Test”measures the hardness of a material by indenting the surface (e.g., fourth major surface 207)with a diamond Berkovich indenter to form an indent to an indentation depth in the range fromabout 50 nm to about 1000 nm (or the entire thickness of the optical stack 203, 203a, or 203b,whichever is less) and measuring the hardness from this indentation at various points along the entire indentation depth range, along a specified segment of this indentation depth (e.g., in the depth range from about 100 nm to about 500 nm), or at a particular indentation depth (e.g., at a depth of 100 nm, at a depth of 500 nm, etc.) generally using the methods set forth in Oliver, W.C. and Pharr, G. M., “An improved technique for determining hardness and elastic modulususing load and displacement sensing indentation experiments”, J. Mater. Res., Vol. 7, No. 6,1992, 1564-1583; and Oliver, W.C. and Pharr, G.M., “Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements toMethodology”, J. Mater. Res., Vol. 19, No. 1, 2004, 3-20. Further, when hardness is measuredover an indentation depth range (e.g., in the depth range from about 100 nm to about 500 nm), the results can be reported as a maximum hardness within the specified range, wherein theATTORNEY DOCKET NO. SP23-219WO maximum is selected from the measurements taken at each depth within that range. As used herein, “hardness” and “maximum hardness” both refer to as-measured hardness values, not averages of hardness values. Similarly, when hardness is measured at an indentation depth, the value of the hardness obtained from the Berkovich Indenter Hardness Test is given for that particular indentation depth.
[00388] The optical stack 203, 203a or 203b, if present, can comprise a hardness ofgreater than about 8 GPa, by the Berkovich Indenter Hardness Test at an indentation depth ofabout 100 nm. The optical stack 203 may exhibit a hardness of about 8 GPa or greater, about9 GPa or greater, about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, or about 15 GPa or greater by the Berkovich Indenter Hardness Test at an indentation depth of about 100 nm. For example, the optical stack203 or 203a, including the surface-modifying layer 113 (e.g., fingerprint-hiding coating)and / or the planarization layer 123, as described herein, may exhibit a hardness of about 8 GPaor greater, about 10 GPa or greater or about 12 GPa or greater, by the Berkovich IndenterHardness Test at an indentation depth of about 100 nm. In aspects, the optical stack 203 or203b can exhibit a hardness ranging from about 8 GPa to about 30 GPa, from about 10 GPa to about 25 GPa, from about 12 GPa to about 20 GPa, from about 16 GPa to about 20 GPa, or any range or subrange therebetween. Such measured hardness values may be exhibited by theoptical stack 203, 203a, or 203b and / or the coated article 101, 201, 211, 221, 3501, 3601, 3611,or 3621 over an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm). Similarly, maximum hardness values of about 8 GPa or greater, about 9 GPa or greater, about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, or about 15 GPa or greater by the BerkovichIndenter Hardness Test may be exhibited by the optical stack 203 and / or the coated article 101,201, 211, 221, 3501, 3601, 3611, or 3621 over an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., from about 100 nm to about 300 nm, from about 100 nm to about 400 nm, from about 100 nm to about 500 nm, from about 100 nm to about 600 nm, from about 200 nm to about 300 nm, from about 200 nm to about 400 nm, from about 200 nm to about 500 nm, or from about 200 nm to about 600 nm).
[00389] As shown in FIGS. 1, 2A-2C, 35, and 36A-36C, the coated article 101, 201,221, 221, 3501, 3601, 3611, or 3621 comprises the surface-modifying layer 113 (e.g.,ATTORNEY DOCKET NO. SP23-219WOfingerprint-hiding coating), disposed over the first major surface 105 of the substrate 103. Thesurface-modifying layer 113 comprises an inner surface 117 facing the first major surface 105of the substrate 103. In aspects, as shown in FIG. 1, the surface-modifying layer 113 (e.g.,inner surface 117) can be disposed on and / or bonded to the first major surface 105 of thesubstrate 103. In aspects, as shown in FIGS.2A-2C and 36A-36C, the surface-modifying layer113 (e.g., fingerprint-hiding coating) can be disposed on the optical stack 203, 203a, or 203b.In aspects as shown in FIG. 35, the surface-modifying layer 113 (e.g., inner surface 117) canbe disposed on and / or bonded to the first surface area 125 of the planarization layer 123(discussed below). In aspects, as shown in FIGS. 1, 2A-2C, the surface-modifying layer 113(e.g., fingerprint-hiding coating) comprises an exterior surface 115 that forms an exteriorsurface of the coated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621. Consequently, auser would interact with the coated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621 by,for example, touching the exterior surface 115 or viewing an image through the exterior surface115. A surface-modifying thickness 119 is defined as an average distance between the innersurface 117 and the exterior surface 115. In aspects, the surface-modifying thickness 119 canbe about 1 nm or more, about 2 nm or more, about 3 nm or more, about 5 nm or more, about 10 nm or more, about 20 nm or more, about 50 nm or more, about 75 nm or less, about 50 nm or less, about 25 nm or less, about 15 nm or less, about 10 nm or less, about 8 nm or less, about 7 nm or less, about 6 nm or less, about 5 nm or less, or about 4 nm or less. In aspects, thesurface-modifying thickness 119 can be in a range from about 1 nm to about 75 nm, from about1 nm to about 50 nm, from about 1 nm to about 25 nm, from about 1 nm to about 15 nm, from about 2 nm to about 10 nm, from about 2 nm to about 8 nm, from about 2 nm to about 5 nm, from about 3 nm to about 5 nm, or any range or subrange therebetween. In aspects, the surface-modifying thickness 119 can be about 10 nm or less, for example in a range from about 1 nmto about 8 nm, from about 1 nm to about 5 nm, from about 2nm to about 4 nm, or any range orsubrange therebetween. The surface-modifying thickness 119 is determined usingellipsometry.
[00390] Throughout the disclosure, “surface-modifying layer” refers to a layer that ischaracterized by changing a physical property or other behavior of the coated article. For example, a surface-modifying layer can modify one or more of a water contact angle, an oleic contact angle, a visibility of a fingerprint (e.g., simulated fingerprint), and / or an ability to remove a fingerprint (e.g., by wiping).
[00391] In aspects, the surface-modifying layer can be an anti-fingerprint coating.Throughout the disclosure, a surface-modifying layer is an “anti-fingerprint” coating if theATTORNEY DOCKET NO. SP23-219WO coating on a substrate can reduce the visibility of, reduce a color shift of, and / or reduce droplet formation of fingerprint oil disposed thereon relative to the substrate without the coating. As used herein, the visibility of a fingerprint refers to an absolute value of a difference in brightness (e.g., CIELAB L* value) for a portion of the anti-fingerprint coating with the fingerprint oil and another portion of the anti-fingerprint coating without the fingerprint oil. As used herein, the color shift of the substrate refers to a difference in measured color as √((a1* - a2*)2+ (b1* - b2*)2), where a* refers to CIELAB a* values, b* refers to CIELAB b* values, subscript 1 refers to a portion of the anti-fingerprint coating without fingerprint oil, and subscript 2 refers to a portion of the anti-fingerprint coating with fingerprint oil. An anti- fingerprint coating can reduce droplet formation, which can increase a visibility and / or color shift of fingerprint oil, by being oleophilic, as defined below. Additionally, the anti-fingerprint coating can enable the removal of aqueous material (e.g., water droplets, sweat droplets) from the coating, for example, by being hydrophobic, as defined below. In further aspects, the anti- fingerprint coating can exhibit an (e.g., as-formed) water contact angle from 90° to 120°, an (e.g., as-formed) oleic acid contact angle of 40° or less, and a coefficient of friction of 0.25 or less. In further aspects, the easy-to-clean coating can be substantially free and / or free of fluorine. In aspects, a diiodomethane contact angle of an anti-fingerprint coating (e.g., as- formed) can be about 60° or more, about 62° or more, about 65° or more, about 80° or less, about 75° or less, about 73° or less, or about 70° or less. In aspects, a diiodomethane contact angle of an anti-fingerprint coating (e.g., as-formed) can range from about 60° to about 80°, from about 62° to about 75°, from about 65° to about 72°, or any range or subrange therebetween. In aspects, an anti-fingerprint coating can be oleophilic. In aspects, a hexadecane contact angle and / or an oleic acid contact angle of an anti-fingerprint coating (e.g., as-formed) can be about 45° or less, about 40° or less, about 30° or less, about 25° or less, about 20° or less, or the anti-fingerprint coating can wet hexadecane and / or oleic acid. In further aspects, the anti-fingerprint coating (e.g., as formed) wets hexadecane and / or oleic acid. Providing a low diiodomethane contact angle (e.g., about 60° or less) and / or a low hexadecane contact angle (e.g., about 30° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oil to be dispersed across the anti-fingerprint coating rather than beading up into pronounced droplets.
[00392] In aspects, the surface-modifying layer can be a fingerprint-hiding coating.Throughout the disclosure, a “fingerprint-hiding coating” can reduce the visibility of and / or reduce a color shift of fingerprint oil disposed thereon relative to a glass-based substrate without the coating. As used herein, the visibility of a fingerprint refers to an absolute value ofATTORNEY DOCKET NO. SP23-219WO a difference in brightness (e.g., CIELAB L* value) for a portion of the fingerprint-hiding coating with the fingerprint oil and another portion of the fingerprint-hiding coating without the fingerprint oil. As used herein, the color shift of the glass-based substrate refers to a difference in measured color as √((a1* - a2*)2+ (b1* - b2*)2), where a* refers to CIELAB a* values, b* refers to CIELAB b* values, subscript 1 refers to a portion of the fingerprint-hiding coating without fingerprint oil, and subscript 2 refers to a portion of the fingerprint-hiding coating with fingerprint oil. Specifically, the fingerprint-hiding coating can cause fingerprint oil to spread out over the surface of the fingerprint-hiding coating. Reducing the thickness of fingerprint oil droplets and / or increasing an area of fingerprint-hiding coating covered by the fingerprint oil can decrease a color shift and / or visibility associated with the fingerprint oil. Fingerprint-hiding coatings that can be oleophilic are to be contrasted with other coatings (e.g., anti-fingerprint coatings) that can reduce droplet formation by being oleophobic. Additionally, the fingerprint-hiding coating can enable the removal of aqueous material (e.g., water droplets, sweat droplets) from the coating, for example, by being hydrophobic, as discussed herein. In further aspects, the fingerprint-hiding coating can exhibit an (e.g., as-formed) water contact angle from 90° to 120°, an (e.g., as-formed) oleic acid contact angle of 40° or less, and a coefficient of friction of 0.25 or less. In further aspects, the fingerprint-hiding coating can be a fluorine-containing material. Alternatively, in further aspects, the fingerprint-hiding coating can be substantially free and / or free of fluorine. In further aspects, the finger-hiding coating can exhibit a hexadecane contact angle of 20° or less (or wet hexadecane) and / or a diiodomethane contact angle of 60° or more.
[00393] In aspects, the surface-modifying layer can be an easy-to-clean coating.Throughout the disclosure, a surface-modifying layer is an “easy-to-clean” coating if the coating on a glass-based substrate can repel material and / or facilitate removal of material disposed thereon relative to the glass-based substrate without the coating. As used herein, an ability to repel material is determined based on a contact angle with higher contact angles associated with greater repulsion. As used herein, an ability to remove material is measured by wiping the material disposed on the surface (e.g., coating or glass-based substrate) with a cheesecloth (see details from the Cheesecloth Abrasion Test with the modification that the material is disposed on the surface before wiping) and the visibility of the material is monitored. A decreased visibility (e.g., fewer wiping cycles to achieve a predetermined reduction is visibility) is associated with a coating facilitating removal of material disposed thereon. In further aspects, the easy-to-clean coating can exhibit an (e.g., as-formed) water contact angle from 90° to 120°, an (e.g., as-formed) oleic acid contact angle of 50° or more, and a coefficientATTORNEY DOCKET NO. SP23-219WO of friction of 0.25 or less. In further aspects, the easy-to-clean coating can be a fluorine- containing material. Alternatively, in further aspects, the easy-to-clean coating can be substantially free and / or free of fluorine. In aspects, a diiodomethane contact angle of an anti- fingerprint coating (e.g., as-formed) can be about 60° or more, about 62° or more, about 65° or more, about 80° or less, about 75° or less, about 73° or less, or about 70° or less. In aspects, a diiodomethane contact angle of an anti-fingerprint coating (e.g., as-formed) can range from about 60° to about 80°, from about 62° to about 75°, from about 65° to about 72°, or any range or subrange therebetween. In aspects, the an anti-fingerprint coating can be oleophilic. In aspects, a hexadecane contact angle of the an anti-fingerprint coating (e.g., as-formed) can be about 45° or less, about 40° or less, about 30° or less, about 25° or less, about 20° or less, or the an anti-fingerprint coating can wet hexadecane. In further aspects, the an anti-fingerprint coating (e.g., as formed) wets hexadecane. Providing a low diiodomethane contact angle (e.g., about 60° or less) and / or a low hexadecane contact angle (e.g., about 30° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oil to be dispersed across the surface-modifying layer rather than beading up into pronounced droplets.
[00394] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)can comprise at least one alkyl silane at the exterior surface 115 and bonded to the rest of thecoated article 101, 201, 211, 212, 3501, 3601, 3611, and / or 3621 (e.g., planarization layer 123,optical stack 203, 203a, or 203b, and / or substrate 103). As used herein, an “alkyl silane” refersto a compound comprising an alkyl chain directly bonded to a silicon atom of a silane group, and the silane group can be bonded to other silane groups (e.g., forming a siloxane or siloxane- like network). In further aspects, the alkyl silane can comprise a string of contiguous carbon atoms from 3 carbons to about 34 carbons (i.e., a C3-C34 alkyl group), for example, from 4 carbons to 34 carbons (i.e., a C4-C34alkyl group) from 6 carbons to 34 carbons (i.e., a C6-C34alkyl group), from 8 carbons to 20 carbons (i.e. a C8-C20alkyl group). In aspects, an alkyl group of the alkyl silane can comprise from 4 carbons to about 34 carbons (i.e., a C4-C34 alkyl group) (e.g., from 6 carbons to 34 carbons (i.e., a C6-C34 alkyl group), from 8 carbons to 20 carbons (i.e. a C8-C20 alkyl group)), for example, an iso-octyl alkyl group, a dodecyl alkyl group, an octadecyl alkyl group, or combinations thereof. Exemplary aspects of alkyl silanes includepropyl silanes (e.g., chloropropyltrimethoxysilane – see FIG. 17B), hexyl silanes (e.g., 1,6-bis(trichlorosilyl)hexane), octylsilanes (e.g., 1,8-bis(chlorodimethylsilyl)octane – see FIG.17A and 1,8-bis(dimethylmethoxysilyl)octane – see FIG. 17H), iso-octylsilanes (e.g., iso-octyltrimethoxysilane), dodecylsilanes (e.g., dodecyltrimethoxysilane), octadecylsilanes (e.g.,octadecyltrimethoxysilane – see FIG. 17G), or combinations thereof. In aspects, the alkylATTORNEY DOCKET NO. SP23-219WO silane may comprise a bipodal or multipodal alkyl silane with two or more silane head groups on each end of the alkyl group of the alkyl silane (e.g. bis-silane or tris-silane). Exemplary aspects of such bipodal alkyl silanes include 1,6-bis(trimethoxysilyl)hexane (bishexane) (seeFIG. 17E) and 1,8-bis(trimethoxysilyl)octane (BISMO) (see FIG. 17F). In aspects, the alkylsilane may include a combination of one or more monopodal alkyl silanes and one or more bipodal alkyl silanes. A mixture of the alkyl silanes can be used to obtain various desirable attributes, e.g. finger-print hiding in combination with good durability. The coating therefore can be composed of two or more functionalities. For instance, the alkyl silane may include one or more bipodal alkyl silanes, such as 1,8-bis(chlorodimethylsilyl) octane, 1,8- bis(dimethylmethoxysilyl)octane, 1,6-bis(trichlorosilyl) hexane, bis(triethoxysilyl) methane, 1,2-bis(triethoxysilyl) ethane, 1,6-bis(trimethoxysilyl) hexane, 1,8-bis(triethoxysilyl) octane, 1,8-bis(trimethoxysilyl) octane, or combinations thereof in addition to one or more monopodal alkyl silanes, such as octadecyl trimethoxysilane, dodecyl trimethoxysilane, or combinations thereof. Without intending to be bound by any particular theory, it is believed that multipodal alkyl silanes (e.g. bipodal alkyl silanes) are thought to create longer chains by polycondensation between molecules. In the case of the mono-functional silanes the non-reactive methyl groups may disrupt chain packing. In the case of di- or tri-functional silanes, polycondensation can occur from multiple sites and the molecule can become more branched, resulting in poor ordering. Due to their bipodal nature, these materials may contain unreacted, terminal hydroxyl groups. In some aspects, it may be beneficial to react or “cap” these groups with a monofunctional, monopodal silane or other molecule. Such examples include monofunctional alkylsilanes where the alkyl chain comprises 3 to 36 carbons. Other suitable steps include methylation such as through the use of hexamethyldisilazane (HMDS). Suitable functionalization for improved durability include linear alkylsilanes where the alkyl chain comprises 3 to 26 carbons. Certain examples include octadecyltrimethoxysilane and dodecyltrimethoxysilane. Such examples are thought to form well ordered SAMs that maintain high water contact angles, even after rubber abrasion testing on bare glass. Good rubber abrasion performance on bare glass result in enhanced durability (steelwool, cheesecloth) whencombined with the planarization layer 123. In aspects, a ratio between the monopodal alkylsilanes to the multipodal alkyl silanes used to form the polymer at the surface-modifying layer113 may be selected to tune the finger-print hiding attributes and the cleanability and / ordurability attributes of the surface-modifying layer 113 (e.g., fingerprint-hiding coating)formed therefrom. Without intending to be bound by any particular theory, it is believed that the monopodal alkyl silane may increase the cleanability and / or durability of the surface-ATTORNEY DOCKET NO. SP23-219WOmodifying layer 113 formed therefrom, and the bipodal silane may increase finger-print hidingattributes of the surface-modifying layer 113 formed therefrom. The deposition of monopodalsilanes and multipodal silanes at the surface-modifying layer 113 may include various ratiosbetween the monopodal silanes and the multipodal silanes of the alkyl silane. In embodiments, the alkyl silane may comprise a ratio of the multimodal alkyl silane to the monopodal alkyl silane of from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2. In aspects, the alkyl silane can be free of one or more of an alkene, an aryl group, an alkenyl group, a ketone, a carboxylic acid group, chlorine, or combinations thereof. In further aspects, the alkyl silane may comprise a methoxy silane (e.g., trimethoxy silane) and / or a trialkoxy silane (e.g., trimethyl silane or triethylsilane in addition to the above- mentioned alkyl group). In further aspects, the silane may comprise an alkyl trimethoxysilane, an alkyl triethoxysilane, an alkyl trichlorosilane, an alkyl trimethoxy silane, an alkyl triethoxy silane, or combinations thereof (e.g. dichloromthoxysilane, chlorodimethoxysilane). In further aspects, the alkyl silane may comprise a chlorosilane, a methyl silane, a methoxy silane, a trimethoxy silane, a triethoxy silane, or combinations thereof (e.g., chlorodimethylsilane, chlorodimethyoxysilane, trichlorosilane). Providing an alkyl silane can reduce a surface energy (e.g., total, dispersive, polar) of the surface-modifying layer (e.g., fingerprint-hiding coating), which can enable the surface-modifying layer (e.g., fingerprint-hiding coating) to be oleophilic. Reacting the substrate and / or an initial coating with an alkoxy silane or a chlorosilane can be well-bonded to the initial coating and enable low surface energy (e.g., total surface energy or about 30 mN / m or less, polar surface energy of about 5 mN / m or less).
[00395] In further aspects, as discussed above, the alkyl silane can comprise a one ormore of the silanes discussed above in addition to an additional alkyl silane that can contribute to the siloxane part of the structure (i.e., the [Si(R”)2O]n part of the polymeric structure discussed in the following paragraphs). In even further aspects, the additional alkyl silane can comprise a dialkylsilane with silanes at both ends of the dialkylsilane, and the alkyl groups of dialkyl silane can be methyl, ethyl, or a combination thereof. An exemplary aspect of thedialkyl silane is a dimethyl silane, namely, dichloro-tetramethyl-disoloxane (see FIG. 17D),although other leaving groups can independently be groups other chlorine (e.g., selected fromATTORNEY DOCKET NO. SP23-219WO those discussed in the previous paragraph). In even further aspects, an amount of the additional alkyl silane as a wt% of a total amount of alkyl silanes can be about 1 wt% or more, about 5 wt% or more, about 10 wt% or more, about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, about 45 wt% or more, about 50 wt% or more, about 55 wt% or more, about 60 wt% or more, about 65 wt% or more, about 70 wt% or more, about 75 wt% or more, about 90 wt% or less, about 85 wt% or less, about 80 wt% or less, about 75 wt% or less, about 70 wt% or less, about 65 wt% or less, about 60 wt% or less, about 55 wt% or less, about 50 wt% or less, about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, or about 30 wt% or less. In even further aspects, an amount of the additional alkyl silane as a wt% of a total amount of the alkyl silanes can be in a range from about 1 wt% to about 90 wt%, from about 5 wt% to about 90 wt%, from about 10 wt% to about 85 wt%, from about 20 wt% to about 80 wt%, from about 25 wt% to about 75 wt%, from about 30 wt% to about 70 wt%, from about 35 wt% to about 65 wt%, from about 40 wt% to about 60 wt%, from about 45 wt% to about 55 wt%, from about 45 wt% to about 50 wt%, or any range or subrange therebetween. In preferred aspects, an amount of the additional alkyl silane as a wt% of a total amount of the alkyl silanes can be from 1 wt% to 90 wt% or from 25 wt% to 75 wt%. Alternatively, the alkyl silanes can exclude an additional alkyl silane and / or consist of a single alkyl silane selected from those discussed in the previous paragraph.
[00396] In aspects, alkyl silane at the exterior of the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) can be bonded to another part of the surface-modifying layer 113(e.g., fingerprint-hiding coating) by a silane group. In further aspects, the bond between the alkyl silane and the another part of the coated article can be a disiloxane group. A disiloxane group can be formed by the condensation of silanes. In even further aspects, the disiloxane group can include one or more dialkyl siloxanes (e.g., dimethylsiloxane(s) and / or diethylsiloxane(s)). As discussed in the in the following paragraphs, the alkyl silane at theexterior of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can be part of (i)a polymer of the alkyl silane or (ii) a block copolymer of the alkyl silane and a siloxane-based polymer.
[00397] In further aspects, the alkyl silane can be part of a polymer of the alkyl silanethat is bonded to another part of the coated article (e.g., the first major surface 105 of thesubstrate or the fourth major surface 207 of the optical stack 203 or 203a). In even furtheraspects, the polymer of the alkyl silane can be a dialkyl siloxane (e.g., dimethylsiloxane, diethylsiloxane, or combinations thereof) polymer. In even further aspects, the monomers of the polymer of the alkyl silane can be bonded together by a disiloxane group. In even furtherATTORNEY DOCKET NO. SP23-219WO aspects, the disiloxane may bond together the monomers of the polymer of the alkyl silane and one or more alkyl chains. In even further aspects, the disiloxane group can include one or more dimethyl siloxanes, diethyl siloxanes, or combinations thereof. For example, a structure of the polymer may comprise {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 or more, q can be 1 or more and / or can be a degree of polymerization. In still further aspects, R can be a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof. In particular aspects, R can be an alkoxide including a methoxy group, an ethoxy group, or combinations thereof. In yet further aspects, R can be a hydroxyl group or a chloro group. In yet further aspects, when n is 1, one or more of the following can also be true: R’ can be CH3, R” can be CH3, m can be 8, p can be 8, or combinations thereof. In still further aspects, n can be 1, and q can be within one or more of the corresponding ranges later in this paragraph. In still further aspects, n can be 2 or more (e.g., from 2 to 10, from 2 to 5, or 2), and q can be within one or more of the corresponding ranges later in this paragraph. For example, when n is 2 or more, one or more of the following can also be true: R’ can be CH3, R” can be CH3, m can be 8, p can be 8, or combinations thereof. In yet further aspects, n can be 2, and q can be within one or more of the corresponding ranges later in this paragraph. For example, when n is 2, one or more of the following can also be true: R’ can be CH3, R” can be CH3,m can be 8, p can be 8, or combinations thereof. In still furtheraspects, R’ and R” can be CH3, which results in the structure shown in FIG. 18A as both askeletal structure and SMILES. Further, as shown in FIG. 18A, the shown structure can bedirectly bonded to a surface of the substrate or optical film. In even further aspects, a degree of polymerization of the polymer can be 1 or more, 2 or more, 5 or more, 10 or more, 20 or more, 50 or more, 100 or less, 75 or less, 60 or less, 40 or less, 25 or less, 15 or less, 10 or less, or 5 or less. In even further aspects, a degree of polymerization of the polymer can be in a range from 1 to 100, from 2 to 100, from 5 to 75, from 10 to 60, from 20 to 40, or any range or subrange therebetween. In even further aspects, a degree of polymerization of the polymer can be about 40 or less, for example, from 1 to 40, from 1 to 25, from 1 to 15, from 1 to 10, from 2 to 5, or any range or subrange therebetween.
[00398] In even further aspects, a polymer of the alkyl silane may comprise a structure{OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH. In aspects, n is 1 and q is 1,ATTORNEY DOCKET NO. SP23-219WOwhich results in the structure shown in FIG. 18B. Further, as shown in FIG. 18B, the shownstructure can be directly bonded to a surface of the substrate or optical film. In aspects whereR is OSi(R’)2[CH2]m’, one or more monomers of the alkyl silane may form one or morebranches, as shown in FIG. 18C. In yet further aspects, when n is 1, one or more of thefollowing can also be true: R can be OCH3,, m can be 8, p can be 8, or combinations thereof. In still further aspects, n can be 1, and q can be within one or more of the corresponding ranges later in this paragraph. In still further aspects, n can be 2 or more (e.g., from 2 to 10, from 2 to 5, or 2), and q can be within one or more of the corresponding ranges later in this paragraph. For example, when n is 2 or more, one or more of the following can also be true: R’ can be CH3, R” can be CH3, m can be 8, p can be 8, or combinations thereof. In yet further aspects, n can be 2, and q can be within one or more of the corresponding ranges later in this paragraph. For example, when n is 2, one or more of the following can also be true: R can be OCH3, m can be 8, p can be 8, or combinations thereof. In still further aspects, R’ and R” can be CH3,which results in the structure shown in FIG. 18A as both a skeletal structure and SMILES.Further, as shown in FIG. 18A, the shown structure can be directly bonded to a surface of thesubstrate or optical film. In even further aspects, a degree of polymerization of the polymer canbe 1 or more, 2 or more, 5 or more, 10 or more, 20 or more, 50 or more, 100 or less, 75 or less, 60 or less, 40 or less, 25 or less, 15 or less, 10 or less, or 5 or less. In even further aspects, a degree of polymerization of the polymer can be in a range from 1 to 100, from 2 to 100, from 5 to 75, from 10 to 60, from 20 to 40, or any range or subrange therebetween. In even further aspects, a degree of polymerization of the polymer can be about 40 or less, for example, from 1 to 40, from 1 to 25, from 1 to 15, from 1 to 10, from 2 to 5, or any range or subrange therebetween.
[00399] In even further aspects, the polymer of the alkyl silane may comprise acondensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34. In further aspects, one or more of the following can also be true: R’ may be CH3, and may be 8. In further embodiments, the condensation product may further comprise monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl,,. In aspects, a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3} or combinations thereof, may be from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, fromATTORNEY DOCKET NO. SP23-219WO 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2. In even further aspects, the polymer of the alkyl silane may comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof. In aspects, a ratio of the monomeric units {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof, may be from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2.
[00400] In even further aspects, the polymer of the alkyl silane may comprise acondensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3and OH, and m is from 3 to 34. In further aspects, one or more of the following can also be true: R may be OCH3, and m may be 6 or 8. In aspects where R is OCH3, the monomeric units may be modified to remove one or more methoxy groups during the formation of the polymer of the alkyl silane. In further aspects, the condensation product may further comprise monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3} or combinations thereof, wherein R” is a (C5-C38) alkyl. In aspects, a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising { R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, may be from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2. In even further aspects, the polymerATTORNEY DOCKET NO. SP23-219WO of the alkyl silane may comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof. In aspects, a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof, may be from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2. In even further aspects, the polymer of the alkyl silane may comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof. In aspects, a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof, may be from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2.In aspects, at least a portion of the monomeric units may be linked to the substrate. In further aspects, the condensation product may further comprise monomeric units comprising {R”Si(R”’)2}, {R”Si(R”’)}, {R”Si}, {R"Si(R”’)2(OH)}, {R"Si(R”’)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and each R”’ is selected from a methoxy group, an ethoxy group, a hydroxy, or a linkage to the substrate.
[00401] In even further aspects, the polymer can be a homopolymer of a single alkylsilane (e.g., a single bis-silane). Alternatively, in even further aspects, the polymer can be a copolymer of more than one alkyl silane. For example, the polymer can be a copolymer of an alkyl silane and an addition alkyl silane that contributes to the siloxane part of the structure, as discussed above. An exemplary aspect of a copolymer in the structure discussed herein is theproduct of copolymerizing 1,8-bis(chlorodimethylsilyl)octane (see FIG. 17A) and dichloro-tetramethyl-disoloxane (see FIG. 17D). An additional exemplary aspect of a copolymer in theATTORNEY DOCKET NO. SP23-219WO structure discussed herein is the product of copolymerizing 1,8-bis(dimethylmethoxysilyl)octane (see FIG. 17H) and dichloro-tetramethyl-disoloxane (seeFIG. 17D). In still further aspects, at least one of the alkyl silanes in the copolymer can be a bis-silane and at least one of the alkyl silanes can include a non-fluorine halogen. For example, a structure of the copolymer can be {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]p[Si(R”)2]x}qR, where m and p are independently selected from 3 to 34, but m and p can be vary betweenadjacent monomers, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore (e.g., n is 1, n is 2 or more, and / or n is 2) and can vary between adjacent monomers, and x is 0 or 1. R can be a hydroxyl group, a chloro group, a bromo group, an alkoxide, an alkyl silane, or combinations thereof. In particular aspects, R can be an alkoxide including a methoxy group, an ethoxy group, or combinations thereof. In still further aspects, n can be 1. In still further aspects, n can be 2 or more (e.g., from 2 to 10, from 2 to 5, or 2), and q can be within one or more of the corresponding ranges later in this paragraph. For example, when n is 2 or more (e.g., from 2 to 10, from 2 to 5, or 2), one or more of the following can also be true: R’ can be CH3, R” can be CH3, m can be 8, p can be 8, or combinations thereof. In even further aspects, a degree of polymerization of the polymer can be 1 or more, 2 or more, 5 or more, 10 or more, 20 or more, 50 or more, 100 or less, 75 or less, 60 or less, 40 or less, 25 or less, 15 or less, or 9 or less. In even further aspects, a degree of polymerization of the polymer can be in a range from 1 to 100, from 2 to 100, from 5 to 75, from 10 to 60, from 20 to 40, or any range or subrange therebetween. In even further aspects, a degree of polymerization of the polymer can be about 40 or less, for example, from 1 to 40, from 1 to 25, from 1 to 15, from 1 to 10, from 2 to 5, or any range or subrange therebetween.
[00402] In further aspects, the alkyl silane can be part of a block copolymer of the alkylsilane that is bonded to the first major surface 105 of the substrate, the planarization layer 123,and / or or the fourth major surface 207 of the optical stack 203, 203a, or 203b. In even furtheraspects, a block copolymer can include a block corresponding to the polymer described in the preceding paragraph. In even further aspects, the block copolymer can comprise a dialkyl siloxane (e.g., dimethylsiloxane and / or diethylsiloxane, or combinations thereof) block. In further aspects, the block copolymer contains alternating blocks (i) containing a C3-C34 alkyl group and (ii) a dialkyl siloxane (e.g., dimethylsiloxane, diethylsiloxane, or combinations thereof). In even further aspects, the monomers in one or more blocks of the block copolymer can be bonded together by a disiloxane group. In even further aspects, the disiloxane group can include one or more dialkyl siloxanes (e.g., dimethylsiloxane, diethylsiloxane, or combinations thereof). In even further aspects, the copolymer can alternate between blocks of one more bisATTORNEY DOCKET NO. SP23-219WO alkyl silanes and an additional alkyl silanes that contribute primarily to the siloxane (e.g., dialkylsiloxane, dimethylsiloxane) part of the resulting copolymer. In even further aspects, a dialkyl siloxane (e.g., dimethylsiloxane, diethylsiloxane, or combinations thereof) block of the block copolymer can correspond to the silica-like network described in the followingparagraphs for the planarization layer 123.
[0403] As used herein, a “free end” of a molecule refers to an end of multiatom chainthat is not bonded to another molecule (or another part of the same molecule at the free end. In this sense, the “free end” is “free” to interact with a potential fingerprint or other material. The “free end” can correspond to a terminal monomer (and / or a terminal portion thereof) of a polymeric material. In aspects, a silane group of the alkyl silane can be at a free end of the alkyl silane. Alternatively or additionally, a free end of the alkyl silane can comprise a non-fluoro halogen (e.g., chlorine). In aspects, the alkyl silane can be a bis-silane or a tris-silane. Anexemplary aspect of a bis-silane is 1,8-bis(chlorodimethylsilyl)octane), as shown in see FIG.17A. As discussed above, the alkyl silane can comprise the structure shown in FIG. 18A, forexample, as (i) the product of homopolymerization of bis(chlorodimethylsilyl)octane) (see FIG. 17A) and / or (ii) the product of copolymerizing 1,8-bis(chlorodimethylsilyl)octane (seeFIG. 17A) and dichloro-tetramethyl-disoloxane (see FIG. 17D). Another exemplary aspect ofa bis-silane is 1,8-bis(dimethylmethoxysilyl)octane, as shown in see FIG. 17H. As discussedabove, the alkyl silane can comprise the structure shown in FIG. 18A, for example, as (i) theproduct of homopolymerization of 1,8-bis(dimethylmethoxysilyl)octane (see FIG. 17H)and / or (ii) the product of copolymerizing 1,8-bis(dimethylmethoxysilyl)octane (see FIG. 17H)and dichloro-tetramethyl-disoloxane (see FIG. 17D). In aspects, the surface-modifying layer113 (e.g., fingerprint-hiding coating) can comprise the alkyl silane bonded directly to anotherpart of the coated article (e.g., first major surface 105 of the substrate, planarization layer 123,the fourth major surface 207 of the optical stack 203, 203a, or 230b). In further aspects, thealkyl silane can be directly bonded through a silane group of the alkyl silane. Alternatively or additionally, a free end of the alkyl silane can comprise a non-fluoro halogen (e.g., chlorine) and / or another silane (e.g., the alkyl silane can be a bis-silane).
[00404] As used herein, an elemental composition of the surface-modifying layer 113(e.g., fingerprint-hiding coating) is determined using X-ray photoelectron spectroscopy (XPS). In aspects, the surface-modifying layer can be fluorine-free. In aspects, the surface-modifyinglayer 113 (e.g., fingerprint-hiding coating) can comprise silicon atoms, oxygen atoms, carbonatoms, and hydrogen atoms. In further aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) can further comprise nitrogen atoms. In further aspects, oxygenATTORNEY DOCKET NO. SP23-219WO atoms in the surface-modifying layer can be more common than any other atom in the surface- modifying layer detected by XPS. In further aspects, the surface-modifying layer can comprise about 30 atom% carbon or less, about 25 atom% carbon or less, about 10 atom% carbon or less, about 2 atom% carbon or more, or about 5 atom% carbon or more. Providing a fluorine-free surface-modifying layer 113 (e.g., fingerprint-hiding coating) can be cheaper to produceand / or more environmentally friendly.
[00405] In aspects, an exterior (e.g., exterior surface 115) of the surface-modifyinglayer 113 (e.g., fingerprint-hiding coating) can be fluorine-free. In aspects, an exterior (e.g.,exterior surface 115) of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) canbe free of a transition-metal containing compound. In aspects, an exterior (e.g., exterior surface115) of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can contain a non-zero amount of a non-fluorine halogen (e.g., chlorine, bromine, iodine). In further aspects, anamount of the non-fluorine halogen at the exterior of the surface-modifying layer 113 can beabout 0.5 atom% or more, about 0.7 atom% or more, about 0.8 atom% or more, about 1 atom% or more, about 1.2 atom% or more, about 1.5 atom% or more, about 2 atom% or less, about 1.5 atom% or less, about 1.3 atom% or less, about 1 atom% or less, about 0.9 atom% or less, about 0.8 atom% or less, or about 0.7 atom% or less. In further aspects, an amount of the non-fluorine halogen at the exterior of the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) can be in a range from about 0.5 atom% to about 2 atom%, from about 0.7 atom% to about 1.5 atom%, from about 0.8 atom% to about 1.5 atom%, from about 1 atom% to about 1.3 atom%, or any range or subrange therebetween. In further aspects, the non-fluorine halogencan be chlorine, and the amount of chlorine at the exterior of the surface-modifying layer 113(e.g., fingerprint-hiding coating) can be within one or more of the ranges mentioned above in this paragraph.
[00406] As shown in FIGS. 35 and 36A-36C, the coated article 3501, 3601, 3611, or3621 comprises the planarization layer 123 positioned between the substrate 103 (e.g., disposedover the first major surface 105 of the substrate 103) and the surface-modifying layer 113 (e.g.,inner surface 117 of the surface-modifying layer 113). The planarization layer 123 comprisesa first surface area 125 facing the first major surface 105 of the substrate 103 and a secondsurface area 127 (opposite the first surface area 125) facing and / or bonded to the surface-modifying layer 113 (e.g., inner surface 117 of the surface-modifying layer 113). In aspects, asshown in FIG. 35, the planarization layer 123 (e.g., second surface area 127) can be disposedon and / or bonded to the first major surface 105 of the substrate 103. In aspects, as shown inFIGS. 36A-36C, the planarization layer 123 e.g., second surface area 127) can be disposedATTORNEY DOCKET NO. SP23-219WOover, disposed on, and / or contact the optical stack 203, 203a, or 203b positioned between theplanarization layer 123 and the substrate 103. A planarization thickness 129 is defined as anaverage distance between the first surface area 125 and the second surface area 127. In aspects,the planarization thickness 129 can be about 10 nm or more, about 20 nm or more, about 50nm or more, about 100 nm or more, about 200 nm or more, about 600 nm or less, about 500 nm or less, about 400 nm or less, about 350 nm or less, or about 300 nm or less. In aspects, theplanarization thickness 129 can range from about 10 nm to about 500 nm, from about 20 nmto about 400 nm, from about 20 nm to about 300 nm, from about 20 nm to about 200 nm, from about 20 nm to about 150 nm, from about 20 nm to about 100 nm, from about 50 nm to about100 nm, or any range or subrange therebetween. In aspects, the planarization thickness 129 canrange from about 10 nm to about 600 nm, from about 20 nm to about 500 nm, from about 50 nm to about 400 nm, from about 100 nm to about 350 nm, from about 200 nm to about 300 nm, or any range or subrange therebetween. In exemplary aspects, the planarization thickness129 can be from 10 nm to 600 nm or from 20 nm to 100 nm. The planarization thickness 129is determined from ellipsometry.
[00407] In aspects, the silica-like network of the planarization layer 123 presentdisclosure can be readily distinguished from other silicon-containing oxides (e.g., a silica capping layer) by the properties discussed herein (e.g., hydroxyl content, hardness, refractive index, power spectral density of the surface, surface roughness Ra). For example, the silica- like network can comprise a greater hydroxyl content than a hydroxyl content of the capping layer; and / or the silica-like network can exhibit a lower hardness, lower elastic modulus, and / or higher refractive index than the corresponding property of the capping layer. As used herein, the term “planarization layer” is not intended to be limited by a specific surface roughness Ra (or a specific reduction in surface roughness Ra relative to the surface that the planarization layer is disposed on). Instead, the planarization can comprise any of the aspects discussed herein, including the hydroxyl content and / or the power spectral density in addition to or instead of surface roughness Ra properties.
[00408] Throughout the disclosure, an elastic modulus (e.g., Young’s modulus) of theplanarization layer 123 is determined using nanoindentation with a Berkovich diamondindenter tip. See: Fischer-Cripps, A.C., “Critical Review of Analysis and Interpretation of Nanoindentation Test Data,” Surface & Coatings Technology, 200, 4153 – 4165 (2006); and Hay, J., Agee, P, and Herbert, E., “Continuous Stiffness measurement During Instrumented Indentation Testing, Experimental Techniques,” 34 (3) 86 – 94 (2010). For coatings, instantaneous estimates of the elastic modulus are measured as a function of indentation depth.ATTORNEY DOCKET NO. SP23-219WO The elastic modulus is taken as the maximum value of the instantaneous estimate of the elasticmodulus for measurements within the 50% of the planarization thickness 129 closest to theexterior surface 115 (i.e., first surface area 125) minus 5 nm of the planarization layer 123 fromthe exterior surface 115. Without wishing to be bound by theory, if a coating is of sufficientthickness, then it is then possible to isolate the properties of the coating from an adjacent coating based on the resulting response profiles as a function of depth. Extraction of reliable nanoindentation data is based on well-established protocols described in the above-mentioned references. Otherwise, these metrics can be subject to significant errors.
[00409] Throughout the disclosure, hardness is measured for planarization layers witha thickness of at least 30 nm as the maximum hardness recorded in a range of from 20 nm thefirst surface area 125 of the planarization layer 123 to 60% of the planarization thickness 129(from the first surface area 125 of the planarization layer 123) in a Berkovich Indenter HardnessTest. It has been found that measurements closer to the surface than 20 nm tend to underestimate the hardness while measurements closer than 40% of the planarization thickness to an underlying layer can be significantly influenced by the properties of the underlying layer. For planarization layers with a thickness of 30 nm or less, it is believed that no reliable hardnessmeasurement can be obtained. In aspects, an elastic modulus of the planarization layer 123 canbe about 9 GPa or more, about 10 GPa or more, about 12 GPa or more, about 15 GPa or more, about 20 GPa or more, about 25 GPa or more, about 70 GPa or less, about 60 GPa or less, about 50 GPa or less, about 40 GPa or less, about 38 GPa or less, about 35 GPa or less, about 30 GPaor less, or about 25 GPa or less. In aspects, an elastic modulus of the planarization layer 123can range from about 9 GPa to about 70 GPa, from about 9 GPa to about 60 GPa, from about 9 GPa to about 50 GPa, from about 10 GPa to about 40 GPa, from about 12 GPa to about 38 GPa, from about 15 GPa to about 35 GPa, from about 20 GPa to about 30 GPa, or any range or subrange therebetween.
[00410] In aspects, the planarization layer 123 can comprise a silica or a partial silica-like network. A silica-like network refers to a coordination of silicon atoms bonded together by oxygen atoms with four Si-O bonds for a silicon atom, corresponding to a SiO2 network. As used herein, a fraction of silicon atoms in a silica-like-network is determined by Fourier- transform infrared (FTIR) spectroscopy based on an intensity of an absorbance associated with a Si-O-Si bend (e.g., from about 1000 cm-1to 1060 cm-1) relative all Si-O-Si bends (including the T-type stretch of POSS at about 1105 cm-1). In aspects, a percentage of silicon atoms in theplanarization layer 123 in a silica-like network can be about 50% or more, about 60% or more,about 65% or more, about 70% or more, about 90% or less, about 80% or less, about 75% orATTORNEY DOCKET NO. SP23-219WO less, or about 70% or less. In aspects, a percentage of silicon atoms in the planarization layer 123 in a silica-like network can range from about 50% to about 90%, from about 60% to about 80%, from about 65% to about 75%, or any range or subrange therebetween. Providing a partial silica-like network can enable the planarization layer to be stiff (e.g., elastic modulus of about 9 GPa or more) while remaining flexible enough to withstand abrasion with the surface- modifying layer disposed thereon.
[00411] A ratio of Si-O-Si bonds to silicon atoms of the planarization layer 123 can bemeasured using (a) XPS to determine an amount of Si-O bonds based on Si 2p fine structurerelative to an overall amount of Si or (b) 29Si solid-state nuclear magnetic resonance (NMR)based on fitting the observed chemical shifts to 6 Gaussian curves corresponding to different coordination structures (e.g., a T-unit, a D-unit, a M-unit, and three Q-units with different numbers of hydroxyls), where the functional group bonded to the silicon atom can be substituted with an organic group (e.g., carbon). In aspects, a ratio of Si-O-Si bonds to siliconatoms in the planarization layer 123 can be about 2 or more, about 2.2 or more, about 2.4 ormore, about 2.6 or more, about 3 or less, about 2.9 or less, about 2.8 or less, or about 2.75 orless. In aspects, a ratio of Si-O-Si bonds to silicon atoms in the planarization layer 123 canrange from about 2 to about 3, from about 2.2 to about 2.9, from about 2.4 to about 2.8, from about 2.6 to about 2.75, or any range or subrange therebetween.
[00412] In aspects, the planarization layer 123 can comprise one or more of (1) apercentage of silicon atoms in a silica-like network within one or more of the ranges discussed above (e.g., from about 50% to about 90%) or (2) a ratio of Si-O-Si bonds to silicon atoms within one or more of the ranges discussed above (e.g., from about 2 to about 3). In aspects,the planarization layer 123 can comprise nitrogen atoms, for example with nitrogen atomsbonded to silicon atoms. For example, the planarization layer 123 can be the product of at leastpartially curing a polysilazane over and / or on the first major surface 105 of the substrate 103that can be reacted with a silane after being at least partially cured (to form a surface-modifyinglayer thereon). Alternatively, the planarization layer 123 can be free from nitrogen. In aspects,the planarization layer 123 can be the product of impinging an ion beam on the first majorsurface 105 of the substrate during and / or after a functionalized polyhedral oligomericsilsesquioxane (POSS) (defined below) is disposed over and / or on the first major surface 105and reacted with a silane after the ion beam treatment (to form a surface-modifying layerthereon). In aspects, the planarization layer 123 can be the result of thermally curing a POSS(e.g., hydrogen POSS) compound disposed over and / or the first major surface 105 of thesubstrate 103 that can be reacted with a silane after being thermally cured (to form a surface-ATTORNEY DOCKET NO. SP23-219WOmodifying layer thereon). In aspects, the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) can comprise at least one alkyl silane at the exterior surface 115 and bonded to (eitherdirectly or indirectly) Si-O groups in the planarization layer 123. In aspects, the surface-modifying layer 113 and / or the planarization layer 123 be free from fluorine and / or nitrogen.In aspects, the surface-modifying layer 113 and / or the planarization layer can consist of carbon,oxygen, silicon, hydrogen, and oxygen.
[00413] One way to quantify an amount (e.g., density) of hydroxyl in the surface-modifying layer 113 (e.g., below the alkyl silane) is based on molar ratios determined bysecondary-ion mass spectroscopy (SIMS). Unless otherwise indicated, samples were cleaned with a low-energy Ar gas cluster ion beam (GCIB) source before analysis with SIMS. A molar ratio at the surface can be measured using static SIMS. Unless otherwise indicated, the molar ratio is for a bulk of the surface-modifying layer using dynamic SIMS (D-SIMS). Unlike static SIMS, dynamic SIMS erodes the surface to provide depth-resolved compositional information. As used herein, D-SIMS was conducted using a time-of-flight secondary ion mass spectrometer (ToF-SIMS) with a dual beam configuration. Unless otherwise indicated, the TOF-SIMS used for the results reported herein was a TOF-SIMS M6 instrument (available from IONTOF GmbH) equipped with a Nanoprobe50 bismuth source. The TOF-SIMS M6 instrument was operated with a dual-beam configuration, where the analysis beam was a 30 kilo-electronVolts (keV) Bi3+beam with a current of about 0.1 pA and the sputter beam was 2 keV Cs+with a current of about 120 nA. The sputter beam was configured form a 300 µm by 300 µm sputter “crater,” and the analysis beam was configured to impinge a 75 µm by 75 µm area centered in the sputter “crater.” Charge compensation was achieved using an electron flood gun operating with 20 nA beam current, 20 eV electron energy, and a 1.5 mm spot size focused on the location impinged by the analysis beam. The chamber was evacuated to a pressure of 5 x 10-7Pascals (5 x 10-9millibar) before being brought to and maintained at a pressure of 5 x 10-5Pascals (5 x 10-7millibar) using argon (e.g., 99.99999% purity). Data was collected in negative ion mode with the analyzer in the “all purpose” mode, an analyzer energy of 3000 V and a cycle time of 100 microseconds. Data was processed using Surface Lab software (version 7.3.125519available from IONTOF GmbH). To obtain molar ratios from 16O1H-, 18O-, and 28Si- signals,the known isotope ratio between 18O- and 17O- was used to calculate and subtract the 17O-interference from the 16O1H- signal. A normalized intensity was defined as the mass-interference-corrected 16O1H signal divided by the 28Si- signal. The normalized intensity(16O1H- / 28Si-) was further corrected to remove background signals (as determined from the normalized intensity (16O1H- / 28Si-) contemporaneously measured from GE Type 124 fusedATTORNEY DOCKET NO. SP23-219WO quartz) to determine a “corrected signal.” The corrected signal was converted to a hydrogen to silicon molar ratio (“molar ratio”) using a calibration curve (derived from a series of natural mid-ocean-ridge basaltic (MORB) glasses with known -OH concentrations and other silica and silicate minerals covering a range from 0.0 wt% to 1.98 wt%) with an equation of “molar ratio” = 1.26 * “corrected signal” - 0.025.
[00414] Throughout the disclosure, the “molar ratio” refers to a molar ratio of hydrogento silicon (i.e., a molar amount of hydrogen divided by a molar amount of silicon) as determined by SIMS analysis of a material (e.g., surface-modifying layer below the alkyl silane). Without wishing to be bound by theory, it is believed that hydrogen is indicative of hydroxyl groups (e.g., silanol, Si-O-H). In aspects, a molar ratio (of hydrogen to silicon) of the surface- modifying layer below the alkyl silane can be about 0.2 or more (e.g., about 0.2 or more), about 0.21 or more, about 0.22 or more, about 0.23 or more, about 0.24 or more, about 0.25 or more, about 0.45 or less, about 0.4 or less, about 0.37 or less, about 0.35 or less, about 0.32 or less, about 0.30 or less, or about 0.28 or less. In aspects, a molar ratio (of hydrogen to silicon) can be in a range from about 0.2 to about 0.45, from about 0.20 to about 0.4 (e.g., from about 0.2 to about 0.4), from about 0.21 to about 0.37, from about 0.22 to about 0.35, from about 0.23 to about 0.32, from about 0.24 to about 0.32, from about 0.24 to about 0.30, from about 0.25 to about 0.28, or any range or subrange therebetween. In exemplary aspects, the molar ratio of hydrogen to silicon can be in a range from 0.20 to 0.4 or from about 0.22 to about 0.35. Forexample, as discussed below with reference to FIG. 34, the surface-modifying layers inaccordance with aspects of the present disclosure (e.g., Examples 35-44) exhibits a molar ratio of hydrogen to silicon of 0.20 or more, from about 0.20 to 0.4, or from about 0.22 to about 0.35. In contrast, conventional methods of silica deposition (Comparative Examples JJ-KK) have a molar ratio of about 0.10 or less, meaning that Examples 35-44 have at least about double (2x) the molar ratio of Comparative Examples JJ-KK. In aspects, the molar ratio at the surface can be within any of the ranges recited above in this paragraph. In aspects, the molar ratio (of hydrogen to silicon) of the surface-modifying layer can be greater than the molar ratio of a reactively sputtered silica layer by a multiple of 2 or more, 2.5 or more, 3 or more, 4 or more, 10 or less, 7 or less, 5 or less, or 4 or less. In aspects, the molar ratio (of hydrogen to silicon) of the surface-modifying layer can be greater than the molar ratio of a reactively sputtered silica layer by a multiple in a range from about 2 to 10, from 2 to 7, from 2.5 to 5, from 2.5 to 4, from 3 to 4, or any range or subrange therebetween. In aspects, an ion intensity of carbon (as a ratio to the ion intensity of silicon) can be about 0.01 or less, about 0.005 or less, about 0.002 or less, or about 0.001 or less, for example, in a range from about 0.00001 toATTORNEY DOCKET NO. SP23-219WO about 0.01, from about 0.00005 to about 0.005, from about 0.0001 to about 0.002, from about 0.0005 to about 0.001, or any range or subrange therebetween. The intensity of carbon is based on measurements that are corrected to remove background signals (as determined from the intensity of carbon measured from fused quartz).
[00415] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)and / or the coated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621 can comprise anaverage transmittance (as described above) of about 80% or more, about 85% or more, about 88% or more, about 89% or more, about 90% or more, about 91% or more, about 92% or more,or about 93% or more. In aspects, the average transmittance of the surface-modifying layer 113(e.g., fingerprint-hiding coating) and / or the coated article 101, 201, 211, 221, 3501, 3601, 3611,or 3621 can range from about 80% to 100%, from about 85% to about 99%, from about 88% to about 97%, from about 89% to about 97%, from about 90% to about 96%, from about 91% to about 95%, from about 92% to about 94%, or any range or subrange therebetween. Inaspects, the transmittance of the surface-modifying layer 113 (e.g., fingerprint-hiding coating)and / or the coated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621 at 550 nm can be withinone or more of the ranges mentioned above in this paragraph for the average transmittance.
[00416] As used herein, haze refers to transmission haze that is measured through thesurface-modifying layer 113 (e.g., fingerprint-hiding coating) and / or the coated article 101,201, 211, 221, 3501, 3601, 3611, or 3621 (through the exterior surface 115) in accordance withASTM D1003-21 at 0° relative to a direction normal to the exterior surface 115. Haze ismeasured using a HAZE-GARD PLUS available from BYK Gardner with an aperture over the source port. The aperture has a diameter of 8 mm. A CIE C illuminant is used as the light sourcefor illuminating the surface-modifying layer 113 (e.g., fingerprint-hiding coating) and / or thecoated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621. In aspects, the surface-modifyinglayer 113 (e.g., fingerprint-hiding coating) and / or the coated article 101, 201, 211, 221, 3501,3601, 3611, or 3621 comprises a haze of about 5% or less, about 2% or less, about 1.5% or less, about 1% or less, about 0.5% or less, or about 0.1% or less, for example from about 0.01% to about 5%, from about 0.01% to about 2%, from about 0.05% to about 1.5%, from about 0.05% to about 1%, from about 0.1% to about 0.5%, or any range or subrange therebetween.
[00417] Throughout the disclosure, contact angles are determined for a drop of acorresponding liquid disposed on the exterior surface (not treated with plasma nor corona) using a 30 gauge needle with the contact angle measured using a goniometer in accordance with ASTM D5946. If a contact angle cannot be reliably determined due to a high degree of droplet spread corresponding to a contact angle of 15° or less, then the coating is said to “wet”ATTORNEY DOCKET NO. SP23-219WO the droplet material. As used herein, water contact angles are measured using a drop of deionized water. As used herein, a coating is “hydrophobic” if it has a water contact angle of 90° or more. As used herein, a coating is “superhydrophobic” if it has a water contact angle of 130° or more. As used herein, an “as-formed” coating refers to a coating that has not been subjected to an abrasive (e.g., see Steel Wool Abrasion Test and Cheesecloth Abrasion Test below). As used herein, a coating is “oleophilic” if it has a hexadecane contact angle of less than 40°.
[00418] As used herein, a “uniformity” of a water contact angle is determined based onmeasurements of water contact angle at least every 5 mm over an area of 50 mm x 50 mm of the exterior surface. Here, Uniformity is calculated as (Maximum – Minimum) / (2 * Average) * 100%, where “Maximum” and “Minimum” refer to the corresponding extremum, and “Average” is the mean value of the water contact angle measurements. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can exhibit a uniformity of a watercontact angle of about 10% or less or about 9% or less. In aspects, the surface-modifying layer113 (e.g., fingerprint-hiding coating) can exhibit a uniformity of a water contact angle in arange from 1% to 10%, from 5% to 9%, or any range or subrange therebetween.
[00419] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)(e.g., as-formed) is hydrophobic but not superhydrophobic. In aspects, the water contact angleof the surface-modifying layer 113 (e.g., fingerprint-hiding coating) (e.g., as-formed) can beabout 90° or more, about 95° or more, about 100° or more, about 105° or more, about 110° or more, about 115° or more, about 120° or less, about 115° or less, about 110° or less, or about105° or less. In aspects, the water contact angle of the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) (e.g., as-formed) can range from about 90° to about 120°, from about 95° to about 115°, from about 95° to about 110°, from about 100° to about 110°, from about 105° to about 110°, or any range or subrange therebetween. In aspects, a diiodomethanecontact angle of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) (e.g., as-formed) can be about 60° or more, about 61° or more, about 62° or more, about 65° or more, about 80° or less, about 75° or less, about 73° or less, or about 70° or less. In aspects, adiiodomethane contact angle of the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) (e.g., as-formed) can range from about 60° to about 80°, from about 61° to about 75°, from about 61° to about 72°, from about 62° to about 70°, or any range or subrangetherebetween. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) canbe oleophilic. In aspects, an oleic acid contact angle of the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) (e.g., as-formed) can be about 50° or less, about 45° or less, aboutATTORNEY DOCKET NO. SP23-219WO 40° or less, about 35° or less, about 30° or less, about 25° or less, about 20° or less, or thesurface-modifying layer 113 (e.g., fingerprint-hiding coating) can wet oleic acid. In furtheraspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) (e.g., as formed)wets oleic acid. Providing a low diiodomethane contact angle (e.g., about 60° or more) and / or a low hexadecane contact angle (e.g., about 20° or less) can reduce the visibility and / or color shift associated with fingerprints by enabling fingerprint oil to be dispersed across the surface-modifying layer 113 (e.g., fingerprint-hiding coating) rather than beading up into pronounceddroplets. Providing a high water contact angle (e.g., about 90° or more, about 95° or more, or about 100° or more) can enhance the removal of aqueous material (e.g., water droplets, sweatdroplets) from the surface-modifying layer 113 (e.g., fingerprint-hiding coating).
[0420] Throughout the disclosure, surface energy (e.g., total surface energy) andcomponents thereof (e.g., polar, dispersive) are calculated using the Wu model based on contactangle measurements, as described above. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) can comprise a total surface energy of about 35 milliNewtons per meter (mN / m) or less, about 32 mN / m or less, about 31 mN / m or less, about 30 mN / m or less, about 29 mN / m or less, about 28 mN / m or less, about 27 mN / m or less, about 25 mN / m or more, about 26 mN / m or more, about 28 mN / m or more, about 30 mN / m or more, about 31mN / m or more, or about 32 mN / m or more. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) can comprise a total surface energy ranging from about 25 mN / m to about 35 mN / m, from about 26 mN / m to about 32 mN / m, from about 26 mN / m to about 30 mN / m, from about 26 mN / m to about 29 mN / m, from about 26 mN / m to about 28 mN / m orany range or subrange therebetween. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) can comprise a dispersive surface energy of about 30 mN / m or less, about 28 mN / m or less, about 27 mN / m or less, about 26 mN / m or less, about 25 mN / m or less,about 24 mN / m or less, or about 23 mN / m or less. In aspects, the surface-modifying layer 113(e.g., fingerprint-hiding coating) can comprise a dispersive surface energy ranging from about 15 mN / m to about 30 mN / m, from about 18 mN / m to about 30 mN / m, from about 20 mN / m to about 28 mN / m, from about 22 mN / m to about 28 mN / m, from about 24 mN / m to about 27mN / m, or any range or subrange therebetween. In aspects, the surface-modifying layer 113(e.g., fingerprint-hiding coating) can comprise a polar surface energy of about 6 mN / m or less, about 5 mN / m or less, about 4 mN / m or less, about 3 mN / m or less, or about 2 mN / m or less.In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can comprise adispersive surface energy ranging from about 0.5 mN / m to about 6 mN / m, from about 1 mN / m to about 6 mN / m, from about 1.5 mN / m to about 6 mN / m, from about 2 mN / m to about 6ATTORNEY DOCKET NO. SP23-219WO mN / m, from about 2 mN / m to about 5 mN / m, from about 2 mN / m to about 4 mN / m, or any range or subrange therebetween. Providing a low polar surface energy and / or a high dispersive surface energy a can enable oils (e.g., fingerprint oil) to be dispersed across the surface (e.g.,oleophilic) of the surface-modifying layer 113 (e.g., fingerprint-hiding coating), which candecrease a visibility and / or a color shift associated with fingerprints.
[00421] Throughout the disclosure, the “Steel Wool Abrasion Test” is used todetermine the durability of a coating. For the Steel Wool Abrasion Test, steel wool (Bonstar #0000) was cut into strips (25 mm x12 mm) and placed on a sheet of aluminum foil to bake in an oven for 2 hours at 100°C. A steel wool strip was fitted to an attachment (10 mm x10 mm) of an abrader (5750, Taber Industries) using a zip tie. Weights totaling 720 grams were added to the Taber arm to result in a total applied load of 1 kilogram. The stroke length was set at 25 mm, the speed was set to 60 cycles per minute, and testing occurred at 23°C. The area to be abraded was marked onto the back of the sample for tracking. A sample of the coating was secured in the abraded and subjected to 2,000 cycles or 3,500 cycles. After the coating is abraded for the predetermined number of cycles, an abraded water contact angle is measured in accordance with the method for the contact angle described above. A high contact angle (e.g., about 80° or more, about 85° or more, about 90° or more) is indicative of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) surviving the Steel Wool Abrasion Test.Decreases in the contact angle below 70° correlate with a loss of the surface-modifying layer113 (e.g., fingerprint-hiding coating). In aspects, the abraded water contact angle after 2,000cycles and / or 3,5000 cycles in the Steel Wool Abrasion Test can be about 80° or more, 85° or more, about 88° or more, or about 90° or more.
[00422] Throughout the disclosure, the “Cheesecloth Abrasion Test” is also used todetermine the durability of a coating. In the Cheesecloth Abrasion Test, 4 layers of cheesecloth wrap (Crockmeter Squares for American Standards, 200877; SDL Atlas USA, Rock Hill, SC) are affixed to a cylindrical tip with a radius of 2 cm of a Linear Taber Abrader (Model 5750; Taber Industries, North Tonawanda, NY) with a constant load of 750 grams. The path-length of each swipe is 15 mm, with each cycle comprising a forward and backward swipe to return the tip to its original position before proceeding with the next cycle. The speed was 30 cycles per minute, testing occurred at 23°C. After the coating is abraded for 200,000 cycles, a cheesecloth-abraded water contact angle is measured in accordance with the method for the contact angle described above. In aspects, a cheesecloth-abraded water contact angle of thesurface-modifying layer 113 (e.g., fingerprint-hiding coating) can be about 80° or more, about85° or more, about 90° or more, about 95° or more, about 100° or more, about 105° or more,ATTORNEY DOCKET NO. SP23-219WO or about 110° or more. In aspects a difference between the water contact angle of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) (as-formed) and the cheesecloth-abradedwater contact angle (after 200,000 cycles) can be about 15° or less, about 12° or less, about 10° or less, or about 8° or less. As demonstrated by the results of the Steel Wool Abrasion Test andthe Cheesecloth Abrasion Test, the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) of the present disclosure can withstand abrasion and maintain good contact angles.
[00423] Throughout the disclosure, the “Rubber Abrasion Test” is also used todetermine the durability of a coating. In the Rubber Abrasion Test, a 6 mm diameter by 20 mm rod of rubber is affixed to a cylindrical tip with a length of 5 mm of a Linear Taber Abrader (Model 5750; Taber Industries, North Tonawanda, NY) with a constant load of 1 kg. The rod of rubber used herein was a Testick (available from Hwarang) with a hardness of 88 (HDC, as measured by a durometer). The path-length of each swipe is 15 mm, with each cycle comprising a forward and backward swipe to return the tip to its original position before proceeding with the next cycle. The speed was 40 cycles per minute, testing occurred at 23°C. After the coating is abraded for 3,000 cycles, a rubber-abraded water contact angle is measured in accordance with the method for the contact angle described above. In aspects, a rubber-abraded watercontact angle of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can be about80° or more, about 85° or more, about 90° or more, about 95° or more, about 100° or more, about 105° or more, or about 110° or more. In aspects a difference between the water contactangle of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) (as-formed) and therubber-abraded water contact angle (after 3,000 cycles) can be about 15° or less, about 12° or less, about 10° or less, or about 8° or less.
[00424] As used herein, “surface roughness” means the Ra surface roughness, which isan arithmetical mean of the absolute deviations of a surface profile from an average position in a direction normal to the surface of the test area. Ra surface roughness values for an 2 µm by 2 µm test area using atomic force microscopy (AFM). In aspects, the surface-modifying layer113 and / or the planarization layer 123 can comprise a surface roughness Ra (e.g., as-formed)of about 1 nm or less, 0.8 nm or less, 0.7 nm or less, about 0.6 nm or less, about 0.5 nm or less, about 0.1 nm or more, about 0.2 nm or more, about 0.3 nm or more, or about 0.4 nm or more.In aspects, the surface-modifying layer 113 and / or the planarization layer 123 can comprise asurface roughness Ra (e.g., as-formed) ranging from about 0.1 nm to about 1 nm, from about 0.2 nm to about 0.8 nm, from about 0.3 nm to about 0.7 nm, from about 0.4 nm to about 0.5 nm, or any range or subrange therebetween.ATTORNEY DOCKET NO. SP23-219WO
[00425] Throughout the disclosure, a coefficient of friction refers to a dynamiccoefficient of friction measured in accordance with ASTM D1894-14. In aspects, the exteriorsurface 115 of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can comprisea dynamic coefficient of friction of about 0.25 or less, about 0.22 or less, about 0.20 or less,about 0.18 or less, or about 0.15 or less. In aspects, the exterior surface 115 of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can comprise a dynamic coefficient offriction in a range from 0.05 to about 0.25, from about 0.10 to about 0.22, from about 0.12 to about 0.20, from about 0.15 to about 0.18, or any range or subrange therebetween.
[00426] Throughout the disclosure, a refractive index of coatings and films is measuredby spectroscopic ellipsometry using a Woollam M-2000 and modelled using Wollam CompleteEase software. Unless otherwise specified, refractive index is measured at 550 nm.In aspects, a refractive index of the planarization layer 123 can be about 1.37 or more, about1.38 or more, about 1.4 or more, about 1.42 or more, about 1.44 or more, about 1.48 or more, about 1.5 or more, about 1.55 or less, about 1.53 or less, about 1.49 or less, about 1.44 or less, about 1.42 or less, or about 1.4 or less. In aspects, a refractive index of the planarization layer123 can range from about from about 1.37 to about 1.55, 1.38 to about 1.55, from about 1.42to about 1.55, from about 1.44 to about 1.55, from about 1.44 to about 1.53, from about 1.48 to about 1.51, or any range or subrange therebetween. In aspects, the refractive index of theplanarization layer 123 can be about 1.51 or less, for example, in a range from about 1.37 toabout 1.51, from about 1.37 to about 1.50, from about 1.37 to about 1.49, from about 1.38 to about 1.44, from about 1.4 to about 1.42, or any range or subrange therebetween. In aspects, arefractive index of the substrate 103 can be greater than or less than the refractive index of theplanarization layer 123. As discussed below, different compositions of the planarization layer123 can have different refractive index values or ranges.
[0427] Throughout the disclosure, properties of the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) are characterized in terms of a behavior of a simulated fingerprint applied in a Simulated Fingerprint Test. As used herein, the Simulated Fingerprint Test comprises: (1) cleaning a surface of the sample to be tested and an artificial silicone fingerprint with isopropyl alcohol; (2) heating artificial sebum in a glass petri dish and then letting the artificial sebum cool to room temperature (25°C); (3) pressing a fingerprint portion of the artificial silicone finger into the cooled artificial sebum; and (3) placing the fingerprint portion of the artificial silicon finger onto the surface of the sample to be tested and transferring the artificial sebum from the fingerprint portion to the surface as a simulated fingerprint.ATTORNEY DOCKET NO. SP23-219WO
[00428] In aspects, a visibility of a fingerprint on the surface-modifying layer 113 (e.g.,fingerprint-hiding coating), as defined above as an absolute value of a difference betweenCIELAB L* values for a portion of the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) with and without fingerprint oil, can be about 15 or less, about 10 or less, about 8 or less, about 5 or less, about 2 or less. In aspects, a visibility of a fingerprint on the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can range from 0 to 15, from about 0.5to about 10, from about 1 to about 8, from about 2 to about 5, or any range or subrangetherebetween. In aspects, a color shift of a fingerprint on the surface-modifying layer 113 (e.g.,fingerprint-hiding coating), as defined above as √((a1* - a2*)2+ (b1* - b2*)2), can be about 15 or less, about 10 or less, about 8 or less, about 5 or less, about 2 or less. In aspects, a color shiftof a fingerprint on the surface-modifying layer 113 (e.g., fingerprint-hiding coating) can rangefrom 0 to 15, from about 0.5 to about 10, from about 1 to about 8, from about 2 to about 5, orany range or subrange therebetween. FIG. 14 and FIG. 16(a) show a photograph of thesimulated fingerprint applied to various coated articles (discussed in more detail in the Examples) with the Simulated Fingerprint Test.
[00429] As used herein, “haze” refers to transmission haze that is measured through thesurface-modifying layer 113 of the coated article 101, 201, 211, 221, 3501, 3601, 3611, or3621 (through the exterior surface 115) in accordance with ASTM D1003-21 at 0° relative toa direction normal to the exterior surface 115. Haze is measured using a HAZE-GARD PLUSavailable from BYK Gardner with an aperture over the source port. The aperture has a diameter of 8 mm. A CIE C illuminant is used as the light source for illuminating the surface-modifyinglayer 113 and / or through the coated article 101, 201, 211, 221, 3501, 3601, 3611, or 3621. Inaspects, when a simulated fingerprint is applied to the surface-modifying layer 113 in theSimulated Fingerprint Test, the surface-modifying layer 113 exhibits a haze (i.e., transmissionhaze measured after the simulated fingerprint is applied) of 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 1% or more, 2% or more, 3% or more, 4% or more, or 5% or more. Inaspects, the surface-modifying layer 113 exhibits a haze (i.e., transmission haze measured afterthe simulated fingerprint is applied) in a range from 1% to 8%, from 2% to 7%, from 3% to 7%, from 3% to 6%, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibits a haze greater than 10%, which is different from the above- mentioned ranges in statistically significant way and demonstrates that the surface-modifyinglayer 113 (e.g., fingerprint-hiding coating) of the present disclosure does a better job of“hiding” visual effects associated with an applied fingerprint than the Comparative Examples.ATTORNEY DOCKET NO. SP23-219WO
[00430] As used herein, a “mean gray level” was determined in a Gray Level Test usingthe Simulated Fingerprint Test. Specifically, the Gray Level Test involves photographing thesurface-modifying layer 113 (e.g., fingerprint-hiding coating) before and after application ofthe simulated fingerprint in the Simulated Fingerprint Test using a Canon Rebel T7 DSLR camera equipped with a Canon EF-S 60 mm Macro Lens and illuminated using a ring light; the camera was operating in manual mode with manual focus; photographs were captured in the RAW format and were processed with ImageJ to determine the mean gray level value in the photograph after application of the simulated fingerprint, where a range of physically possiblemean gray values from 0 to 609. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits a mean gray value from the application of a simulated fingerprint in the Simulated Fingerprint Test of 150 or less, 145 or less, 140 or less, 135 or less, 130 or less, 125 or less, 120 or less, 115 or less, 110 or less, 105 or less, 100 or less, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 95 or more, 98 or more, or 100 or more. In aspects,the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits a mean gray valuefrom the application of a simulated fingerprint in the Simulated Fingerprint Test in a range from 50 to 150, from 60 to 140, from 70 to 130, from 50 to 125, from 60 to 120, from 70 to 115, from 80 to 110, from 90 to 105, from 95 to 100, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibits a mean gray value greater than 140 (e.g., greater than 300), which is different from the above-mentioned ranges in statistically significant way. As discussed below, the Comparative Examples exhibits a mean gray value greater than 140 (or greater than 300) which is different from the above-mentioned ranges instatistically significant way and demonstrates that the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) of the present disclosure does a better job of “hiding” visual effects associated with an applied fingerprint than the Comparative Examples.
[00431] As used herein, a “normalized gray level” was determined using a NormalizedGray Level Test. In the Normalized Gray Level Test uses the before and after photographs described in the previous paragraph for the Gray Level Test that are processed with ImageJ to determine the average gray level values in each photograph. The Normalized Gray Level Test takes a ratio of the average gray level value of the after (with the simulated fingerprint) photograph to the average gray level of the before photograph (i.e., after divided by before). For example, a normalized gray level of 1.0 means that the simulated fingerprint did not change the average gray levels at all while a normalized gray level of 2.0 means that the average gray value of the simulated fingerprint is twice that of the average gray value in the before (reference) photograph. In aspects, the normalized gray level (as measured in the NormalizedATTORNEY DOCKET NO. SP23-219WOGray Level Test) of the coated article (having the surface-modifying layer 113) with thesimulated fingerprint applied to the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) in the Simulated Fingerprint can be about 2.0 or less, about 1.95 or less, about 1.90 or less, about 1.85 or less, about 1.70 or less, about 1.65 or less, about 1.6 or less, about 1.55 or less, about 1.5 or less, about 1.45 or less, about 1.40 or less, about 1.35 or less, about 1.30 or less, about 1.25 or less, about 1.0 or more, about 1.05 or more, about 1.10 or more, about 1.15 or more, about 1.20 or more, or about 1.25 or more. In aspects, the normalized gray level (as measured in the Normalized Gray Level Test) of the coated article (having the surface-modifying layer) with the simulated fingerprint applied to the surface-modifying layer 113(e.g., fingerprint-hiding coating) in the Simulated Fingerprint can be in a range from about 1.0 to about 1.5, from about 1.05 to about 1.45, from about 1.10 to about 1.40, from about 1.15 to about 1.35, from about 1.20 to about 1.30, from about 1.25 to about 1.30, or any range therebetween. As discussed in the examples herein, surface-modifying layers (e.g., fingerprint- hiding coating) in accordance with the presence disclosure can provide a normalized gray level of about 2.0 or less or 1.5 or less that can be 50% or less of other (comparative) coatings tested (e.g., based on functionalized poly(dimethyl siloxane) (PDMS)).
[00432] Unless otherwise, indicated, additional properties exhibited by the surface-modifying layer 113 (e.g., fingerprint-hiding coating) when the simulated fingerprint is appliedin the Simulated Fingerprint Test are measured using Bruker ContourGT-X white light interferometer and the vertical scanning interferometry (VSI) method at 20X objective lens and 0.55X magnification of four 1 mm x 1 mm areas per sample. As used herein, properties measured with the vertical scanning interferometry method are measured and reported consistent with ISO 25178 and ISO 21920.
[00433] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a mean height of the droplets of the simulated fingerprint applied in the Simulated Fingerprint Test of 0.17 µm or less, 0.15 µm or less, 0.13 µm or less, 0.12 µm or less 0.11 µmor less, or 0.10 µm or less. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hidingcoating) exhibits a mean height of the droplets of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 0.01 µm to 0.17 µm, from 0.05 µm to 0.15 µm, from 0.06 µm to 0.13 µm, from 0.07 µm to 0.12 µm or less, from 0.08 µm to 0.11 µm, or from 0.09 µm to 0.10 µm, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a mean height of 0.20 µm or more (e.g., 0.65 µm or more) that is different from the above-mentioned ranges in statistically significant way and conveys aATTORNEY DOCKET NO. SP23-219WO difference in the size of the droplets formed, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00434] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a ratio of a height of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test to an area of the droplet of 0.006 µm / µm2or less, 0.005 µm / µm2or less, 0.0045µm / µm2 or less, or 0.004 µm / µm2 or less. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) exhibits a ratio of a height of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test to an area of the droplet in a range from 0.001 µm / µm2to 0.006 µm / µm2, from 0.002 µm / µm2to 0.005 µm / µm2, from 0.0025 µm / µm2to 0.0045 µm / µm2, from 0.003 µm / µm2to 0.004 µm / µm2, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a height to area ratio of 0.008 µm / µm2or more (e.g., 0.023 µm / µm2or more) that is different from the above-mentioned ranges, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00435] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a ratio of a volume of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test to an area of the droplet of 0.78 µm3 / µm2or less, 0.76 µm3 / µm2or less, 0.75 µm3 / µm2or less, 0.74 µm3 / µm2or less, 0.73 µm3 / µm2or less, 0.70 µm3 / µm2or less, 0.60 µm3 / µm2or less, 0.55 µm3 / µm2or less, or 0.50 µm3 / µm2or less. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits a ratio of a volume of a dropletof the simulated fingerprint applied in the Simulated Fingerprint Test to an area of the droplet in a range from 0.10 µm3 / µm2to 0.78 µm3 / µm2, from 0.20 µm3 / µm2to 0.76 µm3 / µm2, from 0.25 µm3 / µm2to 0.75 µm3 / µm2, from 0.30 µm3 / µm2to 0.74 µm3 / µm2, from 0.35 µm3 / µm2to 0.73 µm3 / µm2, from 0.40 µm3 / µm2to 0.72 µm3 / µm2, or any range or subrange therebetween.
[00436] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a radius of a spherical cap fitted to a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 40 µm or more, 50 µm or more, 60 µm or more, 70 µm or more, 80 µm or more, 90 µm or more, or 100 µm or more. In aspects, the surface-modifying layer113 (e.g., fingerprint-hiding coating) exhibits a radius of a spherical cap fitted to a droplet ofthe simulated fingerprint applied in the Simulated Fingerprint Test in a range from 40 µm to 200 µm, from 50 µm to 180 µm, from 60 µm to 160 µm, from 70 µm to 140 µm, from 80 µm to 120 µm, from 90 µm to 110 µm, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a spherical cap radius of 21 µm or less (e.g., 10 µm or less) that is different from the above-mentioned ranges in statistically significant way and conveysATTORNEY DOCKET NO. SP23-219WO a difference in the size of the droplets formed, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00437] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a center of sphere fitted to a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test that is away from the exterior surface of the surface-modifyinglayer 113 (e.g., fingerprint-hiding coating) by 30 µm or more, 40 µm or more, 50 µm or more,60 µm or more, 70 µm or more, 80 µm or more, or 90 µm or more. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits a center of sphere fitted to adroplet of the simulated fingerprint applied in the Simulated Fingerprint Test that is away fromthe exterior surface of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) byfrom 30 µm to 200 µm, from 40 µm to 180 µm, from 50 µm to 160 µm, from 60 µm to 140 µm, from 80 µm to 120 µm, from 90 µm to 110 µm, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a center of a fitted sphere that is within of 20 µm (e.g., 6 µm or less) from the exterior surface that is different from the above- mentioned ranges in statistically significant way and conveys a difference in the size of the droplets formed, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00438] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a mean effective diameter of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 10 µm or more, 11 µm or more, 12 µm or more, 13 µm or more, 14 µm or more, 15 µm or more, 16 µm or more, 17 µm or more, or 18 µm or more. In aspects,the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits a mean effectivediameter of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 10 µm to 40 µm, from 11 µm to 35 µm, from 12 µm to 30 µm, from 13 µm to 28 µm, from 14 µm to 26 µm, from 15 µm to 24 µm, from 16 µm to 22 µm, from 17 µm to 20 µm, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a mean effective diameter that is less than 8 µm that is different from the above- mentioned ranges in statistically significant way and conveys a difference in the size of the droplets formed, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00439] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a mean area of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 200 µm2or more, 400 µm2or more, 600 µm2or more, 700 µm2or more, 800 µm2or more, 900 µm2or more, or 1000 µm2or more. In aspects, the surface-modifyingATTORNEY DOCKET NO. SP23-219WOlayer 113 (e.g., fingerprint-hiding coating) coating exhibits a mean area of a droplet of thesimulated fingerprint applied in the Simulated Fingerprint Test in a range from 200 µm2to 3000 µm2, from 400 µm2to 2500 µm2, from 500 µm2to 2000 µm2, from 600 µm2to 1900 µm2, from 700 µm2to 1800 µm2, from 800 µm2to 1700 µm2, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a mean area that is less than 200 µm2(e.g., 125 µm2or less) that is different from the above-mentioned ranges in statistically significant way and conveys a difference in the size of the droplets formed, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00440] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a total area of all droplets associated with the simulated fingerprint applied in the Simulated Fingerprint Test of 150000 µm2or more, 170000 µm2or more, 200000 µm2or more, 220000 µm2or more, 240000 µm2or more, or 250000 µm2or more. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits a total area of all dropletsassociated with the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 150000 µm2to 1000000 µm2, from 170000 µm2to 800000 µm2, from 200000 µm2to 600000 µm2, from 220000 µm2to 500000 µm2, from 240000 µm2to 400000 µm2, from 250000 µm2to 300000 µm2, or any range or subrange therebetween. As discussed below, the Comparative Examples exhibit a mean area that is less than 120000 µm2(e.g., 55000 µm2or less) that is different from the above-mentioned ranges in statistically significant way and conveys a difference in the size of the droplets formed, which may be related to differences in the oleic acid contact angle (e.g., oleophilic versus oleophobic).
[00441] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a mean hill form factor Sdff of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 0.65 or more, 0.67 or more, 0.68 or more, 0.69 or more, or 0.70or more. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibitsa mean hill form factor Sdff of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of from 0.65 to 1.00, from 0.65 to 0.90, from 0.67 to 0.85, from 0.68 to 0.80, from 0.69 to 0.75, from 0.70 to 0.73, or any range or subrange therebetween.
[00442] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a mean hill equivalent diameter Shed of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 60 µm or more, 65 µm or more, 70 µm or more, 75 µm or more, 80 µm or more, 85 µm or more, or 90 µm or more. In aspects, the surface-modifyinglayer 113 (e.g., fingerprint-hiding coating) exhibits a mean hill equivalent diameter Shed of adroplet of the simulated fingerprint applied in the Simulated Fingerprint Test in a range fromATTORNEY DOCKET NO. SP23-219WO 60 µm to 200 µm, from 65 µm to 150 µm, from 70 µm to 130 µm, from 75 µm to 110 µm, from 80 µm to 100 µm, or any range or subrange therebetween.
[00443] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a material ratio of hills Smrk1 of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 25% or more, 28% or more, 30% or more, 31% or more, 32% ormore, 33% or more, or 34% or more. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) exhibits a material ratio of hills Smrk1 of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 25% to 50%, from 28% to 45%, from 30% to 40%, from 31% to 38%, from 32% to 35%, or any range or subrange therebetween.
[00444] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits an inverse areal material ratio Smc for an areal material ratio of 10% of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 0.2 µm or more, 0.22 µm or more, 0.25 µm or more, 0.27 µm or more, 0.29 µm or more, 0.32 µm or more, 0.35 µm ormore, 0.37 µm or more, or 0.40 µm or more. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) exhibits an inverse areal material ratio Smc for an areal material ratio of 10% of a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 0.2 µm to 0.7 µm, 0.22 µm to 0.65 µm, 0.25 µm to 0.60 µm, 0.27 µm to 0.55 µm, 0.29 µm to 0.50 µm, from 0.32 µm to 0.45 µm, from 0.35 µm to 0.40 µm, or any range or subrange therebetween.
[00445] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits an areal sectional height difference between areal material ratios of 10% and 90% a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 0.40 µm or more, 0.45 µm or more, 0.5 µm or more, 0.55 µm or more, 0.6 µm or more, 0.65 µm or more,0.70 µm or more, or 0.75 µm or more. In aspects, the surface-modifying layer 113 (e.g.,fingerprint-hiding coating) exhibits an areal sectional height difference between areal material ratios of 10% and 90% a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 0.40 µm to 2.0 µm, from 0.45 µm to 1.5 µm, from 0.5 µm to1.4 µm, from 0.55 µm to 1.3 µm, from 0.6 µm to 1.2 µm, from 0.65 µm to 1.1 µm, from 0.7µm to 1.0 µm, from 0.75 µm to 0.90 µm, or any range or subrange therebetween.
[00446] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a core material value Vmc between areal material ratios of 10% and 90% a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test of 0.10 µm3 / µm2or more, 0.12 µm3 / µm2or more, 0.15 µm3 / µm2or more, 0.18 µm3 / µm2or more, or 0.20 µm3 / µm2orATTORNEY DOCKET NO. SP23-219WOmore. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibits acore material value Vmc between areal material ratios of 10% and 90% a droplet of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 0.10 µm3 / µm2to 1.0 µm3 / µm2, from 0.12 µm3 / µm2to 0.8 µm3 / µm2, from 0.15 µm3 / µm2to 0.6 µm3 / µm2, from 0.18 µm3 / µm2or to 0.4 µm3 / µm2or, from 0.20 µm3 / µm2to 0.30 µm3 / µm2, or any range or subrange therebetween.
[00447] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a root mean square height Sq of the simulated fingerprint applied in the Simulated Fingerprint Test of 0.45 µm or more, 0.50 µm or more, 0.55 µm or more, 0.60 µm or more, or0.65 µm or more. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits a root mean square height Sq of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 0.45 µm to 1.0 µm, from 0.50 µm to 0.90 µm, from 0.55 µm to 0.8 µm, from 0.60 µm to 0.75 µm, or any range or subrange therebetween.
[00448] In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating)exhibits an auto-correlation length Sal of the simulated fingerprint applied in the Simulated Fingerprint Test of 20 µm or more, 25 µm or more, 30 µm or more, 35 µm or more, or 40 µmor more. In aspects, the surface-modifying layer 113 (e.g., fingerprint-hiding coating) exhibitsan auto-correlation length Sal of the simulated fingerprint applied in the Simulated Fingerprint Test in a range from 20 µm to 100 µm, from 25 µm to 80 µm, from 30 µm to 60 µm, from 35 µm to 55 µm, from 40 µm to 50 µm, or any range or subrange therebetween.
[00449] Throughout the disclosure, electrostatic charging is measured using theTribocharging Test. With reference to FIG. 29, the Tribocharging apparatus 2901 comprises arubbing head 2921 comprising a silver coated nylon mesh having circular cross-section with adiameter of 8 mm. The rubbing head 2921 is rubbed along a 25 mm long track (denoted byrubbing region 2913) in a straight line (forward and backward constituting 1 cycle) for 100cycles. The rubbing induces a surface charge in the surface 2905 of the material 2903 beingtested. The surface charge developed over the surface 2905 is measured using a non-contactfieldmeter (Monroe 244A) as a voltage at multiple locations across the surface in a 70 mm by70 mm square (denoted by measurement region 2911 with a total area of 4900 mm2) centeredin the middle of the track (i.e., middle of the rubbing region 2913), which is where the rubbinghead 2921 is shown in FIG. 29. The measurements are taken 100 seconds after finishing the100 rubbing cycles.
[0450] FIG. 30 shows an example contour plot of voltages measured by the non-contact fieldmeter. In FIG. 30, the vertical axis 3003 (i.e., y-axis) and the horizontal axis 3001ATTORNEY DOCKET NO. SP23-219WO (i.e., x-axis) correspond to the physical distance from the middle of track along thecorresponding axis. The 70 mm x 70 mm measurement region (e.g., measurement region 2911in FIG. 29 corresponding to the entire region shown in FIG. 30) is divided into 3 regions: anperipheral contact region, inner region, and a center region. The center contact region 3014 isdefined by an central boundary 3013 that is centered at the middle of the track extending 40mm in the direction that the rubbing head 2921 (see FIG. 29) travelled along the track and 20mm perpendicular to that direction (800 mm2 total area). The inner region 3012 is definedbetween the central boundary 3013 (discussed in the previous sentence) and an inner boundary3011 that is centered at the middle of the track extending 50 mm in the direction that the rubbing head travelled along the track and 50 mm perpendicular to that direction (excluding the centercontact region 3014) (2500 mm2 – 800 mm2 = 1700 mm2 total area) The peripheral contactregion 3010 is defined as the area beyond the inner boundary 3011 (discussed in the previoussentence) that is still within the 70 mm by 70 mm measurement region (4900 mm2– 2500 mm2= 2400 mm2 total area). For the example contour plot of voltages shown in FIG. 30, thecontours go from area 3027 with the greatest voltage build-up (tribocharging) to area 3021 withthe least tribocharging. As shown, the greatest tribocharging was observed in area 3027followed by region 3026 that are primarily located in the center contact region 3014. Lessertribocharging was seen in area 3025 followed by region 3024 that were present in the centercontact region 3014 and the inner region 3012. Area 3023 straddles the inner boundary 3011with even less tribocharging seen in area 3022 in the peripheral contact region 3010 and theleast tribocharging in area 3021. Without wishing to be bound by theory, surfaces with lowertribocharging are better able to disperse charge across the surface than other surfaces with higher tribocharging.
[00451] In the Tribocharging test, a single value can be extracted equal to the absolutevalue of the average voltage measured in the center contact region 3014. Also, three voltagescan be extracted corresponding to the average voltage in each of the center contact region 3014,the inner region 3012, and the peripheral contact region 3010. Further, a voltage differenceequal to the absolute value of a difference between the average voltage in the peripheral contactregion 3010 and the average voltage in the center contact region 3014. In aspects, a voltagemeasured in the Tribocharging test (i.e., corresponding to the absolute value of the averagevoltage measured in the center contact region 3014) can be about 15 Volts (V) or less, about12 V or less, about 10 V or less, about 8 V or less, about 6 V or less, about 5 V or less, about 0 V or more, about 1 V or more, about 2 V or more, about 3 V or more, about 4 V or more, or about 5 V or more. In aspects, a voltage measured in the Tribocharging test (i.e., correspondingATTORNEY DOCKET NO. SP23-219WOto the absolute value of the average voltage measured in the center contact region 3014) can bein a range from about 0 V to about 15 V, from about 1 V to about 12 V, from about 1 V to about 10 V, from about 2 V to about 8 V, from about 3 V to about 6 V, from about 4 V to about 5 V, or any range or subrange therebetween. In aspects, a voltage difference between aperipheral contact region 3010 and a center contact region 3014 (i.e., the absolute value of adifference between the average voltage in the peripheral contact region 3010 and the averagevoltage in the center contact region 3014) can be about 5 V or less, about 4 V or less, about 3V or less, about 2 V or less, about 1 V or less, about 0 V or more, about 0.5 V or more, about 1 V or more, about 1.5 V or more, about 2 V or more, or about 2.5 V or less. In aspects, avoltage difference between a peripheral contact region 3010 and a center contact region 3014(i.e., the absolute value of a difference between the average voltage in the peripheral contactregion 3010 and the average voltage in the center contact region 3014) can be in a range fromabout 0 V to about 5 V, from about 0.5 V to about 4 V, from about 1 V to about 3 V, from about 1.5 V to about 2 V, or any range or subrange therebetween. As discussed herein withreference to FIGS. 31-32, surface-modifying coatings (e.g., fingerprint-hiding coatings) inaccordance with aspects of the present disclosure can exhibit an absolute value of the averagevoltage of the center contact region 3014 of less than 15 V (e.g., less than 10 V, less than 8 V,or about 5 V) and a voltage difference between a peripheral contact region 3010 and a centercontact region 3014 of less than 5 V (e.g., less than 3 V, about 2 V or less, or about 1 V).
[0452] Aspects of the disclosure can comprise a consumer electronic product. Theconsumer electronic product can comprise a front surface, a back surface, and side surfaces. The consumer electronic product can further comprise electrical components at least partially within the housing. The electrical components can comprise a controller, a memory, and adisplay. The display can be at or adjacent to the front surface of the housing. The display cancomprise liquid crystal display (LCD), an electrophoretic displays (EPD), an organic light- emitting diode (OLED) display, or a plasma display panel (PDP). The consumer electronic product can comprise a cover substrate disposed over the display. In aspects, at least one of a portion of the housing or the cover substrate comprises the coated article and / or the surface-modifying layer 113 (e.g., fingerprint-hiding coating) discussed throughout the disclosure. Theconsumer electronic product can comprise a portable electronic device, for example, a smartphone, a tablet, a wearable device, or a laptop.
[00453] The coated article and / or surface-modifying layer 113 (e.g., fingerprint-hidingcoating) disclosed herein may be incorporated into another article, for example, an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets,ATTORNEY DOCKET NO. SP23-219WO computers, navigation systems, wearable devices (e.g., watches), and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that may benefit from some transparency, scratch-resistance, abrasion resistance or a combination thereof. An exemplary article incorporating any of the coated articles and / or surface-modifying layers (e.g., fingerprint-hiding coatings) disclosed herein isshown in FIGS. 3-4. Specifically, FIGS. 3-4 show a consumer electronic device 300 includinga housing 302 having front 304, back 306, and side surfaces 308. Although not shown, theconsumer electronic device can comprise electrical components that are at least partially inside or entirely within the housing. For example, electrical components include at least a controller,a memory, and a display. As shown in FIGS. 3-4, the display 310 can be at or adjacent to thefront surface of the housing 302. The consumer electronic device can comprise a coversubstrate 312 at or over the front surface of the housing 302 such that it is over the display 310.In aspects, at least one of the cover substrate 312 or a portion of housing 302 may include anyof the coated articles and / or surface-modifying layers (e.g., fingerprint-hiding coatings) disclosed herein.
[00454] Aspects of methods of making the foldable apparatus and / or foldable substratein accordance with aspects of the disclosure will be discussed with reference to the flow chartin FIGS. 7-8 and example method steps illustrated in FIGS. 9-13.
[0455] Example aspects of making a coated article 3501, 3601, 3611, or 3621 (e.g.,with the surface-modifying layer disposed on the planarization layer 123) will now bediscussed with reference to FIGS. 5-6 and 9-12 and the flow chart in FIG. 7. In a first step701, methods can start with obtaining a substrate 103. In aspects, the substrate 103 may beprovided by purchase or otherwise obtaining a substrate or by forming the substrate. In aspects,the substrate 103 can comprise a glass-based material, a glass-ceramic material, and / or aceramic-based material. In further aspects, glass-based substrates, glass-ceramic substrates and / or ceramic-based substrates can be provided by forming them with a variety of ribbon forming processes, for example, slot draw, down-draw, fusion down-draw, up-draw, press roll, redraw, or float. In further aspects, glass-ceramic substrates and / or ceramic-based substrates can be provided by heating a glass-based substrate to crystallize one or more ceramic crystals.The substrate 103 comprises a first major surface 105 that can extend along a first plane 104.In aspects, as indicated in FIGS. 2A-2C and 36A-36B, an optical stack 203 comprising ananti-reflective coating and / or a gradient coating comprising a refractive index gradient can bedisposed on and / or bonded to the first major surface 105. Although not shown in FIGS. 9-10,it is to be understood that the optical stack 203 can be disposed on the first major surface 105.ATTORNEY DOCKET NO. SP23-219WOIn aspects, the substrate 103 can be chemically strengthened with one or more compressivestress regions (or central tension regions) comprising any of the aspects related to depth of compression, maximum compressive stress, and / or tensile stress discussed above for the corresponding property.
[00456] In aspects, step 701 can further comprise obtaining a functionalized polyhedraloligomeric silsesquioxane (POSS). As used herein, a polyhedral oligomeric silsesquioxane (POSS) refers to a functionalized oligomer silsesquioxane consisting of RSiO1.5monomers. Exemplary aspects of functionalized POSS can comprise 6, 8, 10, or 12 RSiO1.5monomers, although other aspects are possible. For example, functionalized oligomeric silsesquioxane consisting of 8 RSiO1.5 monomers is an octahedral functionalized POSS (e.g., polyoctahedralsilsesquioxane). FIG. 5 shows a functionalized POSS, namely, an octahedral functionalizedPOSS, where R are functional groups that can be independently selected from the functional groups discussed below.
[00457] In aspects, functionalized oligomeric silsesquioxanes can be formed fromcondensation reactions of silane. As used herein, a condensation reaction produces an R2O byproduct, where R can include any of the R units discussed below and can further comprise hydrogen (e.g., with a hydroxyl or water byproduct). For example, silanes (e.g., R3OSi) can be reacted to form terminal RSiO2monomers. For example, a terminal RSiO2monomer can react with another RSiO2monomer (e.g., terminal, non-terminal) to form an RSiO1.5monomer as an oxygen atom of one monomer forms a bond with a silicon atom of another monomer, producing the condensation byproduct. It is to be understood that the RSiO1.5silsesquioxane monomers are different from siloxane monomers, which can include M-type siloxane monomers (e.g., R3SiO0.5), D-type siloxane monomers (e.g., R2SiO2), and / or silica-type siloxane monomers (SiO2).
[00458] Functionalized oligomeric silsesquioxanes can be functionalized by one ormore functional groups. For methods discussed with reference to the flow chart in FIG.7 (e.g.,thermally evaporating the functionalized oligomeric silsesquioxane), a functional groupfunctionalizing the functionalized oligomeric silsesquioxane can exclude hydrogen. In aspects, the functional group functionalizing the functionalized oligomeric silsesquioxane can exclude bisphenols, fluorine-containing functional groups isocyanates, epoxies, glycidyls, oxirane, sulfur-containing functional groups (e.g., thiols), anhydrides, acrylates, methacrylates, and / or alkynes. In aspects, the functional group functionalizing the functionalized oligomeric silsesquioxane be an alkyl group, an alkene group, an aromatic group (e.g., a phenyl group), a silane (e.g., an alkyl silyl group), or combinations thereof. As used herein, an alkyl groupATTORNEY DOCKET NO. SP23-219WO contains a saturated hydrocarbon with carbon-carbon single bonds and hydrogen bonded to carbon atoms. In aspects, alkyl functional groups can range from 1 to 10 carbons (i.e., C1-C10 alkyl), for example, from 1 carbon to 8 carbons (i.e., C1-C8 alkyl) or from 1 to 4 carbons (i.e., C1-C4 alkyl). Exemplary aspects of alkyl functional groups include methyl, isobutyl, and dimethylsilyl. An exemplary aspect of an aromatic functional group is a phenyl group. An exemplary aspect of a silane includes a dimethylsilyl group. As used herein, an alkene group contains an unsaturated hydrocarbon with one or more carbon-carbon double bonds. Alkenes can optionally include one or more carbon-carbon single bonds (e.g., alkyl chains in the alkene group). In even further aspects, the functionalized POSS can be at least partially functionalized by alkenes containing from 2 to 8 carbons (i.e., C2-C8 alkenes). At least partially functionalizedby a functional group B means that one or more of the R-groups shown in FIG. 5 is B.Completely functionalized mean that 95% or more of all R-groups shown in FIG. 5 are B. Anexemplary aspect of an alkene functionalized POSS is a vinyl POSS, for example, partially vinyl functionalized vinyl / isobutyl POSS (OL1123 available from Hybrid Plastics) or octa- vinyl POSS (OL1170 available from Hybrid Plastics). An exemplary aspect of an aromatic functionalized POSS is octaphenyl POSS (MS0840 available from Hybrid Plastics). Exemplary aspects of alkyl functionalized POSS are octamethyl POSS (MS0830 available from Hybrid Plastics) and octa(iso-butyl) POSS (MS0825 available from Hybrid Plastics). Providing a short chain (e.g., about 8 carbons or less) for functionalizing the functionalizedPOSS can enable the functionalized POSS to be evaporated during step 703. Providing one ormore of the functional groups discussed above functionalizing the functionalizing POSS can reduce the reactivity of the functionalized POSS before it is impinged by the ion beam and / or disposed on the substrate (e.g., by sterically hindering interactions between functionalized POSS), which can enable be used to produce the partially condensed silica-like network described above.
[00459] Alternatively, for example, when methods are to proceed to step 713 (e.g.,applying the functionalized oligomeric silsesquioxane as a solution)–instead of step 703 (e.g.,evaporating a functionalized POSS)–, the functional group functionalizing the functionalizedoligomeric silsesquioxane can be hydrogen or an alkyl group. In aspects, the functional groupfunctionalizing the functionalized oligomeric silsesquioxane can exclude bisphenols, fluorine- containing functional groups isocyanates, epoxies, glycidyls, oxirane, sulfur-containing functional groups (e.g., thiols), anhydrides, acrylates, methacrylates, and / or alkynes. In aspects, the functional group functionalizing the functionalized oligomeric silsesquioxane can be hydrogen, an alkyl group, an alkene group, an aromatic group, a silane, or combinationsATTORNEY DOCKET NO. SP23-219WO thereof. For example, the functional group can be one or more of the functional groups discussed above in the previous paragraph in addition to hydrogen. In further aspects, the functional group functionalizing the functionalized oligomeric silsesquioxane can consist of carbon and / or hydrogen. In even further aspects, the functionalized oligomeric silsesquioxane can be at least partially functionalized by and / or completely functionalized by hydrogen. In further aspects, the functionalized POSS can be at least partially functionalized by alkenes containing from 2 to 8 carbons (i.e., C2-C8alkenes), for example, an ethene, a propene, a butene, a pentene, a hexene, a heptane, or a octene. In even further aspects, the functionalized POSS can be at least partially functionalized by alkenes containing from 2 to 8 carbons (i.e., C2-C8 alkenes).
[00460] Throughout the disclosure, an effective diameter of a molecule (e.g.,functionalized POSS) is measured using dynamic light scattering in accordance with ISO 22412:2017. In aspects, an effective diameter of a functionalized POSS can be about 20 nm or less, about 15 nm or less, about 10 nm or less, about 6 nm or less, about 1 nm or more, about 2 nm or more, or about 4 nm or more. In aspects, an effective diameter of a functionalized POSS can be in a range from about 1 nm to about 20 nm, from about 1 nm to about 15 nm, from about 2 nm to about 15 nm, from about 2 nm to about 10 nm, from about 4 nm to about 10 nm, from about 4 nm to about 6 nm, from about 1 nm to about 6 nm, from about 2 nm to about 6 nm, or any range or subrange therebetween. In further aspects, a mean effective diameter of the functionalized POSS can be within one or more of the ranges discussed above in this paragraph. In further aspects, substantially all and / or all of the functionalized POSS can be within one or more of the ranges for the effective diameter of a functionalized oligomeric silsesquioxane discussed above.
[00461] After step 701, as shown in FIG. 9, methods can proceed to step 703comprising evaporating a functionalized POSS onto the first major surface 105 of the substrate103. In aspects, as shown, step 703 can comprise placing the substrate 103 in a chamber 903(e.g., vacuum chamber) that can be maintained at a reduced pressure. In aspects, the reduced pressure can be about 50,000 Pascals (Pa) or less, about 1,000 Pa or less, about 1 Pa or less, about 0.5 Pa or less, about 10-6Pa or more, about 10-4Pa or more, or about 10-3Pa. In aspects, the reduced pressure can range from about 10-6Pa to about 1,000 Pa, from about 10-4to about 1 Pa, from about 10-3to about 0.5 Pa, from about 10-3Pa to about 10-1Pa, or any range orsubrange therebetween. In aspects, the pressure (e.g., reduced pressure) of the chamber 903can be maintained by operating one or more of the valve 905 and 925. In further aspects, thepressure of the chamber 903 can be reduced or maintained by opening the valve 905 connectedATTORNEY DOCKET NO. SP23-219WOto a pump 907 that can remove gas from the chamber 903. In further aspects, the pressure ofthe chamber 903 can be increased or maintained by opening the valve 925 connected to a gassource 921, which adds gas to the chamber, as indicated by arrow 923. In aspects, the gassource 921 can provide a non-reactive gas (e.g., argon, helium, krypton), oxygen, nitrogen, air,or a combination thereof. Providing a reduced pressure when evaporating the functionalized POSS can increase a rate of evaporation and / or enable a wide range of functionalized POSS materials to be used.
[00462] As shown in FIG. 9, the functionalized POSS 913 can be positioned in acontainer 911 placed within the chamber 903. In the chamber 903, the functionalized POSS913 can evaporate (as indicated by arrow 915) into the gas phase (as indicated by 917) that canbe disposed on the first major surface 105 of the substrate 103 (as indicated by arrow 919).Exemplary aspects of the container 911 include a Knudsen cell or an effusion cell. In aspects,the container 911 can be maintained at a temperature of about 50°C or more, about 65°C ormore, about 75°C or more, about 90°C or more, about 110°C or less, about 200°C or less, about 170°C or less, about 150°C or less, about 135°C or less, about 120°C or less, or about 110°Cor less. In aspects, the container 911 can be maintained at a temperature ranging from about50°C to about 200°C, from about 65°C to about 170°C, from about 75°C to about 150°C, from about 90°C to about 135°C, from about 110°C to about 135°C, or any range or subrange therebetween. Heating the container can facilitate evaporation of the functionalized POSS, which can increase a deposition rate.
[00463] In aspects, a deposition rate of the functionalized POSS 913 can be monitoredusing a sensor comprising a surface that is positioned a predetermined distance from the surface(e.g., first major surface 105 of the substrate 103). In further aspects, the sensor can beconfigured to detect nanogram differences in mass from material deposited on the surface, where the increase in mass and predetermined surface area of the surface can be used to determine an effective deposition rate. It is to be understood that the “effective deposition rate”is not necessarily the actual deposition rate on the surface (e.g., first major surface 105), and,in fact, may overestimate the actual deposition rate by as much as a factor or 2 or 3. An exemplary aspect of the sensor is a quartz crystal microbalance (QCM). As used herein, the “deposition rate” or “evaporation rate” refers to the effective deposition rate as measured by aQCM positioned 500 mm below the surface and 150 mm above the container 911.
[0464] Although not shown, it is to be understood that if an optical stack 203 wasdisposed on the first major surface 105 that the functionalized POSS 913 would be disposedover the first major surface 105 and disposed on the optical stack 203. In aspects, anATTORNEY DOCKET NO. SP23-219WOevaporation rate of the functionalized POSS 913 onto the first major surface 105 can be about0.01 nanometers per second (nm / s) (0.1 A / s) or more, about 0.03 nm / s (0.3 A / s) or more, about 0.05 nm / s (0.5 A / s) or more, about 0.1 nm / s or more (1 A / s), about 0.5 nm / s or less (5 A / s), about 0.3 nm / s (3 A / s) or less, about 0.2 nm / s (2 A / s) or less, or about 0.15 nm / s (1.5 A / s) orless. In aspects, an evaporation rate of the functionalized POSS 913 onto the first major surface105 can range from about 0.01 nm / to about 0.5 nm / s, from about 0.03 nm / s to about 0.3 nm / s,from about 0.05 to about 0.2 nm / s, from about 0.1 nm / s to about 0.15 nm / s, or any range or subrange therebetween. Controlling the evaporation rate within one or more of the above- mentioned ranges can efficiently (e.g., quickly) deposit a substantially uniform coating of thefunctionalized POSS on the first major surface. In aspects, at the end of step 703, a thicknessof the functionalized POSS disposed on the first major surface 105 can be within one or moreof the ranges discussed above with reference to the planarization thickness 129. Withoutwishing to be bound by theory, it is believed that the evaporation of the functionalized POSS and deposition onto the first major surface does not in itself chemically (e.g., covalently) bond the functionalized POSS to the first major surface or modify the structure of the functionalizedPOSS. An Exemplary aspect of the container 911 in a Radak II cell that can be used in thechamber 903, for example, an Angstrom Engineering Evovac chamber. Although not shown,it is to be understood that if an optical stack 203 was disposed on the first major surface 105that the functionalized POSS 913 would be disposed over the first major surface 105 anddisposed on the optical stack 203.
[0465] After step 703 (or concurrent with step 703), as shown in FIG. 9, methods canproceed to step 705 comprising impinging an ion beam traveling as a plume 933 on the firstmajor surface 105 of the substrate 103. As shown, the substrate 103 can be in the chamber 903,which can be the same chamber 903 discussed above with reference to step 703. In aspects, asshown in FIG. 9, a beam source 931 can be configured to emit an ion beam traveling as aplume 933 that is incident on the first major surface 105 of the substrate 103 (or the opticalstack). The beam source 931 can be operated such that the ion beam traveling as a plume 933impinges the entire first major surface 105. In aspects, the ion beam source 931 can comprisean end-Hall ion source, a grided ion source, or an inductively coupled plasma (ICP) ion source.An exemplary aspect of a beam source 931 is an end-Hall ion source. In aspects, the beamsource 931 can generate the ion beam using a discharge current. Without wishing to be boundby theory, it is believed that an extent of reaction (e.g., from functionalized POSS to partial silica-like network) is influenced by the ion beam energy and discharge current. In further aspects, the discharge current can be about 0.25 Amps (A) or more, about 0.3 A or more, aboutATTORNEY DOCKET NO. SP23-219WO 0.35 A or more, about 1 A or less, about 0.75 A or less, or about 0.5 A or less. In further aspects, the discharge current can range from about 0.25 A to about 1 A, from about 0.3 A to about 0.75 A, from about 0.35 A to about 0.5 A, or any range or subrange therebetween. In aspects, thebeam source 931 can be operated at a voltage of about 100 Volts (V), for example, from about50 V to about 220 V, from about 70 V to about 120 V, from about 90 V to about 110 V, or any range or subrange therebetween. In aspects, the ion beam can comprise ions of oxygen, ions of argon, or combinations thereof. The composition of the ion beam can be adjusted throughchoice of the gas source 921 and controlling an amount of gas released from the gas source 921(e.g., using the valve 925). In aspects, the chamber 903 (e.g., vacuum chamber) can bemaintained at a reduced pressure within one or more of the ranges discussed above for thereduced pressure in step 703 (e.g., from about 10-8 Pa to about 10-7 Pa).
[0466] Without wishing to be bound by theory, it is believed that the ion beam disruptsthe cage structure of the functionalized POSS, volatilizes the functional groups functionalizing the functionalized POSS, and / or causes the functionalized POSS to become bonded to thesurface it is disposed on (e.g., the first major surface 105 as shown in FIG. 9 or the fourthmajor surface 207 of the optical stack 203, if present). At the end of step 705, the coating 1033(see FIG.10) formed can comprise a partial silica-like network, for example, with a percentageof silicon atoms in the coating being in a silica-like network within one or more of the rangesdiscussed above for the percentage of silica atoms in the planarization layer 123 in a silica-likenetwork. Additionally or alternatively, at the end of step 705, the coating 1033 (see FIG. 10)formed can comprise a ratio of Si-O-Si bonds to silicon atoms within one or more of the ranges discussed above for the ratio of Si-O-Si bonds to silicon atoms. In further aspects, impingingthe ion beam in step 705 can convert at least a fraction of the silicon atoms in a cage structureof the functionalized POSS to a partial Si-O-Si network (i.e., Si-O-Si bonds). In even furtheraspects, the fraction of silicon atoms converted in step 705 can range from about 50% to about90%, from about 60% to about 80%, from about 65% to about 75%, or any range or subrangetherebetween. In aspects, the coating thickness 1039 of the coating 1033 defined betweenopposing surfaces 1035 and 1037 can be within one or more of the ranges discussed above forthe planarization thickness 129, and / or the coating 1033 can correspond to the planarizationlayer 123.
[0467] In aspects, the evaporating the functionalized POSS 913 of step 703 and theimpinging the ion beam traveling along a beam path of step 705 can occur simultaneously. Asused herein, steps 703 and 705 occurring “simultaneously” means that there is at least onepoint in time where the activities of steps 703 and 705 are both occurring. It is to be understoodATTORNEY DOCKET NO. SP23-219WO that it can still be simultaneous if one of the steps begins before the other step ends and / or ifone of the steps ends before the other one ends, although both steps 703 and 705 can begin atthe same time and / or end at the same time in further aspects. As shown in FIG. 9, the container911 (e.g., Knudsen cell or an effusion cell), the substrate 103, and at least a portion of the beampath can be positioned in the chamber 903 such that the functionalized POSS 913 in the gasphase (as indicated by 917) and / or disposed on the first major surface 105 can be impinged bythe ion beam travelling along the beam path. Performing steps 703 and 705 simultaneouslycan facilitate the formation of a coating 1033 (see FIG. 10) with good adhesion to the substrate103 and / or that is relatively homogenous. Providing a discharge current of about 0.25 A ormore can facilitate the formation of the coating 1033 (see FIG. 10), for example, producing anion beam with sufficient energy to cause the functionalized POSS to react with otherfunctionalized POSS and / or the first major surface 105 of the substrate 103 at an appreciablerate (e.g., compared to lower discharge currents). Providing a discharge current of about 1 A or less can provide an ion beam that is not so strong as to remove any POSS material beingdisposed by the evaporating. Additionally, performing steps 703 and 705 simultaneously candecrease processing time.
[00468] Alternatively, after step 701, as shown in FIG. 11, methods can proceed to step713 comprising disposing the precursor solution 1103 over the first major surface 105 of thesubstrate 103. The precursor solution 1103 can comprise the polysilazane or the POSS in aconcentration within one or more of the ranges discussed in the previous paragraph. In aspects,as shown FIG. 11, the precursor solution 1103 can be dispensed from a container 1101 (e.g.,conduit, flexible tube, micropipette, ink-jet print head, or syringe) over (e.g., onto) the firstmajor surface 105 of the substrate 103 to form a precursor layer 1105. In further aspects, asshown, step 803 can comprise spin coating the precursor solution 1103 over (e.g., onto) thefirst major surface 105, for example, by disposing the second major surface 107 of the substrateover a surface 1115 of a holder 1113 and the holder can be rotated (as shown by arrow 1119)while and / or after the precursor solution 1103 is disposed over the first major surface 105. Ineven further aspects, the holder 1113 can be rotated at 200 revolutions per minute (rpm) ormore, about 500 rpm or more, about 700 rpm or more, about 4,000 rpm or less, about 2,500rpm or less, or about 1,500 rpm or less. In even further aspects, the holder 1113 can be rotatedfrom 200 rpm to about 4,000 rpm, from about 500 rpm to about 2,500 rpm, from about 700 rpm to about 1,500 rpm, or any range or subrange therebetween. Spin coating the precursor solution can form a substantially uniform precursor layer over the first major surface of the substrate.ATTORNEY DOCKET NO. SP23-219WO
[00469] After step 713, as shown in FIG. 12, methods can proceed to step 715comprising heating the precursor layer 1105 of the precursor solution 1103 (see FIG. 11) at afirst temperature for a first period of time to form the coating 1033. In aspects, as shown, thesubstrate 103 can be placed in an oven 1201 maintained at the first temperature for the firstperiod of time. In aspects, the first temperature can be about 150°C or more, about 170°C or more, about 190°C or more, about 400°C or less, about 300°C or less, about 250°C or less, about 230°C or less, or about 210°C or less. In aspects, the first temperature can range from about 150°C to about 400°C, from about 150°C to about 300°C, from about 150°C to about 250°C, from about 170°C to about 230°C, from about 190°C to about 210°C, or any range or subrange therebetween. In aspects, the first period of time can be about 5 minutes or more, about 10 minutes or more, about 20 minutes or more, about 25 minutes or more, about 2 hours or less, about 1.5 hours or less, about 1 hour or less, or about 40 minutes or less. In aspects, the first period of time can range from about 5 minutes to about 2 hours, from about 10 minutes to about 1.5 hours, from about 20 minutes to about 1 hour, from about 25 minutes to about 40minutes, or any range or subrange therebetween. In aspects, the precursor solution 1103 cancomprise a catalyst or be free from a catalyst. In aspects, the precursor solution 1103 cancontain a silane in addition to the polysilazane or the POSS. The silane can comprise any of the aspects discussed above for silanes.
[00470] Without wishing to be bound by theory, heating the precursor layer of theprecursor solution can remove solvent from the precursor layer and / or partially cure the polysilazane or the POSS, for example, to form a silica or a partial silica-like network (e.g.,corresponding to the planarization layer 123) . For example, heating the POSS can cause thesilicon-oxygen network to rearrange to a silica-like network and / or bond to a surface (e.g., firstmajor surface 105) that the precursor solution is disposed on. For example, as shown in FIG.6, the polysilazane can undergo a reaction where ammonia and hydrogen is evolved and oxygen and water is consumed to transform from a structure with an alternating silicon-nitrogen backbone to a silica-like network with silicon-oxygen bonds. Since the polysilazane may onlypartially undergo this reaction, at the end of the step 715, the coating 1033 can comprise silicon,oxygen, nitrogen, and / or hydrogen. Also, it is to be understood that these reactions maycontinue in subsequent steps (e.g., step 707).
[0471] After step 705 or 715, as shown in FIGS. 10 and 13, methods can proceed tostep 707 comprising reacting material (e.g., coating 1033) at the first major surface 105 of thesubstrate 103 with an alkyl silane to form a surface-modifying layer 113 (e.g., fingerprint-hiding coating) that can be disposed over the substrate 103 and / or the coating 1033. In aspects,ATTORNEY DOCKET NO. SP23-219WOthe alkyl silane 1013 (e.g., droplets 1317) can comprise an alkyl silane. In further aspects, thealkyl silane can comprise four or more carbons, for example, from 3 carbons to 34 carbons (e.g., C3-C34 alkyl), from 4 carbons to about 34 carbons (i.e., a C4-C34 alkyl group), from 6 carbons to 20 carbons (e.g., C6-C34 alkyl), from 8 carbons to 18 carbons (e.g., C8-C18 alkyl), from 8 carbons to 12 carbons (e.g., C8-C12 alkyl), or any range or subrange therebetween. Exemplary aspects of alkyl silanes include iso-octyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, or combinations thereof. In further aspects, the alkyl silane can comprise at least two reactive groups. Each of the at least two reactive groups can be independently selected from a silane, a non-fluorine halogen, or a combination thereof provided that at least one of the at least two reactive groups is a silane. In even further aspects, at least two of the at least two reactive groups can be located at opposite ends of the alkyl silane. In further aspects, the alkyl silane can be a bis-silane or a tris-silane. In further aspects, a silane of the alkyl silane can be a trichlorosilane, a dichloromethoxy silane, a chlorodimethoxysilane, a dichlorodimethylesilane, a chlorodimethylsilane, a trimethoxy silane, a triethoxy silane, or combinations thereof. Exemplary aspects of the alkyl silane include1,8-bis(chlorodimethylsilyl)ocatane (see FIG. 17A), chloropropyltrimethoxysilane (see FIG.17B), or combinations thereof. In aspects, the alkyl silane may comprise a bipodal or multipodal alkyl silane with two or more silane head groups on each end of the alkyl group of the alkyl silane (e.g. bis-silane or tris-silane). Exemplary aspects of bipodal alkyl silanesinclude 1,6-bis(trimethoxysilyl)hexane (bishexane) (see FIG. 17E) and 1,8-bis(trimethoxysilyl)octane (BISMO) (see FIG. 17F). In aspects, the alkyl silane may include acombination of one or more monopodal alkyl silanes and one or more bipodal alkyl silanes. A mixture of the alkyl silanes can be used to obtain various desirable attributes, e.g. finger-print hiding in combination with good durability. The coating therefore can be composed of two or more functionalities. For instance, the alkyl silane may include one or more bipodal alkyl silanes, such as 1,8-bis(chlorodimethylsilyl) octane, 1,8-bis(dimethylmethoxysilyl)octane, 1,6- bis(trichlorosilyl) hexane, bis(triethoxysilyl) methane, 1,2-bis(triethoxysilyl) ethane, 1,6- bis(trimethoxysilyl) hexane, 1,8-bis(triethoxysilyl) octane, 1,8-bis(trimethoxysilyl) octane, or combinations thereof in addition to one or more monopodal alkyl silanes, such as octadecyl trimethoxysilane, dodecyl trimethoxysilane, or combinations thereof. Without intending to be bound by any particular theory, it is believed that multipodal alkyl silanes (e.g. bipodal alkyl silanes) are thought to create longer chains by polycondensation between molecules. In the case of the mono-functional silanes the non-reactive methyl groups may disrupt chain packing. In the case of di- or tri-functional silanes, polycondensation can occur from multiple sites andATTORNEY DOCKET NO. SP23-219WO the molecule can become more branched, resulting in poor ordering. Due to their bipodal nature, these materials may contain unreacted, terminal hydroxyl groups. In some aspects, it may be beneficial to react or “cap” these groups with a monofunctional, monopodal silane or other molecule. Such examples include monofunctional alkylsilanes where the alkyl chain comprises 3 to 36 carbons. Other suitable steps include methylation such as through the use of hexamethyldisilazane (HMDS). Suitable functionalization for improved durability include linear alkylsilanes where the alkyl chain comprises 3 to 26 carbons. Certain examples include octadecyltrimethoxysilane and dodecyltrimethoxysilane. Such examples are thought to form well ordered SAMs that maintain high water contact angles, even after rubber abrasion testing on bare glass.. In aspects, a ratio between the monopodal alkyl silanes to the multipodal alkylsilanes used to form the polymer at the surface-modifying layer 113 may be selected to tunethe finger-print hiding attributes and the cleanability and / or durability attributes of the surface-modifying layer 113 (e.g., fingerprint-hiding coating) formed therefrom. Without intending tobe bound by any particular theory, it is believed that the monopodal alkyl silane may increasethe cleanability and / or durability of the surface-modifying layer 113 formed therefrom, and themultipodal silane may increase finger-print hiding attributes of the surface-modifying layer113 formed therefrom. The deposition of monopodal silanes and multipodal silanes at thesurface-modifying layer 113 may include various ratios between the monopodal silanes andthe multipodal silanes of the alkyl silane. In embodiments, the alkyl silane may comprise a ratio of the multimodal alkyl silane to the monopodal alkyl silane of from 10:1 to 1:10, such as from 10:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 9:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 8:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, from 7:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 6:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 5:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 4:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1 from 2:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or from 1:1 to 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, or 1:2. The alkyl-silane of the method may include any aspects described herein with regards to the alkyl-silane of thesurface-modifying layer 113 described herein. In aspects, formation of the surface-modifyinglayer 113 with two or more alkyl silanes, as described herein may be done simultaneously withforming the planarization layer 123 or may be subsequent to forming the planarization layer123. In other embodiments, the functionalities may be separately inkjet printed (e.g., in a CMYK printer setup) in various patterns. This would allow for spatial variation of the functionality. For instance, such aspects may change the functionality over a sensor or camera, or to change the tactile response in a certain area. Capping of any non-reactive end groups,ATTORNEY DOCKET NO. SP23-219WO such as hydroxyls, may be achieved in the same solution or via a separate step. Providing an alkyl silane can reduce a surface energy (e.g., total, dispersive, polar) of the coating, which canenable the resulting surface-modifying layer 113 (e.g., fingerprint-hiding coating) to beoleophilic. At the end of step 707, the silane can be bonded to the material of the coating 1033to form the surface-modifying layer 113 (see FIGS. 35 and 36A-36C).
[0472] In further aspects, as discussed above, the alkyl silane can comprise a one ormore of the silanes discussed above in addition to an additional alkyl silane that can contribute to the siloxane part of the structure (i.e., the [Si(R”)2O]npart of the polymeric structure discussed in the following paragraphs). In even further aspects, the additional alkyl silane can comprise a dialkylsilane with silanes at both ends of the dialkylsilane, and the alkyl groups of dialkyl silane can be methyl, ethyl, or a combination thereof. An exemplary aspect of thedialkyl silane is a dimethyl silane, namely, dichloro-tetramethyl-disoloxane (see FIG. 17D),although other leaving groups can independently be groups other chlorine (e.g., selected from those discussed in the previous paragraph). In even further aspects, an amount of the additional alkyl silane as a wt% of a total amount of alkyl silanes can be about 1 wt% or more, about 5 wt% or more, about 10 wt% or more, about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, about 45 wt% or more, about 50 wt% or more, about 55 wt% or more, about 60 wt% or more, about 65 wt% or more, about 70 wt% or more, about 75 wt% or more, about 90 wt% or less, about 85 wt% or less, about 80 wt% or less, about 75 wt% or less, about 70 wt% or less, about 65 wt% or less, about 60 wt% or less, about 55 wt% or less, about 50 wt% or less, about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, or about 30 wt% or less. In even further aspects, an amount of the additional alkyl silane as a wt% of a total amount of the alkyl silanes can be in a range from about 1 wt% to about 90 wt%, from about 5 wt% to about 90 wt%, from about 10 wt% to about 85 wt%, from about 20 wt% to about 80 wt%, from about 25 wt% to about 75 wt%, from about 30 wt% to about 70 wt%, from about 35 wt% to about 65 wt%, from about 40 wt% to about 60 wt%, from about 45 wt% to about 55 wt%, from about 45 wt% to about 50 wt%, or any range or subrange therebetween. In preferred aspects, an amount of the additional alkyl silane as a wt% of a total amount of the alkyl silanes can be from 1 wt% to 90 wt% or from 25 wt% to 75 wt%. For example, the alkyl silane (e.g., one or more alkyl silanes) and the additional silane can form a copolymer (e.g., roughly alternating copolymer). An exemplary aspect is a mixtureof 1,8-bis(chlorodimethylsilyl)octane (see FIG. 17A) and dichloro-tetramethyl-disoloxane(see FIG. 17D). An additional exemplary aspect is a mixture of 1,8-bis(dimethylmethoxysilyl)octane (see FIG. 17H) and dichloro-tetramethyl-disoloxane (seeATTORNEY DOCKET NO. SP23-219WO FIG.17D). Alternatively, the alkyl silanes can exclude an additional alkyl silane and / or consist of a single alkyl silane selected from those discussed in the previous paragraph.
[0473] FIG. 10 shows one method of silanization. Methods can be performed at atmospheric pressure and / or a pressure within one or more of the ranges discussed above forstep 703. For example, the chamber 1003 can be an inert ampoule is heated by an oven at fromabout 60°C to about 200°C (e.g., about 60°C or more, about 80°C or more, about 90°C or more, about 100°C or more, about 120°C or more, about 140°C or more, about 250°C or less, about 220°C or less, about 200°C or less, about 180°C or less, or about 160°C or less). Samples are optionally plasma treated for surface activation with an O2or Ar plasma, and placed in the ampoule with a drop of silane, sealed and heated for from about 2 hours to about 5 hours. Providing an elevated temperature when evaporating the silane and reacting the silane with the coating can increase a rate of evaporation, enable a wide range of silanes to be used, increase a reaction rate or reactivity of the silane, and / or promote the formation of a covalent bondingto surface 1035 of the coating 1033 (e.g., planarization layer 123). In further aspects, as shownin FIG. 10, the substrate 103 can be placed in a chamber 1003, which can be the same as thechamber 903 discussed above with reference to step 703 and / or step 705. In further aspects,the chamber 1003 can be maintained at a reduced pressure, which can be within one or moreof the ranges discussed above for the reduced pressure in step 703. In aspects, the chamber1003 can be maintained at a temperature within one or more of the range discussed above forthe temperature in step 705. Providing a reduced pressure and / or elevated temperature whenevaporating the silane and reacting the silane with the coating (e.g., planarization layer 123)can increase a rate of evaporation, enable a wide range of silanes to be used, increase a reactionrate or reactivity of the silane, and / or promote the formation of a silica-like network. As shownin FIG. 10, an alkyl silane 1013 can be positioned in a container 1011 placed within thechamber 1003. In the chamber 1003, the alkyl silane 1013 can evaporate (as indicated by arrow1015) into the gas phase (as indicated by 1017) that can be disposed on the exterior surface1035 of the coating 1033 (as indicated by arrow 1019). In aspects, an evaporation rate of thealkyl silane 1013 can be controlled to efficiently (e.g., quickly) deposit and react the silanewith the material of the coating (e.g., on the first major surface).
[00474] Alternatively, a low vacuum chamber with a vapor source such as a YES-1124P (available from Yield Engineering Systems) can be used in step 707. For example, thechamber can be heated at a temperature from about 100°C to about 200°C and evacuated to a pressure of about 10 Pa. Substrates are optionally exposed to a Ar or O2 capacitively coupled plasma generated by low or high frequency RF. After pumping to base pressure the silaneATTORNEY DOCKET NO. SP23-219WO precursor vapor is introduced to the chamber. The silane precursor vapor can be generated using a liquid vaporizer, where liquid can be injected by a pulse pump into a heated vaporization cell with independent temperature control to vaporize it and the vapor can travel through independently heated passage into the chamber. With independent temperature control, condensation in the passage can be prevented. Vaporization of the silane can raise the chamber pressure by from about 1 Pa to about 100 Pa, and the substrates are exposed to the vapor for a time (e.g., from about 2 minutes to about 20 minutes) and the chamber is evacuated with the pump to remove excess vapors and condensation products.
[00475] Alternatively, in another embodiment, a high vacuum coating chamber similarto FIG. 9 can be used in step 707. Substrates can be cleaned with the End-Hall or ICP ionsource, and the silane can be vaporized from either a liquid injection source (similar to that described above), or desorbed from a sorbate (typically enclosed in a canister) using a thermal source (e.g., a resistively heated tungsten boat, an effusion or Knudesn cell, or an electron beam evaporator). Deposition rate and total thickness can be monitored in these systems with a quartz crystal monitor (QCM). This type of chamber is commonly used in production of fluorinated ETC coatings on handheld devices such as cellphones.
[00476] Alternatively or additionally, the alkyl silane (e.g., alkyl silane) can react withthe surface (e.g., first major surface 105, a surface of an optical stack 203, 203a, or 203b, or asurface of the planarization layer 123) to from the surface-modifying layer 113 for apredetermined period of time at a temperature from about 20°C to about 40°C, from about 20°C to about 36°C, from about 22°C to about 30°C, from about 25°C to about 30°C, or any range or subrange therebetween. For example, the alkyl silane can form the surface-modifying layer at ambient conditions (e.g., from about 25°C to about 30°C) to form the surface-modifying layer. In aspects, the predetermined period of time for the alkyl silane to form the surface- modifying layer can be about 1 hour or more, about 2 hours or more, about 3 hours or more, about 4 hours or more, about 6 hours or more, about 24 hours or less, about 12 hours or less, about 8 hours or less, about 6 hours or less, about 4 hours or less, about 3 hours or less, or about 2 hours or less. In aspects, the predetermined period of time for the alkyl silane to form the surface-modifying layer can be in a range from about 1 hour to about 24 hours, from about 2 hours to about 12 hours, from about 3 hours to about 8 hours, from about 4 hours to about 6 hours, or any range or subrange therebetween. It is to be understood that the lower-temperature curing of the alkyl silane to form the surface-modifying layer can be used with any method of disposing the alkyl silane on the surface (e.g., printing, spray, evaporating, solution coating, etc.).ATTORNEY DOCKET NO. SP23-219WO
[00477] Alternatively, in another embodiment, although not shown, step 707 cancomprise solution coating the substrate with a solution containing the alkyl silane. For example, disposing the silane on the substrate can comprise dip coating the substrate in a solution comprising the silane can comprise spin coating the substrate with the solution comprising the silane, spray coating the substrate with a solution comprising the silane, or printing on the substrate with a solution comprising the silane. In aspects, the silane solution can comprise the s...
Claims
ATTORNEY DOCKET NO. SP23-219WO What is claimed is:
1. A coated article comprising:a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein the fingerprint-hiding coating is fluorine-free, wherein the fingerprint-hiding coating exhibits: a water contact angle from 90° to 120°; an oleic acid contact angle of 40° or less; and a coefficient of friction of the exterior surface is 0.25 or less.
2. The coated article of claim 1, wherein the fingerprint-hiding coating comprises an alkylsilane at the exterior surface; wherein: the alkyl silane is bonded to the substrate by a silane group, the alkyl silane is bonded to another part of the fingerprint-hiding coating by a silane group, or both; the silane group of the alkyl silane is at a free end of the alkyl silane; or both.
3. The coated article of claim 2, wherein the fingerprint-hiding coating comprises anoligomer of the alkyl silane, a polymer of the alkyl silane, or both.
4. The coated article of claim 3, wherein the oligomer of the alkyl silane, the polymer ofthe alkyl silane, or both comprises at least one of: a dialkyl siloxane block; a dimethylsiloxane block bonding monomers of the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, together; or a disiloxane group bonding monomers of the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, together.
5. The coated article of any one of claims 2-4, wherein the alkyl silane is substantially freeof chlorine.
6. The coated article of any one of claims 1-5, wherein the fingerprint-hiding coatingcomprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein theATTORNEY DOCKET NO. SP23-219WO oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
7. The coated article of claim 6, wherein, in the structure, at least one of:n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
8. The coated article of claim 6, wherein, in the structure, at least one of:n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
9. The coated article of any one of claims 6-8, wherein the fingerprint-hiding coatingcomprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3and CH2CH3, and m is from 3 to 34.
10. The coated article of claim 9, wherein R’ is CH3, and m is 8.
11. The coated article of claim 9 or claim 10, wherein the condensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
12. The coated article of claim 11, wherein a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof is from 10:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO 13. The coated article of any one of claims 6-12, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
14. The coated article of claim 13, wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
15. The coated article of claim 2, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
16. The coated article of claim 15, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
17. The coated article of claim 15, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
18. The coated article of claim 15 wherein, in the structure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.ATTORNEY DOCKET NO. SP23-219WO 19. The coated article of any one of claims 15-17 wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.
20. The coated article of claim 18, wherein R is OCH3, and m is 8.
21. The coated article of claim 18, wherein R is OCH3, and m is 6.
22. The coated article of any one of claims 18-21, wherein the condensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
23. The coated article of claim 21, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof is from 10:1 to 1:
10.
24. The coated article of any one of claims 21-23, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
25. The coated article of claim 24, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
26. The coated article of claim 24, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO 27. The coated article of any one of claims 21-23, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
28. The coated article of claim 27, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
29. The coated article of claim 27, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:
10.
30. The coated article of any one of claims 1-29, wherein the fingerprint-hiding coating exhibits the oleic acid contact angle of 30° or less.
31. The coated article of any one of claims 1-30, wherein the fingerprint-hiding coating exhibits at least one of: a voltage of about 15 Volts or less in a Tribocharging test; or a voltage difference between a peripheral contact region and a center contact region of about 5 Volts or less in the Tribocharging test.
32. The coated article of any one of claims 1-31, wherein when a simulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits at least one of: an effective diameter of droplets of the simulated fingerprint of 10 µm or more; a mean height of droplets of the simulated fingerprint on the exterior surface of 0.15 µm or less; or a spherical cap radius of droplets of the simulated fingerprint of 40 µm or more.
33. The coated article of any one of claims 1-32, wherein when a simulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits:ATTORNEY DOCKET NO. SP23-219WO a core material value Vmc of a droplet of the simulated fingerprint of 0.10 µm3 / µm2or more between areal material ratios of 10% and 90%.
34. The coated article of claim 33, wherein the fingerprint-hiding coating exhibits at least one of: a ratio of a volume of the droplet to an area of the droplet is 0.78 µm3 / µm2or less; a ratio of a height of the droplet to the area of the droplet is 0.005 µm / µm2or less; a total area of the simulated fingerprint over the exterior surface of 150,000 µm2or more; a haze of 8% or less with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; a center of a sphere modeled on the droplet of the simulated fingerprint is located greater than 30 µm from the exterior surface of the fingerprint-hiding coating; a mean gray level is 150 or less as measured in a Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; or a normalized gray level is 2.0 or less as measured in a Normalized Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test.
35. The coated article of any one of claims 1-34, wherein the fingerprint-hiding coating comprises at least one of: a polar surface energy of from 2 milliNewtons per meter to 6 milliNewtons per meter; or a total surface energy of from 25 milliNewtons per meter to 35 milliNewtons per meter.
36. The coated article of any one of claims 1-35, wherein the fingerprint-hiding coating comprises a thickness from 1 nanometer to 75 nanometers.
37. The coated article of any one of claims 1-36, wherein the exterior surface of the fingerprint-hiding coating comprises from 0.5 atom% to 2 atom% of a non-fluorine halogen.
38. The coated article of any one of claims 1-37, wherein the exterior surface of the fingerprint-hiding coating is free of a transition metal-containing compound.ATTORNEY DOCKET NO. SP23-219WO 39. The coated article of any one of claims 1-38, wherein the fingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
40. The coated article of any one of claims 1-39, further comprising a planarization layer positioned between the substrate and the fingerprint-hiding coating, the fingerprint-hiding coating disposed on the planarization layer, the planarization layer exhibiting at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silicon in the planarization layer is about 0.2 or more.
41. The coated article of claim 40, wherein the planarization layer comprises a refractive index ranging from 1.37 to 1.
55.
42. The coated article of any one of claims 40-41, wherein the planarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
43. The coated article of any one of claims 40-42, wherein the planarization layer exhibits at least one of: an abraded water contact angle of about 80° or more after being abraded for 2,000 cycles in a Steel Wool Abrasion test; a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
44. The coated article of any one of claims 1-43, further comprising at least one of: an anti-reflective coating positioned between the fingerprint-hiding coating and the substrate; orATTORNEY DOCKET NO. SP23-219WO a gradient coating comprising a refractive index gradient positioned between the fingerprint-hiding coating and the substrate.
45. The coated article of any one of claims 1-44, further comprising an optical stack positioned between the fingerprint-hiding coating and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
46. The coated article of claim 45, wherein the optical stack has a stack thickness from about 10 nanometers to about 10 micrometers.
47. The coated article of claim 46, wherein the stack thickness of the optical stack is from about 50 nanometers to about 5 micrometers.
48. The coated article of any one of claims 46-47, wherein the stack thickness of the optical stack is from about 50 nanometers to about 500 nanometers.
49. The coated article of any one of claims 45-48, wherein the optical stack comprises a scratch resistant layer, and the scratch resistant layer has a scratch-resistant thickness from 0.05 micrometers to 3 micrometers.
50. The coated article of any one of claims 45-49, wherein the coated article including the optical stack and the fingerprint-hiding coating exhibits a hardness of 8 GigaPascals or greater measured by a Berkovich Indenter Hardness test.
51. The coated article of any one of claims 45-50, wherein the optical stack comprises one or more of a silicon-containing oxide, a silicon-containing nitride, a silicon-containing oxynitride, and Nb2O5.
52. The coated article of any one of claims 45-51, wherein the optical stack comprises two or more layers with different refractive indices including at least a first low refractive index (RI) layer and a second high refractive index (RI) layer, wherein the absolute value of a difference between the first low RI layer and the second high RI layer is 0.2 or more, and further wherein the optical stack comprises one or more of a silicon-containing oxide, a silicon- containing nitride, a silicon-containing oxynitride, and Nb2O5.ATTORNEY DOCKET NO. SP23-219WO 53. The coated article of any one of claims 1-52, wherein the substrate is a textured substrate.
54. The coated article of claim 53, wherein the coated article further comprises an anti- reflective coating or a gradient coating positioned between the fingerprint-hiding coating and the textured substrate.
55. The coated article of claim 54, wherein a thickness of the anti-reflective coating is from about 200 nanometers to about 3 micrometers.
56. The coated article of any one of claims 1-52, wherein the substrate is a polymer substrate.
57. A coated article comprising: a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selectedfrom 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 or more, q is1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
58. The coated article of claim 57, wherein R” is CH3.
59. The coated article of any one of claims 57-58, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
60. The coated article of any one of claims 57-59, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100;ATTORNEY DOCKET NO. SP23-219WO n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
61. A coated article comprising: a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34..
62. The coated article of claim 61, wherein R’ is CH3.
63. The coated article of claim 61, wherein R’ is CH3, and m is 8.
64. The coated article of any one of claims 61-63, wherein the condensation product further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
65. The coated article of claim 64, wherein a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:
10.
66. The coated article of any one of claims 61-65, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof .ATTORNEY DOCKET NO. SP23-219WO 67. The coated article of claim 66, wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
68. The coated article of any one of claims 57-67, wherein the fingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
69. The coated article of any one of claims 57-68, further comprising an optical stack positioned between the fingerprint-hiding coating and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
70. The coated article of any one of claims 57-69 wherein the substrate is a textured substrate.
71. The coated article of claim 70, wherein the coated article further comprises an anti- reflective coating or a gradient coating positioned between the fingerprint-hiding coating and the textured substrate.
72. The coated article of any one of claims 57-68, wherein the substrate is a polymer substrate.
73. A coated article comprising: a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, andATTORNEY DOCKET NO. SP23-219WO OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
74. The coated article of claim 73, wherein the alkyl silane is chlorine-free.
75. The coated article of claim 73 or claim 74, wherein R’ is OCH3.
76. The coated article of any one of claims 73-75, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
77. The coated article of any one of claims 73-75, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
78. The coated article of any one of claims 73-75 wherein, in the structure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
79. A coated article comprising: a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.ATTORNEY DOCKET NO. SP23-219WO 80. The coated article of claim 79, wherein R is OCH3, and m is 8.
81. The coated article of claim 80, wherein R is OCH3, and m is 6.
82. The coated article of any one of claims 79-81, wherein the condensation product further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
83. The coated article of claim 82, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:
10.
84. The coated article of claim 82, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:
10.
85. The coated article of any one of claims 79-84, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
86. The coated article of claim 85, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
87. The coated article of claim 85, a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:
10.
88. The coated article of any one of claims 79-84, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric unitsATTORNEY DOCKET NO. SP23-219WO comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
89. The coated article of claim 88, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
90. The coated article of claim 89, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
91. The coated article of any one of claims 79-90, wherein the fingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
92. The coated article of any one of claims 79-91, further comprising an optical stack positioned between the fingerprint-hiding coating and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.
93. The coated article of any one of claims 79-92 wherein the substrate is a textured substrate.
94. The coated article of claim 93, wherein the coated article further comprises an anti- reflective coating or a gradient coating positioned between the fingerprint-hiding coating and the textured substrate.
95. The coated article of any one of claims 79-94, wherein the substrate is a polymer substrate.
96. A coated article comprising:ATTORNEY DOCKET NO. SP23-219WO a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independently selected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 or more, q is 1 or more, R is selected from a groupconsisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
97. The coated article of claim 96, wherein the planarization layer comprises at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silica of about 0.2 or more.
98. The coated article of any one of claims 96-97, wherein the planarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
99. The coated article of any one of claims 96-98, wherein R” is CH3.
100. The coated article of any one of claims 96-99, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
101. The coated article of any one of claims 96-99, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100;ATTORNEY DOCKET NO. SP23-219WO n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
102. A coated article comprising: a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34.
103. The coated article of claim 102, wherein the planarization layer comprises at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silica of about 0.2 or more.
104. The coated article of any one of claims 102-103, wherein the planarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
105. The coated article of any one of claims 102-104, wherein R’ is CH3, and m is 8.
106. The coated article of any one of claims 102-105, wherein the condensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, whereinATTORNEY DOCKET NO. SP23-219WO R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
107. The coated article of claim 106, wherein a ratio of the monomeric units comprising {OSi(R’)2[CH2]mSi(R’)2} to the monomeric units comprising {R”Si(OCH3)3} is from 10:1 to 1:
10.
108. The coated article of any one of claims 102-107, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof .
109. The coated article of claim 108, wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
110. The coated article of claim 108, wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:
10.
111. The coated article of any one of claims 102-110, wherein the planarization layer exhibits at least one of: an abraded water contact angle of about 80° or more after being abraded for 2,000 cycles in a Steel Wool Abrasion test; a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
112. The coated article of any one of claims 102-111, further comprising an optical stack positioned between the planarization layer and the substrate, wherein the optical stack comprises an anti-reflective coating, a band-pass filter coating, an edge neutral mirror, a beam splitter coating, a multi-layer high-reflectance coating, or an edge filter coating.ATTORNEY DOCKET NO. SP23-219WO 113. The coated article of any one of claims 102-112, wherein the substrate is a textured substrate.
114. The coated article of claim 113, wherein the coated article further comprises an anti- reflective coating or a gradient coating positioned between the planarization layer and the textured substrate.
115. The coated article of any one of claims 102-114, wherein the substrate is a polymer substrate.
116. A coated article comprising: a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
117. The coated article of claim 116, wherein the planarization layer comprises at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silica of about 0.2 or more.ATTORNEY DOCKET NO. SP23-219WO 118. The coated article of any one of claims 116-117, wherein the planarization layer comprises an elastic modulus ranging from about 9 GigaPascals to about 70 GigaPascals.
119. The coated article of any one of claims 116-118, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
120. The coated article of any one of claims 116-119, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
121. The coated article of any one of claims 116-118, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
122. A coated article comprising: a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.ATTORNEY DOCKET NO. SP23-219WO 123. The coated article of claim 122, wherein R is OCH3, and m is 8.
124. The coated article of claim 122, wherein R is OCH3, and m is 6.
125. The coated article of any one of claims 122-124 , wherein the condensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
126. The coated article of claim 125, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:
10.
127. The coated article of claim 125, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:
10.
128. The coated article of any one of claims 125-127, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
129. The coated article of claim 128, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
130. The coated article of claim 128, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO 131. The coated article of any one of claims 125-127, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
132. The coated article of claim 131, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
133. The coated article of claim 131, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:
10.
134. A method of forming a coated article comprising: disposing an alkyl silane on a first major surface of a substrate, the alkyl silane comprising a C3-C34 alkyl group, and the alkyl silane comprising at least two reactive groups independently selected from a silane, a non-fluorine halogen, or combinations thereof; and reacting the alkyl silane to form a fingerprint-hiding coating on the first major surface of the substrate, wherein the fingerprint-hiding coating exhibits: a water contact angle from 90° to 120°; an oleic acid contact angle of 40° or less; and a coefficient of friction of the exterior surface is 0.25 or less.
135. The method of claim 134, wherein the disposing comprises spray coating the alkyl silane on the first major surface.
136. The method of any one of claims 134-135, wherein the reacting comprises heating the alkyl silane at a temperature of about 80°C to about 250°C for a period of time from about 10 minutes to about 8 hours.
137. The method of any one of claims 134-135, wherein the reacting comprises disposing the alkyl silane on the planarization layer at a temperature from about 20°C to about 40°C for a period of time from about 1 hour to about 24 hours.ATTORNEY DOCKET NO. SP23-219WO 138. The method of any one of claims 134-137, wherein two of the at least two reactive groups are located at opposite ends of the alkyl silane.
139. The method of any one of claims 134-138, wherein the alkyl silane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, or combinations thereof.
140. The method of any one of claims 134-139, wherein the alkyl silane comprises an alkyl chlorodimethylsilane and an alkyl trimethoxysilane.
141. The method of claim 140, wherein the alkyl trimethoxysilane is octadecyl trimethoxysilane.
142. The method of any one of claims 139-141, wherein an amount of the alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
143. The method of claim 142, wherein the amount of the alkyl trimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
144. The method of any one of claims 134-143, wherein the alkyl silane comprises 1,8- bis(chlorodimethylsilyl)ocatane, chloropropyltrimethoxysilane, octadecyl trimethoxysilane, or combinations thereof.
145. The method of any one of claims 134-143, wherein the alkyl silane comprises 1,8- bis(trimethoxysilyl)octane, 1,6-bis(trimethoxysilyl)hexane, octadecyl trimethoxysilane, or combinations thereof.
146. The method of any one of claims 134-145, wherein the alkyl silane is chlorine-free.
147. The method of any one of claims 134-146, wherein the alkyl silane comprises an alkyl trimethoxysilyl and an alkyl trimethoxysilane.ATTORNEY DOCKET NO. SP23-219WO 148. The method of claim 147, wherein the alkyl trimethoxysilane is octadecyl trimethoxysilane.
149. The method of any one of claims 147-148, wherein an amount of the alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
150. The method of claim 149, wherein the amount of the alkyl trimethoxysilane as a wt% of the total amount of the alkyl silane is from about 10% to about 50%.
151. The method of any one of claims 134-150 or 253-259 inclusive, wherein the alkyl silane further comprises a dimethylsilane with silanes at both ends of the dimethylsilane.
152. The method of claim 151, wherein the dimethylsilane is dichloro-tetramethyl- disoloxane.
153. The method of any one of claims 151-152, wherein an amount of the dimethylsilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
154. The method of claim 153, wherein the amount of the dimethylsilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
155. The method of any one of claims 134-146, wherein the alkyl silane consists of a single alkyl silane compound.
156. The method of any one of claims 134-155, wherein the disposing the alkyl silane comprises disposing a solution containing the alkyl silane, wherein a pH of the solution is from 6 to 8.
157. The method of any one of claims 134-156, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both.
158. The method of any one of claims 134-157, wherein the fingerprint-hiding coating further comprises:ATTORNEY DOCKET NO. SP23-219WO the alkyl silane is bonded to the substrate by a silane group, the alkyl silane is bonded to another part of the coated article by a silane group, or both; a silane group of the alkyl silane is at a free end of the alkyl silane; or both.
159. The method of any one of claims 157-158, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a dialkyl siloxane block.
160. The method of any one of claims 157-159, wherein monomeric units comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a disiloxane group.
161. The method of any one of claims 157-160, wherein monomeric units comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a dimethylsiloxane block.
162. The method of any one of claims 157-161, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
163. The method of claim 162, wherein R” is CH3.
164. The method of any one of claims 162-163, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
165. The method of any one of claims 162-163, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; orATTORNEY DOCKET NO. SP23-219WO n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
166. The method of any one of claims 157-161, wherein the fingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3and CH2CH3, and m is from 3 to 34.
167. The method of claim 166, wherein R’ is CH3.
168. The method of claim 166, wherein R’ is CH3, and m is 8.
169. The method of any of claims 166-168 wherein the condensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
170. The method of claim 169, wherein a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:
10.
171. The method of any of claims 169-170 wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
172. The method of claim 171, wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO 173. The method of any one of claims 157-161, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
174. The method of claim 173, wherein the alkyl silane is chlorine-free.
175. The method of any of claims 173-174, wherein R’ is OCH3.
176. The method of any of claims 173-175, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
177. The method of any of claims 173-175, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
178. The method of any of claims 173-175, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
179. The method of any one of claims 157-161, wherein the fingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3and OH, and m is from 3 to 34.ATTORNEY DOCKET NO. SP23-219WO 180. The method of claim 179, wherein R is OCH3, and m is 8.
181. The method of claim 179, wherein R is OCH3, and m is 6.
182. The method of any one of claims 179-181, wherein the condensation product further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
183. The method of claim 182, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof is from 10:1 to 1:
10.
184. The method of claim 182, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:
10.
185. The method of any one of claims 179-184, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
186. The method of claim 185, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
187. The method of claim 185, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:10.ATTORNEY DOCKET NO. SP23-219WO 188. The method of any one of claims 179-184, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
189. The method of claim 188, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:10 190. The method of claim 188, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 11:1 to 1:
10.
191. A method of forming a coated article comprising: evaporating a functionalized polyhedral oligomeric silsesquioxane onto a first major surface of a substrate; impinging an ion beam at the first major surface of the substrate, the impinging occurs in a chamber comprising a chamber pressure ranging from about 10-4Pascal to about 1 Pascal, the ion beam is generated using a discharge current from about 0.25 Amps to about 1 Amp to form a planarization layer; and then reacting material of the planarization layer with a alkyl silane to form a fingerprint- hiding coating, the alkyl silane comprising 3 or more carbons, wherein the silane comprises at least two reactive groups independently selected from a silane, a non-fluorine halogen, or combinations thereof, wherein the fingerprint-hiding coating exhibits: a water contact angle from 90° to 120°; an oleic acid contact angle of 40° or less; and a coefficient of friction of the exterior surface is 0.25 or less.
192. The method of claim 191, wherein the functionalized polyhedral oligomeric silsesquioxane is at least partially functionalized by at least one of: an alkene comprising from 2 to 8 carbons, an alkane comprising from 1 to 8 carbons, or combinations thereof.ATTORNEY DOCKET NO. SP23-219WO 193. The method of any one of claims 191-192, wherein the evaporating the functionalized polyhedral oligomeric silsesquioxane and the impinging occur simultaneously.
194. The method of any one of claims 191-193, wherein the reacting comprises evaporating the alkyl silane at a temperature of about 80°C to about 250°C for a period of time from about 10 minutes to about 8 hours.
195. The method of any one of claims 191-194, wherein the reacting comprises disposing the alkyl silane on the planarization layer at a temperature from about 20°C to about 40°C for a period of time from about 1 hour to about 24 hours.
196. The method of any one of claims 191-195, wherein two of the at least two reactive groups are located at opposite ends of the alkyl silane.
197. The method of any one of claims 191-196, wherein the alkyl silane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, or combinations thereof.
198. The method of any one of claims 191-197, wherein the alkyl silane comprises an alkyl chlorodimethylsilane and an alkyl trimethoxysilane.
199. The method of claim 198, wherein the alkyl trimethoxysilane is octadecyl trimethoxysilane.
200. The method of any one of claims 198-199, wherein an amount of the alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
201. The method of claim 200, wherein the amount of the alkyl trimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
202. The method of any one of claims 191-201, wherein the alkyl silane comprises 1,8- bis(chlorodimethylsilyl)ocatane, chloropropyltrimethoxysilane, octadecyl trimethoxysilane, or combinations thereof.ATTORNEY DOCKET NO. SP23-219WO 203. The method of any one of claims 191-201, wherein the alkyl silane comprises 1,8- bis(trimethoxysilyl)octane, 1,6-bis(trimethoxysilyl)hexane, octadecyl trimethoxysilane, or combinations thereof.
204. The method of any one of claims 191-201, wherein the alkyl silane is chlorine-free.
205. The method of any one of claims 134-204, wherein the alkyl silane comprises an alkyl trimethoxysilyl and an alkyl trimethoxysilane.
206. The method of claim 205, wherein the alkyl trimethoxysilane is octadecyl trimethoxysilane.
207. The method of any one of claims 205-206, wherein an amount of the alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
208. The method of claim 207, wherein the amount of the alkyl trimethoxysilane as a wt% of the total amount of the alkyl silane is from about 10% to about 50%.
209. The method of any one of claims 191-208, wherein the alkyl silane further comprises a dimethylsilane with silanes at both ends of the dimethylsilane.
210. The method of claim 209, wherein the dimethylsilane is dichloro-tetramethyl- disoloxane.
211. The method of any one of claims 209-210, wherein an amount of the dimethylsilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
212. The method of claim 211, wherein the amount of the dimethylsilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
213. The method of any one of claims 191-204, wherein the alkyl silane consists of a single alkyl silane compound.ATTORNEY DOCKET NO. SP23-219WO 214. The method of any one of claims 191-213, wherein the disposing the alkyl silane comprises disposing a solution containing the alkyl silane, wherein a pH of the solution is from 6 to 8.
215. The method of any one of claims 191-214, wherein the planarization layer exhibiting at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a ratio of Si-O-Si bonds to Si atoms in the planarization layer is from about 2 to about 3; or a molar ratio of hydrogen to silicon in the planarization layer is about 0.2 or more.
216. The method of any one of claims 191-215, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both.
217. The method of any one of claims 119-216, wherein the fingerprint-hiding coating further comprises: the alkyl silane is bonded to the planarization layer by a silane group; a silane group of the alkyl silane is at a free end of the alkyl silane; or both.
218. The method of any one of claims 216-217, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a dialkyl siloxane block.
219. The method of any one of claims 216-218, wherein monomeric units comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a disiloxane group.
220. The method of any one of claims 216-219, wherein monomeric units comprising the oligomer of the alkyl silane, monomeric units comprising the polymer of the alkyl silane, or both, are bonded together by a dimethylsiloxane block.
221. The method of any one of claims 216-220, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 orATTORNEY DOCKET NO. SP23-219WO more, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
222. The method of claim 221, wherein R” is CH3.
223. The method of any one of claims 221-222, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
224. The method of any one of claims 221-222, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100; n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; or n is 2 or more, m is 8, p is 8, and q is from 1 to 100.
225. The method of any one of claims 216-220, wherein the fingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34.
226. The method of claim 225, wherein R’ is CH3.
227. The method of claim 225, wherein R’ is CH3, and m is 8.
228. The method of any of claims 225-227, wherein the condensation product further comprises monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
229. The method of claim 228, wherein a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)},ATTORNEY DOCKET NO. SP23-219WO {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:
10.
230. The method of any of claims 228-229, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof 231. The method of claim 230, wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)2}, {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
232. The method of any one of claims 216-220, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R)2[CH2]m[Si(R)2O]nSi(R)2[CH2]pSi(R)2}qR, wherein m and p are independently selected from 3 to 34, each R is independently selected from OCH3, OH, and OSi(R’)2[CH2]m’, m’ is independently selected from 3 to 34, n is 1 or more, q is 1 or more, and each R’ is independently selected from a group consisting of OCH3, and OH.
233. The method of claim 232, wherein the alkyl silane is chlorine-free.
234. The method of any of claims 232-233, wherein R’ is OCH3.
235. The method of any one of claims 232-234, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 8, p is 8, and q is from 1 to 100.
236. The method of any one of claims 232-234, wherein, in the structure, at least one: n is 1, and q is from 1 to 100; or n is 1, m is 6, p is 6, and q is from 1 to 100.
237. The method of any one of claims 232-234, wherein, in the structure, at least one of: n is 2, and q is from 1 to 100;ATTORNEY DOCKET NO. SP23-219WO n is 2, m is 8, p is 8, and q is from 1 to 100; n is 2, m is 6, p is 6, and q is from 1 to 100; n is 2 or more, and q is from 1 to 100; n is 2 or more, m is 8, p is 8, and q is from 1 to 100; or n is 2 or more, m is 6, p is 6, and q is from 1 to 100.
238. The method of any one of claims 216-220, wherein the fingerprint-hiding comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(R)2[CH2]mSi(R)2}, wherein each R is independently selected from OCH3 and OH, and m is from 3 to 34.
239. The method of claim 238, wherein R is OCH3, and m is 8.
240. The method of claim 238, wherein R is OCH3, and m is 6.
241. The method of any one of claims 238-240, wherein the condensation product further comprises monomeric units comprising { {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, wherein R” is a (C5-C38) alkyl, and optionally, wherein at least a portion of the monomeric units are linked to the substrate.
242. The method of claim 241, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 10:1 to 1:
10.
243. The method of claim 241, wherein a ratio of the monomeric units comprising {(OSi(R)2[CH2]mSi(R)2} to the monomeric units comprising {R”Si(OCH3)2}, {R”Si(OCH3)}, {R”Si}, {R"Si(OCH3)2(OH)}, {R"Si(OCH3)(OH)2}, {R"Si(OH)3}, or combinations thereof, is from 1:1 to 1:
10.
244. The method of any one of claims 238-243, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric unitsATTORNEY DOCKET NO. SP23-219WO comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
245. The method of claim 244, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
246. The method of claim 244, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]8Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 1:1 to 1:
10.
247. The method of any one of claims 238-243 wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof.
248. The method of claim 247, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
249. The method of claim 247, wherein a ratio of the monomeric units comprising {(OSi(OCH3)2[CH2]6Si(OCH3)2} to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is from 10:1 to 1:
10.
250. The coated article of any one of claims 6-14, wherein R is selected from a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
251. The coated article of any one of claims 57-60, wherein R is selected from a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
252. The coated article of any one of claims 96-101, wherein R is selected from a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.ATTORNEY DOCKET NO. SP23-219WO 253. The method of any one of claims 134-138, wherein the alkyl silane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, an alkyl dimethylmethoxysilane, an alkyl dimethylethoxysilane or combinations thereof.
254. The method of any one of claims 134-139, wherein the alkyl silane comprises an alkyl dimethylmethoxysilane and an alkyl trimethoxysilane.
255. The method of any one of claims 253-254, wherein the alkyl trimethoxysilane is octadecyl trimethoxysilane.
256. The method of any one of claims 253-255, wherein an amount of the alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
257. The method of claim 256, wherein the amount of the alkyl trimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
258. The method of any one of claims 134-143 or 253-257 inclusive, wherein the alkyl silane comprises 1,8-bis(dimethylmethoxysilyl)octane, octadecyl trimethoxysilane, or combinations thereof.
259. The method of any one of claims 253-258, wherein the alkyl silane is chlorine-free.
260. The method of any one of claims 191-196, wherein the alkyl silane comprises an alkyl trichlorosilane, an alkyl dichloromethoxy silane, an alkyl chlorodimethoxysilane, an alkyl dichloromethylsilane, an alkyl chlorodimethylsilane, an alkyl trimethoxysilane, an alkyl triethoxysilane, an alkyl dimethylmethoxysilane, an alkyl dimethylethoxysilane or combinations thereof.
261. The method of any one of claims 191-196, wherein the alkyl silane comprises an alkyl dimethylmethoxysilane and an alkyl trimethoxysilane.ATTORNEY DOCKET NO. SP23-219WO 262. The method of any one of claims 260-261, wherein the alkyl trimethoxysilane is octadecyl trimethoxysilane.
263. The method of any one of claims 261-262, wherein an amount of the alkyl trimethoxysilane as a wt% of a total amount of the alkyl silane is from about 1% to about 90%.
264. The method of claim 263, wherein the amount of the alkyl trimethoxysilane as a wt% of the total amount of the alkyl silane is from about 25% to about 75%.
265. The method of any one of claims 191-201 or 260-264 inclusive, wherein the alkyl silane comprises 1,8-bis(dimethylmethoxysilyl)octane, octadecyl trimethoxysilane, or combinations thereof.
266. The method of any one of claims 221-231, wherein R is selected from a methoxy group, an ethoxy group, a hydroxy group, or combinations thereof.
267. The method of any one of claims 221-231, wherein R is selected from a methoxy group, an ethoxy group, or combinations thereof.
268. The method of any one of claims 221-231, wherein R is a methoxy group.
269. The coated article of any one of claim 1-5, wherein the fingerprint-hiding coating comprises an oligomer of an alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
270. The coated article of any one of claims 1-5 or 269 inclusive, wherein the fingerprint- hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O}, wherein each R’ is independently selected from CH3 and CH2CH3, and m is from 3 to 34, and monomeric units comprising {R4Si(OCH3)2}, {R4Si(OCH3)}, {R4Si}, { R4Si(OCH3)2(OH)},ATTORNEY DOCKET NO. SP23-219WO {R4Si(OCH3)(OH)2}, { R4Si(OH)3}, or combinations thereof, wherein R4is a (C5-C38) alkyl; optionally, wherein at least a portion of the monomeric units are linked to the substrate; and wherein a ratio of the monomeric units comprising {Si(R’)2[CH2]mSi(R’)2O} to the monomeric units comprising {R4Si(OCH3)2}, {R4Si(OCH3)}, {R4Si}, { R4Si(OCH3)2(OH)}, {R4Si(OCH3)(OH)2}, { R4Si(OH)3}, or combinations thereof, is 10:1 to 1:
10.
271. The coated article of any one of claims 1-6 or 269-270 inclusive, wherein the fingerprint-hiding coating comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a condensation product of monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2} and monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof; and wherein a ratio of the monomeric units comprising {OSi(CH3)2[CH2]8Si(CH3)2}to the monomeric units comprising {(CH3)(CH2)17Si(OCH3)}, {(CH3)(CH2)17Si}, or combinations thereof is 10:1 to 1:
10.
272. The coated article of any one of claims 1-271, wherein the fingerprint-hiding coating exhibits at least one of: a voltage of about 15 Volts or less in a Tribocharging test; or a voltage difference between a peripheral contact region and a center contact region of about 5 Volts or less in the Tribocharging test.
273. The coated article of any one of claims 1-272, wherein when a simulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits at least one of: an effective diameter of droplets of the simulated fingerprint of 10 µm or more; a mean height of droplets of the simulated fingerprint on the exterior surface of 0.15 µm or less; or a spherical cap radius of droplets of the simulated fingerprint of 40 µm or more.
274. The coated article of any one of claims 1-273, wherein when a simulated fingerprint is applied to the fingerprint-hiding coating in a Simulated Fingerprint Test, the fingerprint-hiding coating exhibits: a core material value Vmc of a droplet of the simulated fingerprint of 0.10 µm3 / µm2or more between areal material ratios of 10% and 90%.ATTORNEY DOCKET NO. SP23-219WO 275. The coated article of claim 274, wherein the fingerprint-hiding coating exhibits at least one of: a ratio of a volume of the droplet to an area of the droplet is 0.78 µm3 / µm2or less; a ratio of a height of the droplet to the area of the droplet is 0.005 µm / µm2or less; a total area of the simulated fingerprint over the exterior surface of 150,000 µm2or more; a haze of 8% or less with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; a center of a sphere modeled on the droplet of the simulated fingerprint is located greater than 30 µm from the exterior surface of the fingerprint-hiding coating; a mean gray level is 150 or less as measured in a Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test; or a normalized gray level is 2.0 or less as measured in a Normalized Gray Level Test of coated article with the simulated fingerprint applied to the fingerprint-hiding coating in the Simulated Fingerprint Test.
276. The coated article of any one of claims 1-275, wherein the fingerprint-hiding coating comprises a thickness from 1 nanometer to 75 nanometers.
277. The coated article of any one of claims 1-276, wherein the fingerprint-hiding coating exhibits at least one of: a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
278. The coated article of any one of claims 1-277, further comprising a planarization layer positioned between the substrate and the fingerprint-hiding coating, the fingerprint-hiding coating disposed on the planarization layer, the planarization layer exhibiting at least one of: from 50% to 90% of silicon atoms of the planarization layer are in a silica-like network; a molar ratio of hydrogen to silicon in the planarization layer is about 0.2 or more; orATTORNEY DOCKET NO. SP23-219WO a refractive index ranging from 1.37 to 1.
55.
279. The coated article of claim 278, wherein the planarization layer exhibits at least one of: an abraded water contact angle of about 80° or more after being abraded for 2,000 cycles in a Steel Wool Abrasion test; a cheesecloth-abraded water contact angle of about 80° or more after being subjected to 200,000 cycles of in a Cheesecloth Abrasion Test; or a rubber-abraded water contact angle of about 80° or more after being abraded for 3,000 cycles in a Rubber Abrasion Test.
280. The coated article of any one of claims 1-279, further comprising at least one of: an anti-reflective coating positioned between the fingerprint-hiding coating and the substrate; or a gradient coating comprising a refractive index gradient positioned between the fingerprint-hiding coating and the substrate.
281. The coated article of any one of claims 1-280, wherein the substrate is a metal, glass, glass ceramic, or polymer substrate.
282. The coated article of any one of claims 1-281, wherein the fingerprint-hiding coating is substantially free of halogens.
283. A coated article comprising: a substrate comprising a first major surface; and a fingerprint-hiding coating disposed over the first major surface, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free, the fingerprint-hiding coating is substantially free of halogens and comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure {OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.ATTORNEY DOCKET NO. SP23-219WO 284. A coated article comprising: a substrate comprising a first major surface; a planarization layer disposed over the first major surface, the planarization layer comprising a thickness between a first surface area and a second surface area opposite the first surface area from about 10 nanometers to about 600 nanometers, the second surface area facing the first major surface; and a fingerprint-hiding coating disposed on the first surface area of the planarization layer, the fingerprint-hiding coating comprising an exterior surface of the coated article, wherein: the fingerprint-hiding coating is fluorine-free; the fingerprint-hiding coating is substantially free of halogens and comprises an oligomer of the alkyl silane, a polymer of the alkyl silane, or both, wherein the oligomer of the alkyl silane, the polymer of the alkyl silane, or both, comprise a structure o{OSi(R’)2[CH2]m[Si(R”)2O]nSi(R’)2[CH2]pSi(R”)2}qR, wherein m and p are independentlyselected from 3 to 34, R’ and R” are independently selected from CH3 and CH2CH3, n is 1 ormore, q is 1 or more, R is selected from a group consisting of a hydroxyl group, a chloro group, a bromo group, an alkyl silane, an alkoxide, or combinations thereof.
Citation Information
Patent Citations
Invisible fingerprint coatings and process for forming same
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