CN117186730A

CN117186730A - Coated article and method of making coated article

Info

Publication number: CN117186730A
Application number: CN202210601405.5A
Authority: CN
Inventors: 李灵珂; 李阳
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2022-05-30
Filing date: 2022-05-30
Publication date: 2023-12-08
Also published as: WO2023235279A1

Abstract

The present application relates to coated articles and methods of making coated articles. The coated article includes a first coating disposed on a first major surface of the substrate. The first coating includes a first polymer comprising a plurality of first monomers linked by ether groups or linked by amine groups. The coated article includes a second coating layer over the first coating layer. The second coating includes a second polymer comprising a plurality of second monomers linked by ether groups or linked by amine groups. A method of making a coated article includes disposing a first liquid comprising a first plurality of molecules comprising epoxy groups or glycidyl groups on a first major surface of a substrate. The method includes partially curing the first liquid to form a partially cured coating. The method includes disposing a second liquid over the partially cured coating. The method includes curing the partially cured coating and the second liquid.

Description

Coated article and method of making coated article

Technical Field

The present disclosure relates generally to coated articles and methods of making coated articles, and more particularly to coated articles comprising multiple coatings and methods of making same.

Background

Foldable substrates are commonly used in, for example, display applications, such as: a Liquid Crystal Display (LCD), an electrophoretic display (EPD), an organic light emitting diode display (OLED), a Plasma Display Panel (PDP), or the like.

It is known to provide a coating comprising an organic material on a portion of the display and/or protective cover. For example, such organic materials may include antimicrobial, easy-to-clean, and/or hydrophilic functionality. However, organic coatings can have durability problems, such as being susceptible to abrasion.

It is desirable to develop displays and protective covers that are mounted to the displays. The display and cover should have good impact resistance and puncture resistance. At the same time, the display and cover should be foldable, for example, with a small parallel plate spacing (e.g., about 10 millimeters (mm) or less).

It is therefore desirable to develop coated articles for display devices and/or foldable devices comprising a coating and a substrate (e.g., glass-based substrate, ceramic-based substrate) that have high transparency, low haze, low minimum parallel plate spacing, good scratch resistance, good impact resistance, and good puncture resistance.

Disclosure of Invention

Coated articles comprising a first coating and a second coating and methods of making the same are described herein. The coating disposed on the substrate can provide both high surface hardness and good impact resistance. For example, the second coating may provide a high surface hardness (e.g., a pencil hardness of about 3H in the as-formed state, a pencil hardness of about 4H or greater or about 5H or greater after a duration of 16 hours in an 85 ℃ environment at 85% relative humidity). Providing high surface hardness can provide scratch resistance of the coated article. For example, the first coating can increase the impact resistance of the coated article (e.g., withstand a strike height of 10cm or greater, increasing the strike threshold height by about 5cm or greater relative to the same substrate without the coating), for example, by absorbing and/or dissipating impact energy. Providing a functionalized oligomeric silsesquioxane as part of the second coating may further increase the hardness of the resulting coating and/or coated article. Providing a coating on a substrate increases the durability of the coated article by, for example, filling in surface imperfections in the substrate and/or protecting the surface imperfections in the substrate from damage.

The coating may provide good adhesion in the coated article. Providing a first coating (comprising ether linkages or other functional groups as a result of the reaction of epoxy or glycidyl groups) may provide good adhesion to the substrate, such as hydrogen bonding, covalent bonding, or other interactions (e.g., dipole-dipole interactions) with the material at the substrate surface through the oxygen of the epoxy or glycidyl groups. For example, the adhesion between the first coating and the substrate may be about 1B or greater or about 4B or greater (as-shaped state, or after 16 hours in an 85% relative humidity, 85 ℃ environment). Providing a first coating and a second coating (comprising ether linkages or other functional groups as a result of reaction of epoxy groups or glycidyl groups) may provide good adhesion between the first coating and the second coating, such as hydrogen bonding, covalent bonding, or other interactions (e.g., dipole-dipole interactions) between these coatings through oxygen of the epoxy groups or glycidyl groups. For example, the adhesion between the first coating and the second coating may be greater than the adhesion between the first coating and the substrate. Furthermore, having the first liquid (corresponding to the first coating) only partially cured prior to disposing the second liquid (corresponding to the second coating) may increase adhesion therebetween, such as by increasing bonding and other interactions therebetween as a result of subsequent curing of the second liquid to form the second coating disposed on the first coating.

The method of the present disclosure includes disposing a liquid that solidifies to form a coating on a substrate. Providing the precursor of the first coating as the first liquid achieves that the first liquid conforms to the contours of the substrate (e.g., transition surface area and other details of the substrate). Forming the coating from a substantially solvent-free liquid can increase its cure rate, which can reduce processing time. Furthermore, the solvent-free liquid may reduce (e.g., reduce, eliminate) the use of rheology modifiers and increase homogeneity, which may increase the optical clarity (e.g., transmittance) of the resulting coating. Furthermore, the solvent-free composition may reduce the incidence of visually observable defects (e.g., bubbles from volatile gases due to any solvent evaporation) in the resulting coating. Processing efficiency and manufacturing costs may be increased by irradiating the liquid for a short period of time to cure the liquid to form the coating. Alternatively, providing a composition that does not contain a photoinitiator (e.g., a thermally curable composition) may eliminate yellowing problems.

Providing a transition surface region (e.g., a first transition surface region and/or a second transition surface region) may reduce (e.g., minimize) optical distortion and/or visual visibility of thickness variation from substrate thickness to center thickness. Providing a smooth shaped first transition region and/or second transition region may reduce optical distortion.

Providing a first polymer and/or a second coating that includes oxygen atoms in the polymer backbone can increase the flexibility of the corresponding polymer and the resulting coating, which can increase ultimate elongation, durability, and/or impact resistance (e.g., drop height). Providing a first polymer and/or a second polymer portion having a glass transition temperature that falls outside of an operating range (e.g., about 0 ℃ to about 40 ℃, about-20 ℃ to about 60 ℃) may achieve consistent properties over the operating range. Providing a coating that is free of a photoinitiator (e.g., a thermally curable composition) may eliminate yellowing problems.

Providing a first coating and/or a second coating that is substantially free and/or free of silica nanoparticles may reduce processing problems (e.g., agglomeration, coalescence, phase separation) associated with forming the first coating, may improve optical properties (e.g., maintain low haze and/or high transmittance, even after aging at elevated temperatures and/or humidity) of the coating and/or the resulting coated article, and may reduce mechanical properties (e.g., hardness, modulus, strain, impact resistance) of the resulting coating and/or coated article, as compared to a corresponding coating and/or coated article without silica nanoparticles.

Some exemplary aspects of the present disclosure are described below, with the understanding that any of the features of the various aspects may be used alone or in combination with one another.

Aspect 1: a coated article, comprising:

a substrate comprising a substrate thickness defined between a first major surface and a second major surface opposite the first major surface;

a first coating disposed on the first major surface of the substrate, the first coating comprising a first polymer comprising a plurality of first monomers linked by ether groups or by amine groups; and

a second coating disposed on the first coating, the second coating comprising a second polymer comprising a plurality of second monomers linked by ether groups or by amine groups,

wherein the first coating is disposed between the substrate and the second coating, the second coating comprising a pencil hardness of about 3H or greater in the as-formed state.

Aspect 2: the coated article of aspect 1, wherein the ether groups to which the plurality of first monomers are attached are formed by: reaction of epoxy groups or glycidyl groups of a first monomer of the plurality of first monomers; or the amine group to which the plurality of first monomers are attached is formed by: reacting an epoxy group or a glycidyl group with an amine group of a first monomer of the plurality of first monomers; and the ether group to which the plurality of second monomers are attached is formed by: reaction of epoxy groups or glycidyl groups of a second monomer of the plurality of second monomers; or the amine groups to which the plurality of second monomers are attached are formed by: such that the epoxy group or the glycidyl group reacts with an amine group of a second monomer of the plurality of second monomers.

Aspect 3: the coated article of any of aspects 1-2, wherein the second polymer comprises amine groups along the backbone of the second polymer.

Aspect 4: the coated article of any of aspects 1-3, wherein the second polymer comprises a siloxane.

Aspect 5: a coated article, comprising:

a first coating disposed on the first major surface of the substrate, the first coating comprising a first polymer comprising a plurality of first monomers linked by ether groups; and

a second coating disposed on the first coating, the second coating comprising a second polymer comprising a plurality of second monomers linked by ether groups,

Aspect 6: the coated article of aspect 5, wherein the ether groups to which the first plurality of monomers are attached are formed by reaction of epoxy groups or glycidyl groups of first monomers of the first plurality of monomers, and the ether groups to which the second plurality of monomers are attached are formed by reaction of epoxy groups or glycidyl groups of second monomers of the second plurality of monomers.

Aspect 7: the coated article of any of aspects 1, 5, or 6, wherein the plurality of second monomers comprises a cycloaliphatic epoxide.

Aspect 8: the coated article of any of aspects 1, 5 or 6, wherein the second polymer is free of amines along the backbone of the second polymer.

Aspect 9: the coated article of any of aspects 1-8, wherein the second coating comprises a second plurality of functionalized oligomeric silsesquioxanes, a first functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes being combined (bond) with a second functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes as part of the second polymer.

Aspect 10: the coated article of aspect 9, wherein the second plurality of functionalized oligomeric silsesquioxanes are functionalized with either a glycidyl functional group or an epoxycyclohexyl functional group.

Aspect 11: the coated article of any of aspects 1-10, wherein the first plurality of monomers comprises a cycloaliphatic epoxide.

Aspect 12: the coated article of any of aspects 1-8, wherein the first coating comprises a first plurality of functionalized oligomeric silsesquioxanes, a first functionalized oligomeric silsesquioxanes of the first plurality of functionalized oligomeric silsesquioxanes being combined (bond) with a second functionalized oligomeric silsesquioxanes of the first plurality of functionalized oligomeric silsesquioxanes as part of the first polymer.

Aspect 13: the coated article of aspect 12, wherein the first plurality of functionalized oligomeric silsesquioxanes are functionalized with either a glycidyl functional group or an epoxycyclohexyl functional group.

Aspect 14: the coated article of any of aspects 1-13, wherein the first coating comprises a bond to the substrate of about 1B or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 15: the coated article of aspect 14, wherein the bond between the first coating and the substrate is about 4B or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 16: the coated article of any of aspects 1-15, wherein the as-formed adhesion between the first coating and the substrate is about 4B or greater.

Aspect 17: the coated article of aspect 16, wherein the as-formed adhesion between the first coating and the second coating is greater than the as-formed adhesion between the first coating and the substrate.

Aspect 18: the coated article of any of aspects 1-17, wherein the second coating comprises silica nanoparticles.

Aspect 19: the coated article of any of aspects 1-18, wherein the second coating has a pencil hardness of about 4H or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 20: the coated article of aspect 19, wherein the second coating has a pencil hardness of about 5H or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 21: the coated article of any of aspects 1-20, wherein the first coating comprises a minimum first thickness range of about 5 microns to about 100 microns.

Aspect 22: the coated article of any of aspects 1-21, wherein the second coating comprises an average second thickness range of about 1 micron to about 25 microns.

Aspect 23: the coated article of aspect 22, wherein the average second thickness ranges from about 1.5 microns to about 5 microns.

Aspect 24: the coated article of any of aspects 1-23, wherein the first coating comprises an elastic modulus in the range of about 1 megapascal to about 2,000 megapascals.

Aspect 25: the coated article of any of aspects 1-24, wherein the second coating comprises an elastic modulus in the range of about 100 megapascals to about 5,000 megapascals.

Aspect 26: the coated article of any of aspects 1-25, wherein the first coating comprises a composition different from the second coating.

Aspect 27: the coated article of any of aspects 1-26, wherein the substrate has a thickness in a range from about 25 microns to about 2 millimeters.

Aspect 28: the coated article of aspect 27, wherein the substrate has a thickness in the range of about 125 microns to about 200 microns.

Aspect 29: the coated article of any of aspects 1-28, wherein the substrate comprises a glass-based substrate or a ceramic-based substrate.

Aspect 30: the coated article of any of aspects 1-29, wherein the coated article is capable of withstanding a pen strike from a height of 10 centimeters onto the second coating.

Aspect 31: the coated article of any of aspects 1-30, wherein a first pen-down threshold height of the coated article for a pen-down impinging on the second coating is about 5 centimeters or more greater than a second pen-down threshold height on another substrate with the same individual substrate.

Aspect 32: the coated article of any of aspects 1-31, wherein the second coating contacts the first coating and the first coating contacts the first major surface of the substrate.

Aspect 33: the coated article of any of aspects 1-32, wherein the coated article achieves a parallel plate spacing of 3 millimeters.

Aspect 34: the coated article of any of aspects 1-32, wherein the coated article achieves a parallel plate spacing of about 1 millimeter to about 10 millimeters.

Aspect 35: the coated article of any of aspects 1-34, wherein the coated article comprises an average transmittance of about 90% or higher averaged over a light wavelength range of 400 nm to 700 nm.

Aspect 36: the coated article of any of aspects 1-35, wherein the refractive index of the substrate differs from the refractive index of the first coating by a magnitude of about 0.1 or less.

Aspect 37: the coated article of any of aspects 1-35, wherein the refractive index of the substrate differs from the refractive index of the second coating by a magnitude of about 0.1 or less.

Aspect 38: the coated article of any of aspects 1-37, wherein the first coating is free of photoinitiator and/or the second coating is free of photoinitiator.

Aspect 39: the coated article of any one of aspects 1-38, wherein the substrate comprises: a first compressive stress region extending from the first major surface to a first depth of compression, a second compressive stress region extending from the second major surface to a second depth of compression, a first depth of layer of one or more alkali metal ions associated with the first depth of compression, and a second depth of layer of one or more alkali metal ions associated with the second depth of compression.

Aspect 40: the coated article of aspect 39, wherein the first compressive stress region comprises a first maximum compressive stress of about 400 megapascals or greater and the second compressive stress region comprises a second maximum compressive stress of about 400 megapascals or greater.

Aspect 41: the coated article of any of aspects 39-40, wherein the first compressive stress region comprises a plurality of ion-exchanged metal ions that create a compressive stress.

Aspect 42: the coated article of any of aspects 1-41, wherein the substrate comprises:

a first portion comprising a thickness of the substrate;

a second portion comprising a thickness of the substrate; and

a central portion between the first portion and the second portion, the central portion including a central thickness defined between a first central surface region and a second central surface region opposite the first central surface region, and the central thickness being less than the substrate thickness, the first central surface region being recessed a first distance relative to the first major surface and defining a recess,

wherein the first coating occupies the recess.

Aspect 43: the coated article of aspect 42, wherein the center thickness ranges from about 10 microns to about 80 microns.

Aspect 44: the coated article of aspect 43, wherein the center thickness ranges from about 25 microns to about 60 microns.

Aspect 45: the coated article of any of aspects 42-44, wherein a maximum first thickness of the first coating in a thickness direction of the substrate is greater than a first distance the first central surface region is recessed from the first major surface.

Aspect 46: the coated article of any of aspects 42-45, wherein the first central surface region is recessed from the first major surface a first distance of about 5% to about 75% as a percentage of the substrate thickness.

Aspect 47: a consumer electronic product, comprising:

a housing comprising a front surface, a back surface, and side surfaces;

an electronic component at least partially within the housing, the electronic component comprising a controller, a memory, and a display, the display being located at or adjacent a front surface of the housing; and

a cover substrate disposed over the display,

wherein at least one of a portion of the housing or the cover substrate comprises the coated article of any one of aspects 1-46.

Aspect 48: a method of forming a coated article, comprising:

Disposing a first liquid on a first major surface of the substrate, the first liquid comprising a first plurality of molecules including epoxy groups or glycidyl groups;

partially curing the first liquid to form a partially cured coating;

disposing a second liquid over the partially cured first coating, the second liquid comprising a second plurality of molecules, the second plurality of molecules comprising epoxy groups or glycidyl groups; and then

The partially cured coating and the second liquid are cured to form a second coating disposed on the first coating.

Aspect 49: the method of aspect 48, wherein partially curing the first liquid comprises heating the first liquid at a first temperature ranging from about 100 ℃ to about 250 ℃ for a first period of time ranging from about 10 minutes to about 90 minutes.

Aspect 50: the method of aspect 49, wherein curing the partially cured coating and the second liquid comprises heating the partially cured coating and the second liquid at a second temperature ranging from about 100 ℃ to about 250 ℃ for a second period of time ranging from about 1.5 hours to about 5 hours.

Aspect 51: the method of aspect 50, wherein the second period of time is twice the first period of time or longer.

Aspect 52: the method of any of aspects 50-51, wherein the second temperature is equal to or greater than the first temperature.

Aspect 53: the method of any of aspects 50-52, wherein the first temperature ranges from about 120 ℃ to about 180 ℃.

Aspect 54: the method of any of aspects 50-53, wherein the second temperature ranges from about 150 ℃ to about 200 ℃.

Aspect 55: the method of any of aspects 50-54, wherein curing the partially cured coating and the second liquid comprises: heating the partially cured coating and the second liquid at a third temperature for a third period of time before the second temperature heats the partially cured coating and the second liquid for the second period of time, wherein the third temperature is less than the second temperature and the third period of time is less than the second period of time.

Aspect 56: the method of aspect 55, wherein the third temperature ranges from about 100 ℃ to about 150 ℃.

Aspect 57: the method of any of aspects 55-56, wherein the third period of time ranges from about 5 minutes to about 60 minutes.

Aspect 58: the method of aspect 48, wherein the partially curing of the first liquid comprises irradiating the first liquid.

Aspect 59: the method of aspects 48, 49 or 58, wherein curing the partially cured coating and the second liquid comprises irradiating the partially cured coating and the second liquid.

Aspect 60: a method of forming a coated article, comprising:

allowing the first liquid to cure to form a first coating;

disposing a second liquid on the first coating, the second liquid comprising a second plurality of molecules, the second plurality of molecules comprising epoxy groups or glycidyl groups; and then

The second liquid is allowed to cure to form a second coating disposed on the first coating.

Aspect 61: the method of aspect 60, wherein curing the first liquid comprises heating the first liquid at a first temperature ranging from about 120 ℃ to about 180 ℃ for a first period of time ranging from about 1.5 hours to about 5 hours.

Aspect 62: the method of any of aspects 60-61, wherein curing the second liquid comprises heating the second liquid at a second temperature range of about 120 ℃ to about 180 ℃ for a second period of time of about 1.5 hours to about 5 hours.

Aspect 63: the method of aspect 60, wherein curing the first liquid comprises irradiating the first liquid and curing the second liquid comprises irradiating the second liquid.

Aspect 64: the method of any of aspects 48-63, wherein the second coating comprises a second polymer comprising a plurality of second monomers connected by ether groups, and curing the second liquid to form the second coating comprises reacting epoxy or glycidyl groups of the plurality of second monomers to form the ether groups.

Aspect 65: the method of aspect 64, wherein the second liquid is substantially free of amine.

Aspect 66: the method of any of aspects 48-63, wherein the second coating comprises a second polymer comprising a plurality of second monomers connected by amine groups, and curing the second liquid to form the second coating comprises reacting epoxy groups or glycidyl groups with amine groups of a second monomer of the plurality of second monomers.

Aspect 67: the method of any of aspects 64-66, wherein the second polymer comprises a siloxane.

Aspect 68: the method of any of aspects 64-67, wherein the second polymer comprises the plurality of second monomers comprising a cycloaliphatic epoxide.

Aspect 69: the method of any of aspects 64-68, wherein the second coating comprises a second plurality of functionalized oligomeric silsesquioxanes, a first functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes being combined (bond) with a second functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes as part of the second polymer.

Aspect 70: the method of aspect 69, wherein the second plurality of functionalized oligomeric silsesquioxanes are functionalized with either a glycidyl functional group or an epoxycyclohexyl functional group.

Aspect 71: the method of any of aspects 64-70, wherein the second liquid is substantially free of solvent.

Aspect 72: the method of any of aspects 64-71, wherein the second liquid comprises a cycloaliphatic epoxide.

Aspect 73: the method of aspect 66, wherein the second liquid comprises a tertiary amine or imidazole.

Aspect 74: the method of aspect 66, wherein the second liquid comprises poly (propylene oxide).

Aspect 75: the method of aspect 74, wherein the weight range of poly (propylene oxide) is about 20 wt% to about 30 wt% based on the weight% of the second liquid.

Aspect 76: the method of any of claims 74-75, wherein the second liquid comprises a fourth plurality of functionalized oligomeric silsesquioxanes in a range of about 60 wt.% to about 80 wt.% based on the weight of the second liquid.

Aspect 77: the method of any of aspects 72-76, wherein the second liquid comprises oxetane (oxetane).

Aspect 78: the method of aspect 77, wherein the weight of the oxetane ranges from about 5 wt% to about 30 wt% based on the weight% of the second liquid.

Aspect 79: the method of any of aspects 64-78, wherein the first coating comprises a first polymer comprising a plurality of first monomers linked by ether groups formed by reaction of epoxy groups or glycidyl groups of a first monomer of the plurality of first monomers.

Aspect 80: the method of any of aspects 64-78, wherein the first coating comprises a first polymer comprising a plurality of first monomers connected by amine groups formed by reaction of epoxy groups or glycidyl groups with amine groups of first monomers of the plurality of first monomers.

Aspect 81: the method of any of aspects 79-80, wherein the plurality of first monomers comprises a cycloaliphatic epoxide.

Aspect 82: the method of any of aspects 79-81, wherein the first coating comprises a first plurality of functionalized oligomeric silsesquioxanes, a first functionalized oligomeric silsesquioxanes of the first plurality of functionalized oligomeric silsesquioxanes being combined with a second functionalized oligomeric silsesquioxanes of the first plurality of functionalized oligomeric silsesquioxanes (bond) as part of the first polymer.

Aspect 83: the method of aspect 82, wherein the first plurality of functionalized oligomeric silsesquioxanes are functionalized with either a glycidyl functional group or an epoxycyclohexyl functional group.

Aspect 84: the method of any of aspects 79-83, wherein the first liquid comprises a cycloaliphatic epoxide.

Aspect 85: the method of aspect 84, wherein the weight of the cycloaliphatic epoxide ranges from about 60 weight percent to about 100 weight percent, based on the weight percent of the first liquid.

Aspect 86: the method of any of aspects 84-85 wherein the first liquid comprises oxetane (oxetane).

Aspect 87: the method of aspect 86, wherein the weight of the oxetane ranges from about 5 wt% to about 30 wt% based on the weight of the first liquid.

Aspect 88: the method of any of aspects 48-87, wherein the first liquid is substantially free of solvent.

Aspect 89: the method of any of aspects 48-88, wherein the first coating comprises a composition that is different from the second coating.

Aspect 90: the method of any of aspects 48-89, wherein the first coating comprises a bond to the substrate of about 1B or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 91: the method of aspect 90, wherein the bond between the first coating and the substrate is about 4B or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 92: the method of any of aspects 48-91, wherein the as-formed adhesion between the first coating and the substrate is about 4B or greater.

Aspect 93: the method of aspect 92, wherein the as-formed adhesion between the first coating and the second coating is greater than the as-formed adhesion between the first coating and the substrate.

Aspect 94: the method of any of aspects 48-93, wherein the second coating comprises a pencil hardness of about 3H or greater in the as-formed state.

Aspect 95: the method of any of aspects 48-94, wherein the second coating comprises silica nanoparticles.

Aspect 96: the method of any of aspects 48-95, wherein the second coating has a pencil hardness of about 4H or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 97: the method of aspect 96, wherein the second coating has a pencil hardness of about 5H or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

Aspect 98: the method of any of aspects 48-97, wherein the first coating comprises a minimum first thickness range of about 5 microns to about 100 microns.

Aspect 99: the method of any of aspects 48-98, wherein the second coating comprises an average second thickness ranging from about 1 micron to about 25 microns.

Aspect 100: the method of aspect 99, wherein the average second thickness ranges from about 1.5 microns to about 5 microns.

Aspect 101: the method of any of aspects 48-100, wherein the first coating comprises an elastic modulus in the range of about 1 megapascal to about 2,000 megapascals.

Aspect 102: the method of any of aspects 48-101, wherein the second coating comprises an elastic modulus in the range of about 100 megapascals to about 5,000 megapascals.

Aspect 103: the method of any of aspects 48-102, wherein the substrate has a thickness in a range from about 25 microns to about 2 millimeters.

Aspect 104: the method of aspect 103, wherein the substrate thickness ranges from about 125 microns to about 200 microns.

Aspect 105: the method of any of aspects 48-104, wherein the substrate comprises a glass-based substrate or a ceramic-based substrate.

Aspect 106: the method of any of aspects 48-105, wherein the coated article is capable of withstanding a pen strike from a height of 10 centimeters onto the second coating.

Aspect 107: the method of any of aspects 48-106, wherein the first strike threshold height of the coated article for a strike onto the second coating is about 5 cm or more greater than the second strike threshold height on another substrate with the same substrate alone.

Aspect 108: the method of any of claims 48-107, wherein the second coating contacts the first coating and the first coating contacts the first major surface of the substrate.

Aspect 109: the method of any of aspects 48-108, wherein the coated article achieves a parallel plate spacing of 3 millimeters.

Aspect 110: the method of any of aspects 48-108, wherein the coated article achieves a parallel plate spacing of about 1 millimeter to about 10 millimeters.

Aspect 111: the method of any of aspects 48-110, wherein the coated article comprises an average transmittance of about 90 percent or higher averaged over a light wavelength range of 400 nanometers to 700 nanometers.

Aspect 112: the method of any of aspects 48-111, wherein the refractive index of the substrate differs from the refractive index of the first coating by a magnitude of about 0.1 or less.

Aspect 113: the method of any of aspects 48-111, wherein the refractive index of the substrate differs from the refractive index of the second coating by a magnitude of about 0.1 or less.

Aspect 114: a polymer-based moiety comprising a polymer comprising a plurality of first monomers linked by ether groups or by amine groups, the polymer-based moiety being a cured product of a composition comprising:

a functionalized oligomeric silsesquioxane in an amount of about 60 wt% to about 90 wt%; and

oxetane is present in an amount of about 5 wt% to about 10 wt%.

Aspect 115: the polymer-based part of claim 114, wherein the composition further comprises a difunctional amine-terminated polymer in an amount from about 15 wt% to about 25 wt%.

Aspect 116: the polymer-based moiety of aspect 115, wherein the difunctional amine-terminated polymer comprises poly (dimethylsiloxane) or poly (propylene oxide).

Aspect 117: the polymer-based moiety of any of aspects 114-116, wherein the composition further comprises a trifunctional amine-terminated polymer in an amount of about 5 wt% to about 15 wt%.

Aspect 118: the polymer-based moiety of aspect 117, wherein the trifunctional amine-terminated polymer is a polyether.

Aspect 119: the polymer-based part of any one of claims 114-118, wherein the composition further comprises a curing catalyst in an amount of about 0.1 wt% to about 3 wt%.

Aspect 120: the polymer-based moiety comprises a polymer comprising a plurality of first monomers linked by ether groups or by amine groups, the polymer-based moiety being the cured product of a composition comprising:

the cycloaliphatic epoxide is present in an amount of about 75% to about 90% by weight.

A functionalized oligomeric silsesquioxane in an amount of about 3 wt% to about 10 wt%; and

oxetane is present in an amount of about 5 wt% to about 10 wt%.

Aspect 121: the polymer-based part of aspect 120, wherein the composition further comprises nanoparticles in an amount of about 0.1 wt% to about 5 wt%.

Aspect 122: the polymer-based part of any one of aspects 114-121, wherein the composition further comprises a cationic photoinitiator in an amount of about 0.1 wt% to about 5 wt%.

Aspect 123: the polymer-based moiety of any one of aspects 114-122, wherein the functionalized oligomeric silsesquioxane is functionalized with a glycidyl functional group or an epoxycyclohexyl functional group.

Aspect 124: the polymer-based moiety of any one of aspects 114-123, wherein the oxetane comprises trimethylol propane oxetane.

Aspect 125: the polymer-based part of any one of aspects 114-124, wherein the polymer-based part comprises a pencil hardness of about 3H or greater in the as-formed state.

Aspect 126: a method of making a composition comprising curing a composition comprising:

oxetane is present in an amount of about 5 wt% to about 10 wt%.

Aspect 127: the method of aspect 126, wherein the composition further comprises a difunctional amine-terminated polymer in an amount from about 15 wt% to about 25 wt%.

Aspect 128: the method of aspect 127, wherein the difunctional amine-terminated polymer comprises poly (dimethylsiloxane) or poly (propylene oxide).

Aspect 129: the method of any of aspects 126-128, wherein the composition further comprises a trifunctional amine-terminated polymer in an amount of about 5 wt% to about 15 wt%.

Aspect 130: the method of aspect 129, wherein the trifunctional amine-terminated polymer is a polyether.

Aspect 131: the method of any of aspects 126-130, wherein the composition further comprises a curing catalyst in an amount of about 0.1 wt% to about 3 wt%.

Aspect 132: a method of making a composition comprising curing a composition comprising:

oxetane is present in an amount of about 5 wt% to about 10 wt%.

Aspect 133: the method of aspect 132, wherein the composition further comprises nanoparticles in an amount of about 0.1% to about 5% by weight.

Aspect 134: the method of any of aspects 126-133, wherein the composition further comprises a cationic photoinitiator in an amount of about 0.1% to about 5% by weight, and the curing of the composition comprises irradiating the composition.

Aspect 135: the method of any of aspects 126-134, wherein the functionalized oligomeric silsesquioxane is functionalized with a glycidyl functional group or an epoxycyclohexyl functional group.

Aspect 136: the method of any of aspects 126-135, wherein the oxetane comprises trimethylol propane oxetane.

Aspect 137: the polymer-based part of any one of aspects 126-136, wherein the polymer-based part comprises a pencil hardness of about 3H or greater in the as-formed state.

Throughout this disclosure, the drawings are used to emphasize certain aspects. Thus, unless expressly stated otherwise, it should be assumed that the relative dimensions of the various regions, portions and substrates shown in the figures are proportional to their actual relative dimensions.

Drawings

The above features and advantages and other features and advantages of aspects of the present disclosure are better understood by reading the following detailed description with reference to the drawings, in which:

1-2 are schematic illustrations of an exemplary coated article in a flat configuration, wherein the schematic illustration of the folded configuration can be seen as shown in FIG. 3, according to aspects;

FIG. 3 is a schematic illustration of an exemplary coated article in a folded configuration in accordance with aspects of the present disclosure, wherein a schematic illustration of a flat configuration may be seen as shown in FIGS. 1-2;

FIG. 4 is a cross-sectional view of a test apparatus for determining the minimum parallel plate spacing of an exemplary modified coated article along line 4-4 of FIG. 3;

FIG. 5 is a schematic plan view of an exemplary consumer electronic device according to aspects;

FIG. 6 is a perspective schematic view of the exemplary consumer electronic device of FIG. 5;

FIG. 7 is a flow chart illustrating an exemplary method of manufacturing a coating and/or coated article according to aspects of the present disclosure; and

fig. 8-13 schematically show steps in a method of manufacturing a coated article according to aspects of the present disclosure.

Detailed Description

Aspects will be described more fully herein with reference to the accompanying drawings in which exemplary aspects are shown. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

The coatings and/or coated articles of aspects of the present disclosure may be used in, for example, coated articles 101, 201, and/or 301 as shown in fig. 1-4, respectively. However, it is to be understood that the coated article is not limited to such applications and may be used in other applications. Unless otherwise indicated, feature discussions for aspects of one coating or coated article may be equally applicable to corresponding features of any aspect of the present disclosure. For example, throughout the present disclosure, identical part numbers may indicate that, in some aspects, the features referred to are identical to each other, and that discussion of the features referred to in one aspect may be equally applicable to the features referred to in any other aspect of the present disclosure, unless otherwise indicated.

Fig. 1-2 schematically show exemplary aspects of a coated article 101 or 201 in an unfolded (e.g., flat configuration) according to aspects of the present disclosure, while fig. 3-4 schematically show exemplary aspects of a coated article 301 in a folded configuration according to aspects of the present disclosure. As shown in fig. 1, the coated article 101 may include a substrate 103 (e.g., a foldable substrate). As shown in fig. 2 and 4, the coated article 201 or 301 may include a substrate 203 (e.g., a foldable substrate). In aspects, the substrate 103 or 203 can include a glass-based substrate and/or a ceramic-based substrate having a pencil hardness of 8H or more (e.g., 9H or more). As used herein, pencil hardness is measured with a standard pencil grade pencil using ASTM D3363-20. Providing a coating on a substrate increases the durability of the coated article by, for example, filling in surface imperfections in the substrate and/or protecting the surface imperfections in the substrate from damage. Further, the substrate may include a glass-based substrate and/or a ceramic-based substrate to enhance puncture resistance and/or impact resistance.

As used herein, "glass-based" includes both glass and glass-ceramic, wherein the glass-ceramic has: one or more crystalline phases, and an amorphous residual glass phase. Based on The material of the glass (e.g., glass-based substrate) may comprise an amorphous material (e.g., glass) and optionally one or more crystalline materials (e.g., ceramic). Amorphous materials and glass-based materials may be strengthened. As used herein, the term "strengthened" may refer to a material that has been chemically strengthened by, for example, ion exchanging smaller ions in the surface of the substrate with larger ions, as discussed below. However, other strengthening methods may be employed, such as thermal tempering or mismatch in coefficients of thermal expansion between substrate portions to create regions of compressive stress and central tension to form a strengthened substrate. Exemplary glass-based materials (which may be free of lithium oxide or contain lithium oxide) include: soda lime silicate glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali-containing aluminoborosilicate glass, alkali-containing phosphosilicate glass, and alkali-containing aluminophosphosilicate glass. In aspects, the glass-based material can include an alkali-containing glass or an alkali-free glass, either of which can be free or contain lithium oxide. In aspects, the glass material may be alkali-free and/or include a low level of alkali metal (e.g., about 10 mole% or less of R ₂ O, where R ₂ O includes Li ₂ O、Na ₂ O、K ₂ O or a broader list provided below). In one or more aspects, the glass-based material can comprise, in mole percent (mol%): siO (SiO) ₂ About 40 mol% to about 80%, al ₂ O ₃ About 5 mol% to about 30 mol%, B ₂ O ₃ 0 to about 10 mole% of ZrO ₂ 0 mol% to about 5 mol%, P ₂ O ₅ 0 mol% to about 15 mol%, tiO ₂ 0 to about 2 mole%, R ₂ O0 mol% to about 20 mol%, and RO 0 mol% to about 15 mol%. As used herein, R ₂ O will refer to alkali metal oxides, e.g. Li ₂ O、Na ₂ O、K ₂ O、Rb ₂ O and Cs ₂ O. As used herein, RO will refer to MgO, caO, srO, baO and ZnO. "glass-ceramic" includes materials produced by controlled crystallization of glass. In an aspect of the present invention,the glass-ceramic has a crystallinity of from about 1% to about 99%. Examples of suitable glass ceramics may include Li ₂ O-Al ₂ O ₃ -SiO ₂ System (i.e., LAS system) glass ceramic, mgO-Al ₂ O ₃ -SiO ₂ System (i.e., MAS system) glass ceramic, znO×Al ₂ O ₃ ×nSiO ₂ (i.e., ZAS systems) and/or glass ceramics comprising a primary crystalline phase comprising β -quartz solid solution, β -spodumene, cordierite, petalite and/or lithium disilicate. The glass-ceramic substrate may be strengthened using a chemical strengthening process. In one or more aspects, the MAS system glass ceramic substrate can be a glass ceramic substrate that is a glass ceramic substrate ₂ SO ₄ Strengthening in molten salt, so that 2Li can occur ⁺ Is coated with Mg ²⁺ And (5) exchanging.

As used herein, "ceramic-based" includes both the case of ceramics and glass ceramics, wherein the glass ceramics have: one or more crystalline phases, and an amorphous residual glass phase. Ceramic-based materials may be strengthened (e.g., chemically strengthened). In aspects, the ceramic-based material may be formed by heating a glass-based material to form a ceramic (e.g., crystalline) portion. In other aspects, the ceramic-based material may include one or more nucleating agents that promote the formation of a crystalline phase. In aspects, the ceramic-based material may include one or more oxides, nitrides, oxynitrides, carbides, borides, and/or silicides. Exemplary aspects of the ceramic oxide include: zirconia (ZrO) ₂ ) Zirconium (ZrSiO) ₄ ) Alkali metal oxides (e.g. sodium oxide (Na) ₂ O)), alkaline earth metal oxides (e.g., magnesium oxide (MgO)), titanium dioxide (TiO) ₂ ) Hafnium oxide (Hf) ₂ O), yttrium oxide (Y) ₂ O ₃ ) Iron oxide, beryllium oxide, vanadium oxide (VO ₂ ) Fused silica, mullite (a mineral comprising a combination of alumina and silica) and spinel (MgAl ₂ O ₄ ). Exemplary aspects of ceramic nitrides include: silicon nitride (Si) ₃ N ₄ ) Aluminum nitride (AlN), gallium nitride (GaN), beryllium nitride (Be) ₃ N ₂ ) Boron Nitride (BN), tungsten nitride (WN), vanadium nitride, alkaline earthMetal nitrides (e.g., magnesium nitride (Mg ₃ N ₂ ) Nickel nitride and tantalum nitride). Exemplary aspects of oxynitride ceramics include: silicon oxynitride, aluminum oxynitride and SiAlON (a combination of aluminum oxide and silicon nitride, and may have the following chemical formula, for example Si) _12-m-n Al _m+n O _n N _16-n 、Si _6-n Al _n O _n N _8-n Or Si (or) _2-n Al _n O _1+n N _2-n Where m, n and the generated subscripts are all non-negative integers). Exemplary aspects of carbides and carbonaceous ceramics include: silicon carbide (SiC), tungsten carbide (WC), iron carbide, boron carbide (B) ₄ C) Alkali metal carbides (e.g. lithium carbide (Li) ₄ C ₃ ) Alkaline earth metal carbides (e.g. magnesium carbide (Mg) ₂ C ₃ ) And graphite. Exemplary aspects of the boride include: chromium boride (CrB) ₂ ) Molybdenum boride (Mo) ₂ B ₅ ) Tungsten boride (W) ₂ B ₅ ) Iron boride, titanium boride, zirconium boride (ZrB) ₂ ) Hafnium boride (HfB) ₂ ) Vanadium Boride (VB) ₂ ) Niobium boride (NbB) ₂ ) And lanthanum boride (LaB) ₆ ). Exemplary aspects of the silicide include: molybdenum disilicide (MoSi) ₂ ) Tungsten disilicide (WSi) ₂ ) Titanium disilicide (TiSi) ₂ ) Nickel silicide (NiSi), alkaline earth silicide (e.g. sodium silicide (NaSi)), alkali silicide (e.g. magnesium silicide (Mg) ₂ Si)), hafnium disilicide (HfSi) ₂ ) And platinum silicide (PtSi).

In aspects, the substrate 103 or 203 can include a polymer-based portion that includes a young's modulus of about 3 gigapascals (GPa) or greater. Exemplary material aspects for the polymer-based first portion and/or the polymer-based second portion include, but are not limited to, blends, nanoparticles, and/or fiber composites of one or more of the following: styrene-based polymers (e.g., polystyrene (PS), styrene Acrylonitrile (SAN), styrene Maleic Anhydride (SMA)), phenylene-based polymers (e.g., polyphenylene sulfide (PPS)), polyvinyl chloride (PVC), polysulfone (PSU), polyphenylene dicarboximide (PPA), polyoxymethylene (POM), polylactide (PLA), polyimide (PI), polyhydroxybutyrate (PHB), polyglycolide (PGA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and/or Polycarbonate (PC).

Throughout this disclosure, the elastic modulus (e.g., young's modulus) of the substrate 103 or 203 (e.g., glass-based material, ceramic-based material) is measured using an indentation method according to ASTM E2546-15. In aspects, the substrate 103 or 203 comprising a glass-based material or a ceramic-based material may include the following elastic moduli: about 10 gigapascals (GPa) or more, about 50GPa or more, about 60GPa or more, about 70GPa or more, about 100GPa or less, or about 80 or less. In aspects, the substrate 103 or 203 comprising a glass-based material or a ceramic-based material may include the following ranges of elastic moduli: about 10GPa to about 100GPa, about 50GPa to about 100GPa, about 60GPa to about 80GPa, about 70GPa to about 80GPa, or any range or subrange therebetween.

As shown in fig. 1-2, the substrate 103 or 203 can include a first major surface 105 or 205 and a second major surface 107 or 207 opposite the first major surface 105 or 205. As shown in fig. 1-2, the first major surface 105 or 205 may extend along the first face 104 or 204a. As further shown in fig. 1-2, the substrate 103 or 203 can include a second major surface 107 or 207 extending along the second face 106 or 204 b. In aspects, as shown, the second face 106 or 204b may be parallel to the first face 104 or 204a. As used herein, the substrate thickness 109 or 222 can be defined between the first major surface 105 or 205 and the second major surface 107 or 207 as the spacing between the first face 104 or 204a and the second face 106 or 204 b. In aspects, the substrate thickness 109 or 222 can extend in the thickness direction 202, which can be perpendicular to the first major surface 105 or 205. In aspects, the substrate thickness 109 or 222 can be: about 10 micrometers (μm) or more, about 25 μm or more, about 40 μm or more, about 60 μm or more, about 80 μm or more, about 100 μm or more, about 125 μm or more, about 150 μm or more, about 3 millimeters (mm) or less, about 2mm or less, about 1mm or less, about 800 μm or less, about 500 μm or less, about 300 μm or less, about 200 μm or less, about 180 μm or less, or about 160 μm or less. In aspects, the substrate thickness 109 or 222 can be in the following range: about 10 μm to about 3mm, about 25 μm to about 2mm, about 40 μm to about 2mm, about 60 μm to about 2mm, about 80 μm to about 2mm, about 100 μm to about 1mm, about 100 μm to about 800 μm, about 100 μm to about 500 μm, about 125 μm to about 300 μm, about 125 μm to about 200 μm, about 150 μm to about 160 μm, or any range or subrange therebetween.

In aspects, as shown in fig. 2, the substrate 203 of the coated article 201 can include a first portion 223 and a second portion 233. As shown, the first portion 223 may include a substrate thickness 222 between the first surface region 225 and the second surface region 227, and the second portion 233 may include a substrate thickness 222 between the third surface region 235 and the fourth surface region 237. In aspects, as shown, the first surface region 225 and the third surface region 235 can extend along the first face 204a, and the first major surface 205 can extend along the first face 204 a. Similarly, as shown, the second surface region 227 and the fourth surface region 237 may extend along the second face 204b, and the second major surface 207 may extend along the second face 204 b. In other aspects, the substrate 203 can include a central portion 281 between the first portion 223 and the second portion 233. In even other aspects, the central portion 281 may include a first central surface region 215 located between the first surface region 225 and the third surface region 235 that is recessed relative to the first face 204a by a first distance 208 that defines the recess 211. In other aspects, as shown, the central portion 281 may include a second central surface region 217 located between the second surface region 227 and the fourth surface region 237. In even other aspects, as shown, the second central surface region 217 can extend along a common plane (e.g., the second plane 204 b) with the second major surface 207, the second surface region 227, and/or the fourth surface region 237. In even other aspects, the central portion 281 may include a central thickness 212 defined between the first central surface region 215 and the second central surface region 217, e.g., as a distance between the third face 204c and the second face 204b, the first central surface region 215 may extend along the third face 204c, and the second central surface region 217 may extend along the second face 204 b. Although not shown, the substrate may include a second recess opposite the first recess, which provides a second central surface area recessed relative to the second major surface rather than coplanar with the second major surface. Further, although not shown, the substrate may include a recess defined between the second central surface region and the second major surface, while the first central surface region may be coplanar with the first major surface.

In aspects, the center thickness 212 may be: about 10 μm or more, about 25 μm or more, about 80 μm or more, about 100 μm or more, about 1mm or less, about 500 μm or less, or about 200 μm or less. In aspects, the center thickness 212 may be in the following range: about 10 μm to about 1mm, for example 25 μm to about 500 μm, about 100 μm to about 200 μm, or any range or subrange therebetween. In other aspects, the center thickness 212 may be about 100 μm or less, for example, in the following range: about 10 μm to about 80 μm, about 25 μm to about 60 μm, about 35 μm to about 50 μm, or any range or subrange therebetween. In aspects, the center thickness 212 may be, in percent of the substrate thickness 222: about 0.5% or greater, about 1% or greater, about 2% or greater, about 5% or greater, about 6% or greater, about 20% or less, about 13% or less, about 10% or less, or about 8% or less. In aspects, the center thickness 212 may be in the following range, as a percentage of the substrate thickness 222: about 0.5% to about 20%, about 1% to about 13%, about 2% to about 10%, about 5% to about 8%, about 6% to about 8%, or any range or subrange therebetween. In an aspect, the first distance 208 may be, in percent of the substrate thickness 222: about 1% or greater, about 2% or greater, about 5% or greater, about 10% or greater, about 12% or greater, about 15% or greater, about 18% or greater, about 20% or greater, about 99% or less, about 90% or less, about 75% or less, about 60% or less, about 50% or less, about 40% or less, about 30% or less, or about 25% or less. In other aspects, the first distance 208 may be in the following range, as a percentage of the substrate thickness 222: about 1% to about 99%, about 2% to about 90%, about 5% to about 75%, about 10% to about 60%, about 12% to about 50%, about 15% to about 40%, about 18% to about 30%, about 20% to about 25%, or any range or subrange therebetween.

As shown in fig. 2, the central portion 281 may include a first transition surface region 229 that is attached between and extends between the first central surface region 215 and the first surface region 225. In an aspect, the first transition width 214 of the first transition surface region 229 may be measured as a minimum distance between the first central surface region 215 of a portion extending along the third face 204c and the first surface region 225 of a portion extending along the first face 204 a. As shown in fig. 2, the central portion 281 may include a second transition surface region 239 attached between and extending between the first central surface region 215 and the third surface region 235. In an aspect, the second transition width 216 of the second transition surface region 239 may be measured as the minimum distance between the first central surface region 215 of the portion extending along the third face 204c and the third surface region 235 of the portion extending along the first face 204 a. In aspects, the first transition width 214 and/or the second transition width 216 may be: about 0.5mm or greater, about 0.6mm or greater, about 0.7mm or greater, about 0.8mm or greater, about 0.9mm or greater, about 5mm or less, about 3mm or less, about 2mm or less, about 1.5mm or less, or about 1mm or less. In aspects, the first transition width 214 and/or the second transition width 216 may be in the following ranges: about 0.5mm to about 5mm, about 0.6mm to about 3mm, about 0.7mm to about 2mm, about 0.8mm to about 1.5mm, about 0.9mm to about 1mm, or any range or subrange therebetween. Providing a transition surface region (e.g., a first transition surface region and/or a second transition surface region) may reduce (e.g., minimize) optical distortion and/or visual visibility of thickness variation from substrate thickness to center thickness.

In aspects, as shown in fig. 2, the thickness of the first transition region 210 including the first transition surface region 229 may be reduced between the substrate thickness 222 of the first portion 223 and the center thickness 212 of the center portion 281. In other aspects, as shown, the thickness of the first transition region 210 may be smoothly decreasing between the substrate thickness 222 of the first portion 223 and the center thickness 212 of the center portion 281, monotonically decreasing, and/or smoothly and individually decreasing. In aspects, as shown in fig. 2, the thickness of the second transition region 218 including the second transition surface region 239 may be reduced between the substrate thickness 222 of the second portion 223 and the center thickness 212 of the center portion 281. In other aspects, as shown, the thickness of the second transition region 218 may be smoothly decreasing, monotonically decreasing and/or smoothly and individually decreasing between the substrate thickness 222 of the second portion 223 and the center thickness 212 of the center portion 281. As used herein, a thickness smoothly decreases if the change in cross-sectional area is smooth (e.g., gradual) rather than a steep (e.g., stepped) change in thickness. As used herein, if the thickness is reduced for one portion and remains the same or is reduced or a combination thereof for the rest of the time (i.e., the thickness is reduced in one direction but never increases), the thickness is monotonically reduced in that direction. Providing a smoothly shaped first transition region and/or second transition region may reduce optical distortion.

In aspects, as shown in fig. 2, the first transition surface region 229 may include a linear sloped surface extending between the first central surface region 215 and the first surface region 225. In aspects, as shown in fig. 2, the second transition surface region 239 may include a linear sloped surface extending between the first central surface region 215 and the third surface region 235. In aspects, although not shown, the first transition surface region and/or the second transition surface region may include a concave-up shape (e.g., the local slope of the corresponding transition surface region smoothly transitions to the slope of the first central surface region 215 while the local slope of the corresponding transition surface region is significantly different from the slope of the first surface region 225. In aspects, although not shown, the first transition surface region and/or the second transition surface region may comprise an S-shape, e.g., a local slope of the corresponding transition surface region is greater in magnitude at a midpoint of the corresponding transition surface region than where the corresponding transition surface region meets the first major surface 205 and where the corresponding transition surface region meets the first central surface region 215.

As shown in fig. 2, the width of the central portion 281 between the first portion 223 and the second portion 233 is equal to the minimum distance between the first portion 223 and the second portion 233. In aspects, the width 287 of the central portion 281 may be the minimum parallel plate spacing of the coated article: about 1-fold or greater, about 1.4-fold or greater, about 1.5-fold or greater, about 2-fold or greater, about 3-fold or less, about 2.5-fold or less, or about 2-fold or less. In aspects, the width 287 of the central portion 281 may be in the following range: about 1.4 times to about 3 times, about 1.5 times to about 2.5 times, about 1.5 times to about 2 times, or any range or subrange therebetween. Without wishing to be bound by theory, the length of the bend in the circular configuration between the parallel plates may be about 0.8 times the parallel plate spacing 407. In an aspect, the width 287 of the central portion 281 may be: about 1mm or greater, about 2mm or greater, about 4mm or greater, about 5mm or greater, about 10mm or greater, about 20mm or greater, about 40mm or greater, about 200mm or less, about 100mm or less, or about 60mm or less. In aspects, the width 287 of the central portion 281 may be in the following range: about 1mm to about 200mm, about 10mm to about 175mm, about 20mm to about 150mm, about 30mm to about 125mm, about 40mm to about 100mm, about 50mm to about 90mm, about 60mm to about 80mm, or any range or subrange therebetween. In aspects, the width 287 of the central portion 281 may be about 60mm or less, e.g., as follows: about 1mm to about 60mm, about 2mm to about 40mm, about 5mm to about 30mm, about 10mm to about 20mm, or any range or subrange therebetween. Controlling the width of the central portion may facilitate folding of the coated article without failure.

As shown in fig. 1-2, the coated article 101 or 201 can include a first coating 113 disposed on a substrate 103 or 203 (e.g., first major surface 105 or 205). In aspects, as shown, the first coating 113 can include a first contact surface 115 and a second contact surface 117 opposite the first contact surface 115. In other aspects, as shown, the second contact surface 117 can face toward and/or contact (e.g., be bonded to) the first major surface 105. In even other aspects, as shown in fig. 2, the second contact surface 117 may face and/or contact (e.g., be bonded to) the first central surface region 215. In other aspects, as shown in fig. 2, at least a portion of the first coating 113 may be disposed in the recess 211. In other aspects, as shown in fig. 2, at least a portion of the first coating 113 occupies the recess 211. In other aspects, as shown, the first coating 113 may completely fill the recess 211, but in other aspects the recess may not be completely filled, e.g., leaving room for electronic and/or mechanical devices.

As shown in fig. 1-2, a maximum first thickness 119 of the first coating 113 and a minimum first thickness 219 of the first coating 113 are defined between the first contact surface 115 and the second contact surface 117. As used herein, the maximum first thickness 119 is defined as the maximum distance between the first contact surface 115 and the second contact surface 117 in the direction 202 of the substrate thickness 109 or 222. As used herein, the minimum first thickness 219 is defined as the minimum distance between the first contact surface 115 and the second contact surface 117 in the direction 202 of the substrate thickness 109 or 222. In aspects, as shown in fig. 1, the maximum first thickness 119 may be substantially equal to the minimum first thickness 219. In aspects, as shown in fig. 2, the maximum first thickness 119 can be different (i.e., greater) than the minimum first thickness 219, e.g., by a first distance 208 that the first central surface region 215 is recessed from the first face 204a (e.g., the first major surface 205) when the first coating 113 is disposed in the recess 211 and extends above the first major surface 205 of the substrate 203. In other aspects, as shown, the second contact surface 117 of the first coating may include: a first portion 247a facing and/or contacting first central surface region 215, a second portion 247b facing and/or contacting first surface region 225, and/or a third portion 247c facing and/or contacting third surface region 235. In an aspect, the minimum first thickness 219 may be: about 1 μm or more, about 5 μm or more, about 10 μm or more, about 15 μm or more, about 100 μm or less, about 80 μm or less, about 50 μm or less, or about 30 μm or less. In aspects, the minimum first thickness 219 may be in the following range: about 1 μm to about 100 μm, about 5 μm to about 80 μm, about 10 μm to about 50 μm, about 15 μm to about 30 μm, or any range or subrange therebetween. In an aspect, as shown in fig. 2, the maximum first thickness 119 can be greater than the first distance 208 by which the first central surface region 215 is recessed from the first face 204a (e.g., the first major surface 205). Providing a first coating may provide good impact resistance to the coated article.

In aspects, the first coating 113 may include a first polymer including a plurality of first monomers connected through ether groups or connected through amine groups. As used herein, the first polymer includes two or more linkages (e.g., ether groups, amine groups) between linked monomers of the plurality of first monomers. As used herein, "monomer" refers to a molecule that binds to another molecule to form a first polymer, which is not necessarily the same as the other "monomers" in the resulting polymer. In other aspects, the plurality of first monomers may include the same monomer. In even other aspects, a pair of the plurality of first monomers can include one or more bonding molecules (e.g., additional monomers) that bind the pair of first monomers together in the first polymer. In other aspects, the plurality of first monomers can include a mixture of two or more different molecules that react to form the first polymer. In other aspects, the ether groups to which the plurality of first monomers are attached may be formed by reaction of epoxy groups or glycidyl groups of the first monomers of the plurality of first monomers. Exemplary aspects of the epoxy functionality include: epoxides, alkyl epoxides (e.g., epoxyethyl, epoxypropyl), and cycloalkyl epoxides (e.g., epoxide cyclohexyl). Exemplary aspects of the glycidyl functionality include: amine glycidyl groups, alkyl glycidyl groups (e.g., glycidyl propyl groups), ether glycidyl groups (e.g., glycidoxy groups), siloxane glycidyl groups (e.g., glycidoxy groups), and combinations thereof (e.g., glycidoxypropyl groups, glycidoxypropyl dimethylsiloxy groups). In even other aspects, the first plurality of monomers may include cycloaliphatic epoxides. As used herein, alicyclic refers to a molecule that comprises a cyclic molecule (e.g., a ring) wherein each atom in the backbone of the cyclic molecule is a carbon atom. The backbone of a cyclic molecule refers to atoms that form a closed ring (e.g., all carbons in cyclohexane). In other aspects, the plurality of first monomers may include a cycloaliphatic epoxide comprising two or more cycloaliphatic rings. Exemplary aspects of alicyclic epoxide molecules (comprising two or more alicyclic rings) include: (3 ', 4-epoxycyclohexane) methyl 3, 4-epoxycyclohexylcarboxylate (e.g., celloxide 2021P (available from Daicel corporation)) and two cyclohexene oxides (e.g., 1' -bis (2, 3-epoxycyclohexane)) having carbon-carbon bonds between the cyclohexyl rings (e.g., celloxide 8010 (available from Daicel corporation)). In aspects, the first polymer may further comprise a linkage between adjacent pairs of first monomers of the plurality of first monomers comprising an alcohol functional group or an ether linkage formed by reaction of an oxetane molecule. An exemplary aspect of the oxetane molecule is trimethylol propane oxetane (TMPO).

In other aspects, one or more amine groups to which the plurality of first monomers are attached may be formed by reaction of an epoxy group or a glycidyl group with an amine group. Exemplary aspects of the amine include: primary alkylamines (e.g., aminopropyl), secondary alkylamines (methylaminopropyl, ethylaminoisobutyl), primary cycloalkylamine groups (e.g., aminocyclohexyl, hexane diamine, trimethyl hexamethylenediamine, isophorone diamine, 4' -methylene-bis [ 2-methylcyclohexylamine ], 4,7, 10-trioxa-1, 13-tridecylamine), secondary cycloalkylamines (e.g., methylaminocyclohexyl), and combinations thereof. In aspects, the first polymer can include other functional groups in addition to the functional groups discussed above (e.g., ethers, amines). In aspects, the first polymer may be free of amine groups along the backbone of the first polymer. As used herein, an atom (e.g., nitrogen in an amine group) is in the backbone of a polymer when: excluding any functional groups located at the ends of the polymer, the longest chain of covalently bonded atoms in the polymer includes the atom (e.g., nitrogen in an amine group). In other aspects, the first coating may be substantially free of amine.

In aspects, the first polymer may include oxygen atoms in the backbone of the first polymer. In other aspects, the oxygen atoms in the backbone may be part of an ether group that connects adjacent pairs of first polymers. Exemplary aspects of polymers comprising oxygen atoms in the backbone of the polymer include: poly (ethylene oxide), poly (propylene oxide), poly (hydroxyethyl methacrylate), poly (lactic acid), poly (caprolactone), poly (glycolic acid), poly (hydroxybutyrate), poly (dimethylsiloxane), cellulose, poly (ethylene terephthalate), and derivatives and/or copolymers thereof. In even other aspects, the polymer may comprise poly (dimethylsiloxane) and/or poly (propylene oxide). In other aspects, the poly (propylene oxide) can be attached to another portion of the second polymer through an ether group (e.g., formed by reaction of an epoxy group or a glycidyl group) or an amine group. In other aspects, the siloxane may be attached to another portion of the second polymer through an ether group (e.g., formed by reaction of an epoxy group or a glycidyl group) or an amine group. In other aspects, the first polymer may comprise a first monomer comprising: difunctional glycols (e.g., ethylene glycol diglycidyl ether), difunctional diethylene glycols (e.g., diethylene glycol diglycidyl ether), difunctional cyclohexanediols (e.g., 1, 2-cyclohexanediol diglycidyl ether), neopentyl glycol (e.g., neopentyl glycol diglycidyl ether), trifunctional trimethoxypropane (e.g., trimethylolpropane triglycidyl ether), tetrafunctional erythritol (e.g., pentaerythritol glycidyl ether), and trifunctional tris (4-hydroxyphenyl) methane (e.g., tetrakis (4-hydroxyphenyl) methane triglycidyl ether). In aspects, the first polymer may be substantially free of aromatic groups in the monomer units. In aspects, the first polymer may be substantially free of fluorine, urethane, isocyanate, acrylate, and/or polycarbonate. Providing a first polymer that includes oxygen atoms in the backbone of the first polymer may increase flexibility to the first polymer and the resulting coating, which may increase its ultimate elongation, durability, and/or impact resistance (e.g., drop height).

In aspects, the first polymer may include a first plurality of functionalized oligomeric silsesquioxanes. In other aspects, the plurality of first monomers may alsoComprising the first plurality of functionalized oligomeric silsesquioxanes. As used herein, functionalized oligomeric silsesquioxanes means that the organosilicon compound comprises at least two compounds denoted RSiO _1.5 Wherein there are three oxygen atoms, each oxygen atom shared with another monomer bound thereto, and R is a functional group that "functionalizes" the oligomeric silsesquioxane to form a functionalized oligomeric silsesquioxane, but R of one monomer is not necessarily the same as R of another monomer. In aspects, RSiO in functionalized oligomeric silsesquioxanes _1.5 The amount of monomer may be an integer of 4 or more, 6 or more, 8 or more, 50 or less, 30 or less, 20 or less, 16 or less, about 12 or less, or 10 or less. In aspects, RSiO in functionalized oligomeric silsesquioxanes _1.5 The amount of monomer may be an integer in the following range: 4 to 50,4 to 30,6 to 20,6 to 16,8 to 12,8 to 10, or any range or subrange therebetween.

In aspects, the functionalized oligomeric silsesquioxanes may also include RSiO in addition to that discussed above _1.5 Any number of RSiO other than monomer units ₂ Monomers, where, likewise, R may be at RSiO ₂ Monomers and RSiO _1.5 A change occurs between monomers in either or both monomers. In other aspects, RSiO ₂ The monomer may be a blocked monomer, meaning that it is attached to only one other monomer. For simplicity, these "end-capping monomers" will be referred to as RSiO ₂ It is to be understood that RSiO ₂ The monomer may refer to any of the following: RSiO _3.5 、RSiO _2.5 、R ₂ SiO _3.5 、R ₂ SiO _2.5 、R ₂ SiO _1.5 、R ₃ SiO _3.5 、R ₃ SiO _2.5 、R ₃ SiO _1.5 Or R is ₃ SiO _0.5 Wherein a first R in a single endcapping monomer may be the same as or different from another R (e.g., one R or all R) in the same single endcapping monomer. In other aspects, RSiO ₂ The monomer may be combined with two other monomers. For example, RSiO ₂ The monomer may be combined with another RSiO ₂ One RSiO _1.5 Monomers or two RSiO _1.5 And (3) monomer combination. For simplicity, "non-blocked RSiO ₂ Monomer "may refer to any of the following: RSiO ₃ 、RSiO ₂ 、R ₂ SiO ₃ Or R is ₂ SiO ₂ Wherein a single "non-capped RSiO ₂ The first R in "may be the same as the single" non-blocked RSiO ₂ "the other R (e.g., one R or all R) are the same or different. In other aspects, RSiO ₂ The amount of monomers may be less than or equal to RSiO _1.5 The amount of monomers. For example, when RSiO ₂ The amount of monomer was 4 and RSiO _1.5 When the number of monomers is 4 or greater, ladder-like functionalized oligomeric silsesquioxanes are formed, wherein each RSiO _1.5 Monomer linkage to two other RSiO _1.5 Monomer and RSiO _1.5 Monomers or RSiO ₂ Any one of the monomers.

In other aspects, the functionalized oligomeric silsesquioxanes may include 1 to 3 RSiO ₂ Monomers (e.g., 1, 2, 3). In even other aspects, adjacent RSiO _1.5 The monomer pairs may be interconnected by two or more non-overlapping paths, wherein each path includes, in addition to the adjacent RSiO _1.5 At least one monomer outside the pair of monomers, and the first path connects to the second path without passing through the adjacent pair of monomers. For example, the open-cage functionalized oligomeric silsesquioxane may include adjacent rsios interconnected by two or more non-overlapping pathways _1.5 A monomer pair, and the first path is connected to the second path without passing through the adjacent monomer pair, while also containing 1 to 3 RSiO ₂ And (3) a monomer. It is to be understood that RSiO _1.5 The silsesquioxane monomer is different from the siloxane monomer (which would include an M-type siloxane monomer (e.g., R ₃ SiO _0.5 ) D-type siloxane monomers (e.g., R ₂ SiO ₂ ) And/or a silica type siloxane monomer (SiO) ₂ ). In aspects, the functionalized oligomeric silsesquioxanes can be prepared from RSiO _1.5 And (3) a monomer. As used herein, polyhedral oligomeric silsesquioxanes (POSS) refers toIs made of RSiO _1.5 Functionalized oligomeric silsesquioxanes composed of monomers. Exemplary aspects of the functionalized POSS may include 6, 8, 10, or 12 rsios _1.5 Monomers, but other aspects are also possible. For example, by 8 RSiO _1.5 The monomer-built functionalized oligomeric silsesquioxanes are octahedral functionalized POSS (e.g., polyoctahedral silsesquioxanes).

The functionalized oligomeric silsesquioxanes may be functionalized by one or more functional groups. As used herein, the functional groups that functionalize the functionalized oligomeric silsesquioxanes will exclude hydrogen, bisphenol, and/or fluorine containing functional groups. In aspects, the functional groups for the functionalized oligomeric silsesquioxanes may include epoxides, glycidyl groups, oxiranes, and/or anhydrides. In other aspects, the functional group for functionalizing the oligomeric silsesquioxane may be a glycidyl functional group or an epoxycyclohexyl functional group. Throughout this disclosure, functionalized POSS functionalized with glycidyl groups is referred to as GPOSS. Exemplary aspects of the glycidyl functionality include: amine glycidyl groups, alkyl glycidyl groups (e.g., glycidyl propyl, glycidyl isobutyl), ether glycidyl groups (e.g., glycidoxy), siloxane glycidyl groups (e.g., glycidyldimethylolsilyl) and combinations thereof (e.g., glycidoxypropyl dimethylsiloxy). Commercially available examples of GPOSS include: 3-glycidoxypropyl functionalized POSS (e.g., EP0408 (Hybrid Plastics), EP0409 (Hybrid Plastics)), 3-glycidoxypropyl functionalized POSS (e.g., 560624 (Sigma Aldrich)) glycidoxypropyl functionalized POSS (e.g., EP0418 (Hybrid Plastics)), and 3-glycidoxypropyl dimethoxysilyl (e.g., 593869 (Sigma Aldrich), EP0435 (Hybrid Plastics)). Exemplary aspects of the epoxy functionality include: epoxides, alkyl epoxides (e.g., epoxyethyl, epoxypropyl), and cycloalkyl epoxides (e.g., epoxide cyclohexyl). Commercially available examples of epoxy functionalized POSS include (3, 4, epoxycyclohexyl) ethyl functionalized POSS (e.g., 560316 (sigma aldrich). Exemplary aspects of anhydrides include maleic anhydride, succinic anhydride, acetic anhydride, and alkyl anhydrides (e.g., acetic anhydride, propionic anhydride).

As used herein, a functionalized oligomeric silsesquioxane is functionalized with at least one of the functional groups listed in the preceding paragraph. In aspects, the functionalized oligomeric silsesquioxanes (e.g., functionalized POSS) can include two or more R groups comprising the functional groups listed in the preceding paragraphs that functionalize the oligomeric silsesquioxanes. In other aspects, substantially each R group in the functionalized oligomeric silsesquioxane may include the functional groups listed in the preceding paragraphs that functionalize the oligomeric silsesquioxane. In even other aspects, all R groups comprising the functional groups listed in the preceding paragraph may comprise the same functional groups. In even other aspects, the functionalized oligomeric silsesquioxanes may be functionalized with two or more different functional groups as set forth in the preceding paragraph. In other aspects, the functionalized oligomeric silsesquioxanes may be functionalized with a first functional group (R) selected from those listed in the preceding paragraph and a second functional group (R2) selected from those listed in the preceding paragraph, wherein R is different from R2. In other aspects, one or more of the R groups may include functional groups other than those listed in the preceding paragraphs. For example, other potential R groups include hydrogen, alkyl, cycloalkyl, alcohol, and amine. In even other aspects, the third functional group (R3) of the functionalized oligomeric silsesquioxane may include hydrogen or an alkyl, cycloalkyl, alcohol, or amine functional group without including one of the functional groups listed in the preceding paragraphs.

Throughout this disclosure, dynamic light scattering according to ISO 22412:2017 is employed to measure the effective diameter of a molecule (e.g., a functionalized oligomeric silsesquioxane). In aspects, the effective diameter of one of the plurality of functionalized oligomeric silsesquioxanes may be: about 20nm or less, about 15nm or less, about 10nm or less, about 6nm or less, about 1nm or more, about 2nm or more, or about 4nm or more. In aspects, the effective diameter of one of the plurality of oligomeric silsesquioxanes can be in the following range: about 1nm to about 20nm, about 2nm to about 15nm, about 4nm to about 10nm, about 4nm to about 6nm, or any range or subrange therebetween. In other aspects, the average effective diameter of the plurality of functionalized oligomeric silsesquioxanes can be within one or more of the ranges of effective diameters of functionalized oligomeric silsesquioxanes discussed above. In other aspects, substantially all and/or all of the plurality of functionalized oligomeric silsesquioxanes may be within one or more of the ranges of effective diameters of the functionalized oligomeric silsesquioxanes discussed above.

In aspects, a first functionalized oligomeric silsesquioxane of the first plurality of functionalized oligomeric silsesquioxanes may be combined with a second functionalized oligomeric silsesquioxanes of the first plurality of functionalized oligomeric silsesquioxanes as part of the first polymer. In other aspects, the first functionalized oligomeric silsesquioxane may be located at a first end of a first polymer opposite a second end of the first polymer where the second functionalized oligomeric silsesquioxane is located. In other aspects, the first functionalized oligomeric silsesquioxane may be spaced apart from the second functionalized oligomeric silsesquioxane by at least 20 atoms along the backbone of the first polymer. Providing a first polymer having a plurality of functionalized oligomeric silsesquioxanes, wherein the plurality of functionalized oligomeric silsesquioxanes are spaced apart (e.g., at least 20 atoms apart along the backbone of the first polymer and/or at opposite ends of the first polymer), can reduce (e.g., prevent) coalescence of the plurality of functionalized oligomeric silsesquioxanes, which can provide good optical properties (e.g., high transmittance, low haze), good durability, and/or good adhesion.

In aspects, the weight percent (wt.%) of the plurality of functionalized oligomeric silsesquioxanes in the first coating 113 can be: about 60 wt% or more, about 65 wt% or more, 100 wt% or less, about 80 wt% or less, about 75 wt% or less, or about 70 wt% or less. In aspects, the weight% of the plurality of functionalized oligomeric silsesquioxanes in the first coating 113 can be in the following range: about 60 wt% to 100 wt%, about 60 wt% to about 80 wt%, about 60 wt% to about 75 wt%, about 65 wt% to about 70 wt%, or any range or subrange therebetween. In aspects, the wt% of the plurality of functionalized oligomeric silsesquioxanes can be about 20 wt% or less, e.g., in the following range: 0 wt% to about 20 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 10 wt%, or any range or subrange therebetween. The concentration of the functionalized oligomeric silsesquioxanes and siloxanes may be determined using X-ray photoelectron spectroscopy (XPS) and/or raman spectroscopy of the sample of the corresponding coating, wherein the intensity of the silicon or silicon-oxygen bonds (in XPS) would correspond to the concentration of the functionalized oligomeric silsesquioxanes (e.g., POSS) and siloxanes (e.g., polysiloxanes). In aspects, the first coating 113 can be substantially free of functionalized oligomeric silsesquioxanes.

Throughout this disclosure, thermogravimetric analysis (TGA) can be employed to determine the proportion (e.g., wt%) of a coating comprising an organic material. In aspects, the weight% of organic material (e.g., cycloaliphatic epoxide, amine) in the first coating 113 can be: about 20 wt% or greater, about 25 wt% or greater, about 30 wt% or greater, about 40 wt% or greater, about 50 wt% or greater, 100 wt% or less, about 90 wt% or less, about 80 wt% or less, about 70 wt% or less, or about 60 wt% or less. In aspects, the weight% of the organic material in the first coating layer 113 may be in the following range: about 20 wt% to 100 wt%, about 25 wt% to about 90 wt%, about 30 wt% or more to about 80 wt%, about 40 wt% to about 70 wt%, about 50 wt% to about 60 wt%, or any range or subrange therebetween.

Throughout this disclosure, a composition or coating (e.g., first coating 113, second coating 123) is "substantially free" of a component if: which comprises this component in an amount of about 0.25% by weight or less (except in the case of substantially no solvent as defined below). In aspects, the first coating 113 may be substantially free of nanoparticles. In aspects, the first coating 113 may be substantially free and/or free of silica nanoparticles. As used herein, silica nanoparticles refer to particles comprising an effective diameter of at least 20nm and comprising silica. The silica nanoparticles may comprise solid particles or mesoporous particles. The silica nanoparticles may be larger (e.g., comprise a larger effective diameter) than the functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes. The silica nanoparticles may be formed from colloidal silica and/or via a sol gel process. Without wishing to be bound by theory, the silica nanoparticles may aggregate (especially at elevated temperatures), which detracts from the mechanical and/or optical properties of the first coating and/or the coated article. Providing a first coating that is substantially free and/or free of silica nanoparticles may reduce processing problems (e.g., agglomeration, coalescence, phase separation) associated with forming the first coating, may improve optical properties of the coating and/or the coated article (e.g., maintain low haze and/or high transmittance even after aging at elevated temperatures and/or humidity), and may reduce mechanical properties (e.g., hardness, modulus, strain, impact resistance) of the resulting coating and/or coated article, as compared to a corresponding coating and/or coated article without silica nanoparticles.

In aspects, the first coating 113 may include a photoinitiator. As used herein, a photoinitiator is a compound that is sensitive to one or more wavelengths that reacts upon absorption of light comprising the one or more wavelengths to produce one or more free radical or ionic species that initiate the reaction. In other aspects, the photoinitiator may be sensitive to one or more wavelengths of Ultraviolet (UV) light. In other approaches, the photoinitiator may include a cationic photoinitiator, which is a photoinitiator configured to initiate a cationic reaction (e.g., cationic polymerization). Exemplary aspects of photoinitiators that are sensitive to UV light include, but are not limited to: benzoin ethers, benzil (benzoin) ketals, dialkoxyacetophenones, hydroxyalkylphenones, aminoalkylphenones, acylphosphine oxides, thioxanthones, hydroxyalkylketones and thioxanthone amines. In other aspects, the photoinitiator may be sensitive to one or more wavelengths in the visible light. Exemplary aspects of photoinitiators that are sensitive to visible light include, but are not limited to: 5, 7-diiodo-3-butoxy-6-fluoroalkane, bis (4-methoxybenzoyl) diethylgermanium, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 3-methyl-4-aza-6-spiroalkene, and thiomerocyanine borate (thiocyanine borate). In other aspects, the photoinitiator may be sensitive to wavelengths at which other components of the first coating are substantially transparent. In other aspects, the photoinitiator may initiate a cationic reaction (e.g., cationic polymerization), for example, the photoinitiator may include: triarylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate and bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate. In other aspects, the photoinitiator may include a radical photoinitiator configured to generate one or more radicals, e.g., the photoinitiator may include acetophenone-based compounds (e.g., dimethoxyphenylacetophenone), azobisisobutyronitrile (AIBN), and aromatic peroxides (e.g., benzoyl peroxide). Commercially available photoinitiators include, but are not limited to, the Irgacure product line from BASF corporation. In aspects, the first coating 113 may include the following wt% photoinitiators (wt%): about 0.1 wt% or more, about 0.2 wt% or more, about 0.5 wt% or more, about 6 wt% or less, about 5 wt% or less, about 4 wt% or less, about 3 wt% or less, about 2 wt% or less, or about 1 wt% or less. In aspects, the first coating 113 may be substantially free of fluorine-based compounds. As used herein, a coating may be substantially free of fluorine-based compounds while containing trace amounts of fluorine in the minor components of the corresponding coating (e.g., about 6 wt% or less of the photoinitiator), corresponding to about 0.25 wt% or less of total fluorine. In other aspects, the first coating 113 may be free of fluorine-based compounds. In aspects, the first coating 113 may be substantially free and/or free of photoinitiators. Providing a coating that is free of a photoinitiator (e.g., a thermally curable composition) may eliminate yellowing problems.

As shown in fig. 1-2, the coated article 101 or 201 can include a second coating 123 disposed on the first coating 113 (e.g., the first contact surface 115). In aspects, as shown, the second coating 123 can include a third contact surface 125 and a fourth contact surface 127 opposite the third contact surface 125. In other aspects, as shown, the fourth contact surface 127 can face toward and/or contact the first contact surface 115 of the first coating 113. In other aspects, as shown, the fourth contact surface 127 can face the first major surface 105 or 205 of the substrate 103 or 203. In other aspects, as shown, the first coating 113 can be located between the substrate 103 or 203 and the second coating 123. In even other aspects, as shown, the second coating 123 (e.g., fourth contact surface 127) can contact the first coating 113 (e.g., first contact surface 115), and the first coating 113 (e.g., second contact surface 117) can contact the first major surface 105 of the substrate 103 or 203 and/or can contact the first central surface region 215 (if present) of the substrate 203.

As shown in fig. 1-2, the average second thickness 129 of the second coating 123 is defined as the average distance between the third contact surface 125 and the fourth contact surface 127. In an aspect, as shown, the average second thickness 129 extends in a thickness direction 202. In an aspect, the average second thickness 129 may be: about 1 μm or greater, about 1.25 μm or greater, about 1.5 μm or greater, about 2 μm or greater, about 50 μm or less, about 20 μm or less, about 10 μm or less, about 5 μm or less, or about 3 μm or less. In aspects, the average second thickness 129 of the second coating 123 can be in the following range: about 1 μm to about 50 μm, about 1.25 μm to about 20 μm, about 1.5 μm to about 10 μm, about 1.5 μm to about 5 μm, about 2 μm to about 3 μm, or any range or subrange therebetween. Providing a second thickness coating falling within one or more of the above ranges may provide good hardness without significantly compromising the impact resistance of the resulting article.

In aspects, the second coating 123 may include a second polymer including a plurality of second monomers connected through ether groups or connected through amine groups. As used herein, the second polymer includes two or more linkages (e.g., ether groups, amine groups) between adjacent monomers of the plurality of second monomers. In other aspects, the plurality of second monomers may include the same monomer. In even other aspects, a pair of second monomers of the plurality of first monomers can include one or more bonding molecules (e.g., additional monomers) that bind the pair of second monomers together in a second polymer. In other aspects, the plurality of second monomers can include a mixture of two or more different molecules that react to form the second polymer. In other aspects, the ether groups to which the plurality of second monomers are attached may be formed by reaction of epoxy groups or glycidyl groups of the second monomers of the plurality of second monomers. In even other aspects, the plurality of second monomers may include cycloaliphatic epoxides. In other aspects, the plurality of second monomers may include a cycloaliphatic epoxide comprising two or more cycloaliphatic rings. Exemplary aspects of alicyclic epoxide molecules (comprising two or more alicyclic rings) include: (3 ', 4-epoxycyclohexane) methyl 3, 4-epoxycyclohexylcarboxylate (e.g., celloxide 2021P (available from Daicel corporation)) and two cyclohexene oxides (e.g., 1' -bis (2, 3-epoxycyclohexane)) having carbon-carbon bonds between the cyclohexyl rings (e.g., celloxide 8010 (available from Daicel corporation)). In other aspects, the second polymer may further comprise linkages between adjacent pairs of second monomers of the plurality of second monomers, including alcohol functional groups or ether linkages formed by reaction of oxetane molecules. An exemplary aspect of the oxetane molecule is trimethylol propane oxetane (TMPO).

In other aspects, one or more amine groups to which the plurality of second monomers are attached may be formed by reaction of an epoxy group or a glycidyl group with an amine group. In aspects, the second polymer may include other functional groups in addition to the functional groups discussed above (e.g., ethers, amines). In aspects, the second polymer may be free of amine groups along the backbone of the second polymer. In other aspects, the second coating may be substantially free of amine.

In aspects, the second polymer may include a second plurality of functionalized oligomeric silsesquioxanes. In other aspects, the plurality of second monomers may further include the second plurality of functionalized oligomeric silsesquioxanes. In other aspects, the second plurality of functionalized oligomeric silsesquioxanes can include any of the properties discussed above with respect to the first plurality of functionalized oligomeric silsesquioxanes. In other aspects, the functional groups for the functionalized oligomeric silsesquioxanes may include epoxides, glycidyl groups, oxiranes, and/or anhydrides. In other aspects, the functional group for functionalizing the oligomeric silsesquioxane may be a glycidyl functional group or an epoxycyclohexyl functional group. In aspects, a first functionalized oligomeric silsesquioxane of the second plurality of functionalized oligomeric silsesquioxanes may be combined with a second functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes as part of a second polymer. In other aspects, the first functionalized oligomeric silsesquioxane may be located at a first end of a second polymer opposite the second end of the second polymer where the second functionalized oligomeric silsesquioxane is located. In other aspects, the first functionalized oligomeric silsesquioxane may be spaced apart from the second functionalized oligomeric silsesquioxane by at least 20 atoms along the backbone of the second polymer. Providing a second polymer having a plurality of functionalized oligomeric silsesquioxanes, wherein the plurality of functionalized oligomeric silsesquioxanes are spaced apart (e.g., at least 20 atoms apart along the backbone of the second polymer and/or at opposite ends of the second polymer), can reduce (e.g., prevent) coalescence of the plurality of functionalized oligomeric silsesquioxanes, which can provide good optical properties (e.g., high transmittance, low haze), good durability, and/or good adhesion.

In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes in the second coating 123 can be: about 50 wt% or more, about 60 wt% or more, about 65 wt% or more, about 80 wt% or less, about 75 wt% or less, or about 70 wt% or less. In aspects, the weight% of the plurality of functionalized oligomeric silsesquioxanes in the second coating 123 can be in the following range: about 50 wt% to about 80 wt%, about 60 wt% to about 75 wt%, about 65 wt% to about 70 wt%, or any range or subrange therebetween. In aspects, the second coating 123 can be substantially free of functionalized oligomeric silsesquioxanes.

In aspects, the weight% of organic material (e.g., cycloaliphatic epoxide, amine) in the second coating 123 can be: about 20 wt% or greater, about 25 wt% or greater, about 30 wt% or greater, about 40 wt% or greater, about 50 wt% or greater, 100 wt% or less, about 90 wt% or less, about 80 wt% or less, about 70 wt% or less, or about 60 wt% or less. In aspects, the weight% of the organic material in the second coating layer 123 may be in the following range: about 20 wt% to 100 wt%, about 25 wt% to about 90 wt%, about 30 wt% or more to about 80 wt%, about 40 wt% to about 70 wt%, about 50 wt% to about 60 wt%, or any range or subrange therebetween.

In aspects, the second coating 123 may be substantially free of nanoparticles. In aspects, the second coating 123 can be substantially free and/or free of silica nanoparticles. Providing the second coating 123 substantially free and/or free of silica nanoparticles may reduce processing problems (e.g., agglomeration, coalescence, phase separation) associated with the second coating 123, may improve optical properties (e.g., maintain low haze and/or high transmittance, even after aging at elevated temperatures and/or humidity) of the coating and/or the resulting coating and/or the coated article, and may reduce mechanical properties (e.g., hardness, modulus, strain, impact resistance) of the resulting coating and/or the coated article, as compared to a corresponding coating and/or coated article without silica nanoparticles.

In aspects, the second coating 123 may include nanoparticles. In other aspects, the nanoparticle may comprise: silica nanoparticles, alumina nanoparticles, zirconia nanoparticles, titania nanoparticles, carbon black, and/or combinations thereof. In aspects, the second coating 123 may include silica nanoparticles and/or alumina nanoparticles. In other aspects, the weight% of silica nanoparticles and/or alumina nanoparticles in the second coating 12 (second coating) can be about 1 weight% or greater, about 5 weight% or greater, about 30 weight% or less, or about 10 weight% or less. In other aspects, the weight% of the linkages (e.g., various linkages) in the second coating 123 can be in the following range: about 1% to about 30%, about 5% to about 10%, or any range or subrange therebetween. In other aspects, the silica nanoparticles and/or alumina nanoparticles can have an average effective diameter of about 10nm or greater, about 20nm or greater, about 30nm or greater, about 100nm or less, about 50nm or less, or about 40nm or less. In other aspects, the average effective diameter ranges from about 10nm to about 100nm, from about 20nm to about 50nm, from about 30nm to about 40nm, or any range or subrange therebetween. In other aspects, the silica nanoparticles and/or alumina nanoparticles may not be associated with the functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes in the second coating. Providing nanoparticles can increase the hardness and/or impact resistance of the coated article.

In aspects, the second coating 123 may include a photoinitiator. In other aspects, the photoinitiator may include a cationic photoinitiator, which is a photoinitiator configured to initiate a cationic reaction (e.g., cationic polymerization). In aspects, the second coating 123 may include the following wt% photoinitiators (wt%): about 0.1 wt% or more, about 0.2 wt% or more, about 0.5 wt% or more, about 6 wt% or less, about 5 wt% or less, about 4 wt% or less, about 3 wt% or less, about 2 wt% or less, or about 1 wt% or less. In aspects, the second coating 123 may be substantially free of fluorine-based compounds. In other aspects, the second coating 123 may be free of fluorine-based compounds. In aspects, the second coating 123 can be substantially free of photoinitiator (e.g., free of photoinitiator). Providing a coating that is free of a photoinitiator (e.g., a thermally curable composition) may eliminate yellowing problems.

In aspects, the second polymer may include oxygen atoms in the backbone of the first polymer. In other aspects, the oxygen atoms in the backbone may be part of an ether group that connects adjacent pairs of second monomers. In even other aspects, the polymer may include a siloxane, (e.g., poly (dimethylsiloxane) and/or poly (propylene oxide)). In other aspects, the poly (propylene oxide) can be attached to another portion of the second polymer through an ether group (e.g., formed by reaction of an epoxy group or a glycidyl group) or an amine group. In other aspects, the siloxane may be attached to another portion of the second polymer through an ether group (e.g., formed by reaction of an epoxy group or a glycidyl group) or an amine group. In other aspects, the second polymer may comprise a second monomer comprising: difunctional glycols (e.g., ethylene glycol diglycidyl ether), difunctional diethylene glycols (e.g., diethylene glycol diglycidyl ether), difunctional cyclohexanediols (e.g., 1, 2-cyclohexanediol diglycidyl ether), neopentyl glycol (e.g., neopentyl glycol diglycidyl ether), trifunctional trimethoxypropane (e.g., trimethylolpropane triglycidyl ether), tetrafunctional erythritol (e.g., pentaerythritol glycidyl ether), and trifunctional tris (4-hydroxyphenyl) methane (e.g., tetrakis (4-hydroxyphenyl) methane triglycidyl ether). In aspects, the second polymer may be substantially free of aromatic groups in the monomer units. In aspects, the second polymer may be substantially free of fluorine, urethane, isocyanate, acrylate, and/or polycarbonate. Providing a second polymer that includes oxygen atoms in the backbone of the second polymer may increase flexibility to the second polymer and the resulting coating, which may increase its ultimate elongation, durability, and/or impact resistance (e.g., drop height).

Table 1 presents examples A-L according to aspects of the present disclosure, the components of which may be present in the first coating and/or the second coating. As shown, in examples a-L, both the first and second coatings comprise a reacted epoxide (e.g., a glycidyl group), which may be in the form of an alcohol or ether linkage adjacent to the amine. In examples B, D, I and K-L, both the first and second coatings contained amine in the corresponding polymer. In examples C-D and L, both the first coating and the second coating comprise POSS. In embodiments J-L, the second coating will include nanoparticles. In embodiments a-D, the first coating and the second coating will comprise the same component; however, as shown in examples E-L, the first coating will comprise a different composition than the second coating. For example, as shown in examples F-I, the second coating may include POSS, while the first coating may not. Furthermore, it is to be understood that in embodiments a-D, when the first and second coatings comprise the same component, the relative proportions of the components in the first coating and the second component may be the same or different.

Table 1: composition of the coating

The first polymer and/or the second polymer may include a glass transition (Tg) temperature. As used herein, dynamic Mechanical Analysis (DMA) is employed, and DMA 850, e.g., a TA instrument, is employed to measure glass transition temperature, storage modulus, and loss modulus. Samples for DMA analysis included membranes fixed by tension clamps. As used herein, storage modulus refers to the in-phase (in-phase) component of a polymer or polymer-based material in response to dynamic testing. As used herein, loss modulus refers to the out-of-phase component of a responsive polymer or polymer-based material during dynamic testing. As used herein, the glass transition temperature corresponds to the maximum of tgΔ, which is the ratio of loss modulus to storage modulus. In aspects, the glass transition temperature of the first polymer and/or the second polymer can be outside the operating range (e.g., about-20 ℃ to about 60 ℃) of the coated article. In aspects, the glass transition temperature of the first polymer and/or the second polymer will be: about 0 ℃ or less, about-20 ℃ or less, about-40 ℃ or less, about-140 ℃ or more, about-80 ℃ or more, or about-60 ℃ or more. In aspects, the glass transition temperature of the first polymer and/or the second polymer may be in the following range: about-120 ℃ to about 0 ℃, about-120 ℃ to about-20 ℃, about-80 ℃ to about-40 ℃, about-80 ℃ to about-60 ℃, or any range or subrange therebetween. In aspects, the glass transition temperature of the first polymer and/or the second polymer will be: about 60 ℃ or higher, about 80 ℃ or higher, about 100 ℃ or higher, about 200 ℃ or lower, about 160 ℃ or lower, or about 120 ℃ or lower. In aspects, the glass transition temperature of the first polymer and/or the second polymer may be in the following range: about 60 ℃ to about 200 ℃, about 60 ℃ to about 160 ℃, about 80 ℃ to about 120 ℃, about 80 ℃ to about 100 ℃, or any range or subrange therebetween. Providing a first polymer and/or a second polymer portion having a glass transition temperature that falls outside of an operating range (e.g., about 0 ℃ to about 40 ℃, about-20 ℃ to about 60 ℃) may achieve consistent properties over the operating range.

Throughout this disclosure, tensile strength, ultimate elongation (e.g., strain to failure) and yield point of a polymeric material (e.g., first coating, second coating) are determined using ASTM D638, using a tensile testing machine (e.g., instron3400 or Instron 6800), at 23 ℃ and 50% relative humidity, with a type I dog bone shaped sample. Throughout the present disclosure, ISO 527-1:2019 is used to measure the elastic modulus and/or Poisson's ratio of a polymeric material. In aspects, the elastic modulus of the first coating 113 may be: about 1 megapascal (MPa) or greater, about 5MPa or greater, about 10MPa or greater, about 20MPa or greater, about 100MPa or greater, 200MPa or greater, about 500MPa or greater, about 2,000MPa or less, about 1,500MPa or less, about 1,000MPa or less, about 800MPa, about 100MPa or less, about 75MPa or less, about 50MPa or less, or about 30MPa or less. In aspects, the elastic modulus of the first coating layer 113 may be in the following range: about 1MPa to about 2,000MPa, about 10MPa to about 1,500MPa, about 20MPa to about 1,500MPa, about 100MPa to about 1,500MPa, about 200MPa to about 1,000MPa, about 500MPa to about 800MPa, or any range or subrange therebetween. In aspects, the elastic modulus of the first coating layer 113 may be in the following range: about 1MPa to about 100MPa, about 5MPa to about 75MPa, about 10MPa to about 50MPa, about 20MPa to about 30MPa, or any range or subrange therebetween.

In aspects, the elastic modulus of the second coating 123 may be: about 100 megapascals (MPa) or greater, about 200MPa or greater, about 500MPa or greater, about 1,000MPa or greater, about 5,000MPa or less, about 3,000MPa or less, about 2,000MPa or less, or about 1,000MPa or less. In aspects, the modulus of elasticity of the second coating may be in the following range: about 100MPa to about 5,000MPa, about 200MPa to about 3,000MPa, about 500MPa to about 2,000MPa, about 1,000MPa to about 2,000MPa, or any range or subrange therebetween.

Throughout this disclosure, tensile strength, ultimate elongation (e.g., strain to failure) and yield point of the first and second coatings 113 and 123 are determined using ASTM D412A using a tensile testing machine (e.g., instron 3400 or Instron 6800) at 23 ℃ and 50% relative humidity, in a type I dog bone shaped sample. In aspects, the tensile strength of the first coating 113 and/or the second coating 123 can be: about 2 megapascals (MPa) or greater, 10MPa or greater, about 20MPa, about 25MPa or greater, about 30MPa or greater, about 50MPa or greater, about 45MPa or less, about 40MPa or less, or about 35MPa or less. In aspects, the tensile strength of the first coating 113 and/or the second coating 123 may be in the following range: about 2MPa to about 50MPa, about 10MPa to about 45MPa, about 20MPa to about 40MPa, about 25MPa to about 35MPa, or any range or subrange therebetween.

In aspects, the final elongation of the first coating 113 and/or the second coating 123 can be: about 3% or greater, about 4% or greater, about 5% or greater, about 6% or greater, about 20% or less, about 10% or less, about 8% or less, or about 7% or less. In aspects, the final elongation of the first coating 113 and/or the second coating 123 may be in the following range: about 3% to about 20%, about 4% to about 10%, about 5% to about 8%, about 6% to about 8%, about 7% to about 8%, or any range or subrange therebetween.

In aspects, the second coating 123 and/or the coated article 101 or 201 can include a contact angle of deionized water on the third contact surface 125 of the second coating 123. Throughout this disclosure, contact angles were measured at 25 ℃ according to ASTM D7334-08 (2013). In other aspects, the contact angle may be: about 10 ° or greater, about 40 ° or greater, about 60 ° or greater, about 65 ° or greater, about 70 ° or greater, about 140 ° or less, about 110 ° or less, about 100 ° or less, about 95 ° or less, or about 90 ° or less. In other aspects, the contact angle may be in the following range: about 10 ° to about 140 °, about 40 ° to about 110 °, about 60 ° to about 100 °, about 65 ° to about 95 °, about 70 ° to about 90 °, or any range or subrange therebetween. In other aspects, the coating may be hydrophilic, for example, including the following ranges of contact angles: about 90 ° to about 140 °, about 90 ° to about 110 °, about 90 ° to about 105 °, about 95 ° to about 100 °, or any range or subrange therebetween. In other aspects, the coating may be hydrophobic.

Throughout this disclosure, the coefficient of dynamic friction is measured according to ASTM D1894-14. In aspects, the third contact surface 125 of the second coating 123 can include the following coefficient of dynamic friction: about 0.1 or greater, about 0.3 or greater, about 0.4 or greater, about 0.8 or less, about 0.6 or less, or about 0.5 or less. In aspects, the third contact surface 125 of the second coating 123 can include a range of dynamic coefficients of friction as follows: about 0.1 to about 0.8, about 0.3 to about 0.6, about 0.4 to about 0.5, or any range or subrange therebetween.

In aspects, the coated article may further comprise additional coatings, including one or more of the following: an easy-to-clean coating, a low friction coating, an oleophobic coating, or a diamond-like coating. In other aspects, the additional coating may be disposed over the third contact surface of the second coating. In aspects, the low friction coating may include a highly fluorinated silane coupling agent, such as an alkylfluorosilane having an oxomethyl group side chain on the silicon atom. In such aspects, the easy-to-clean coating may comprise the same material as the low friction coating. In other aspects, the easy-to-clean coating may include a protonatable group, such as an amine, for example an alkylaminosilane having an oxomethyl group side chain on the silicon atom. In such aspects, the oleophobic coating can comprise the same material as the easy-to-clean coating. In aspects, the diamond-like coating comprises carbon and may be produced by applying a high voltage potential in the presence of a hydrocarbon plasma. In aspects, the second coating 123 can function as a scratch-resistant coating and/or a wear-resistant coating.

In aspects, the first coating 113, the second coating 123, the substrate 103 or 203, and/or the coated article 101 and/or 201 may be optically transparent. In aspects, the first coating 113, the second coating 123, the substrate 103 or 203, and/or the coated article 101 and/or 201 can be measured over a wavelength range from 400nm to 700nm including the following average transmittance: about 90% or greater, about 91% or greater, about 92% or greater, about 93% or greater, 100% or less, about 96% or less, about 95% or less, or about 94% or less. Throughout this disclosure, transmittance (and average transmittance) is measured according to ASTM C1649-14 (2021). The transmittance and haze values recorded herein were measured using an LAMBDA 650 spectrophotometer available from Perkin Elmer company. For the first coating 113, the second coating 123, and/or the substrate 103 or 203, the transmittance (e.g., average transmittance) is measured through a sheet of the corresponding material of 1.0 mm. In other aspects, the first coating 113, the second coating 123, the substrate 103 or 203, and/or the coated article 101 and/or 201 can be measured over an optical wavelength range of 400nm to 700nm including the following average transmittance ranges: about 90% to 100%, about 91% to about 96%, about 92% to about 95%, about 92% to about 94%, about 93% to about 94%, or any range or subrange therebetween. In aspects, the first coating 113 and/or the second coating 123 may be substantially free of crystals and/or air bubbles visible at 100 times magnification.

In aspects, the first coating 113, the second coating 123, the substrate 103 or 203, and/or the coated article 101 and/or 201 can include haze. As used herein, haze refers to the transmitted haze measured according to ASTM E430 with light incident directly on a surface (e.g., the third contact surface 125 of the second coating 123, the first contact surface 115 of the first coating 113, the first major surface 105 of the substrate 103 or 203, and/or the second major surface 107 of the substrate 103 or 203) in a direction normal to the corresponding surface. Haze was measured using an LAMBDA 650 spectrophotometer available from Perkin Elmer company with an aperture and hemispherical optical measurement system on the source port. The diameter of the aperture was 8mm. The coating and/or the coated article is irradiated using CIE C illuminant as light source. The haze of the coating was measured in such a way that the coating was mounted on a glass-based substrate comprising a thickness of 1.0 millimeter (mm). In other aspects, the haze of the first coating 113, the second coating 123, and/or the coated article 101 and/or 201 can be: about 0.01% or greater, about 0.1% or greater, about 0.2% or greater, about 1% or less, about 0.5% or less, about 0.4% or less, or about 0.3% or less. In other aspects, the haze of the first coating 113, the second coating 123, and/or the coated article 101 and/or 201 may be in the following range: about 0.01% to about 1%, about 0.01% to about 0.5%, about 0.1% to about 0.4%, about 0.1% to about 0.3%, about 0.2% to about 0.3%, or any range or subrange therebetween. Providing a low haze substrate may achieve good visibility through the substrate, the corresponding coating, and/or the coated article.

Throughout this disclosure, the refractive index is a function of the wavelength of light passing through the material. Throughout this disclosure, for light of a first wavelength, the refractive index of a material is defined as the ratio of the speed of light in a vacuum to the speed of light in the corresponding material. Without wishing to be bound by theory, the refractive index of a material may be determined using the ratio of the sin function of a first angle to the sin function of a second angle, wherein light of a first wavelength is incident from air onto a surface of the material at the first angle and is refracted at the surface of the material such that the light propagates in the material at the second angle. Both the first angle and the second angle are measured with respect to an angle normal to the surface of the material. As used herein, refractive index is measured according to ASTM E1967-19, wherein the first wavelength comprises 589nm. In an aspect, the refractive index of the first coating 113 may be: about 1.4 or greater, about 1.45 or greater, about 1.49 or greater, about 1.50 or greater, about 1.53 or greater, about 1.6 or less, about 1.55 or less, about 1.54 or less, or about 1.52 or less. In aspects, the refractive index of the first coating 113 may be in the following range: about 1.4 to about 1.6, about 1.45 to about 1.55, about 1.49 to about 1.54, about 1.50 to about 1.53, about 1.50 to about 1.52, or any range or subrange therebetween.

The substrate 103 or 203 may include a second refractive index. In aspects, the refractive index of the substrate 103 or 203 may be: about 1.4 or greater, about 1.45 or greater, about 1.49 or greater, about 1.50 or greater, about 1.53 or greater, about 1.6 or less, about 1.55 or less, about 1.54 or less, or about 1.52 or less. In aspects, the refractive index of the substrate 103 or 203 may be in the following range: about 1.4 to about 1.6, about 1.45 to about 1.55, about 1.49 to about 1.55, about 1.50 to about 1.54, about 1.50 to about 1.52, or any range or subrange therebetween. Throughout this disclosure, the magnitude of the difference between two values or the absolute difference between the two values is the absolute value of the difference between the two values. In aspects, the absolute difference between the first refractive index of the first coating 113 and the second refractive index of the substrate 103 or 203 may be: about 0.01 or less, about 0.008, about 0.005 or less, about 0.004 or less, about 0.001 or more, about 0.002 or more, or about 0.003. In aspects, the absolute difference between the first refractive index of the first coating 113 and the second refractive index of the substrate 103 or 203 may be in the following range: about 0.001 to about 0.01, about 0.002 to about 0.008, about 0.003 to about 0.005, about 0.003 to about 0.004, or any range or subrange therebetween. In aspects, the first refractive index may be greater than, less than, or equal to the second refractive index.

The second coating 123 may include a third refractive index. In aspects, the third refractive index of the second coating 123 can be in one or more of the ranges discussed above with respect to the first refractive index of the first coating 113. In an aspect, the third refractive index may be substantially equal to the first refractive index. In an aspect, an absolute difference between the first refractive index of the first coating layer 113 and the third refractive index of the second coating layer 123 may be: about 0.01 or less, about 0.008, about 0.005 or less, about 0.004 or less, about 0.001 or more, about 0.002 or more, or about 0.003. In aspects, the absolute difference between the first refractive index of the first coating layer 113 and the third refractive index of the second coating layer 123 may be in the following range: about 0.001 to about 0.01, about 0.002 to about 0.008, about 0.003 to about 0.005, about 0.003 to about 0.004, or any range or subrange therebetween. In aspects, the second refractive index may be greater than, less than, or equal to the third refractive index. In aspects, the absolute difference between the second refractive index of the substrate 103 or 203 and the third refractive index of the second coating 123 may be: about 0.01 or less, about 0.008, about 0.005 or less, about 0.004 or less, about 0.001 or more, about 0.002 or more, or about 0.003. In aspects, the absolute difference between the second refractive index of the substrate 103 or 203 and the third refractive index of the second coating layer 123 may be in the following range: about 0.001 to about 0.01, about 0.002 to about 0.008, about 0.003 to about 0.005, about 0.003 to about 0.004, or any range or subrange therebetween. In aspects, the first refractive index may be greater than, less than, or equal to the third refractive index.

As used herein, the hardness (e.g., pencil hardness) of the coated article 101 and/or 201 is measured on the third contact surface 125 of the second coating 123. As used herein, the properties of a "as-formed" material refer to the relative humidity that has not been subjected to a modification temperature (e.g., falling outside a temperature range of about 10 ℃ to about 30 ℃) or an elevation (e.g., greater than 60% relative humidity) after the material is formed (e.g., cured). In aspects, the pencil hardness of the coated article 101 and/or 201 and/or the second coating 123 measured in the as-formed state (i.e., the as-formed pencil hardness) can be: about 2H or greater, about 3H or greater, about 4H or greater, about 5H or greater, about 6H or greater, about 7H or greater, about 8H or greater, or about 9H or greater. In aspects, the pencil hardness of the coated article 101 and/or 201 and/or the second coating 123 measured in the as-formed state (i.e., the as-formed pencil hardness) can be in the following range: about 3H to about 9H, about 4H to about 9H, about 5H to about 8H, about 6H to about 7H, or any range or subrange therebetween.

In aspects, the pencil hardness of the coated article 101 and/or 201 and/or second coating 123 measured after the corresponding coated article and/or second coating is maintained in an 85% relative humidity, 85 ℃ environment for 16 hours may be: about 2H or greater, about 3H or greater, about 4H or greater, about 5H or greater, about 6H or greater, about 7H or greater, about 8H or greater, or about 9H or greater. In aspects, the pencil hardness of the coated article 101 and/or 201 and/or second coating 123 measured after the corresponding coating and/or second coating is maintained in an 85% relative humidity, 85 ℃ environment for 16 hours may be in the following range: about 4H to about 9H, about 5H to about 8H, about 6H to about 7H, or any range or subrange therebetween.

The first coating 113 may include adhesion to the substrate 103 or 203. Throughout this disclosure, adhesion of the coating to the substrate can be measured using a cross-hatch adhesion test according to ASTM D3359-09 method B, using a cross-hatch paint adhesion test kit purchased from Gardco corporation. In aspects, the first coating 113 (e.g., of the coated article 101 and/or 201) can include an adhesion to the as-formed state of the substrate 103 or 203 of 1B or higher, 2B or higher, 3B or higher, 4B or higher, 5B or higher, 6B or higher. In aspects, the first coating 113 can include the following ranges of adhesion to the as-formed state of the substrate 103 or 203: 1B to 6B,2B to 6B,3B to 6B,4B to 5B, or any range or subrange therebetween. In aspects, the as-formed adhesion between the first coating 113 and the second coating 123 may be greater than the as-formed adhesion between the first coating 113 and the substrate 103 or 203.

In aspects, the adhesion between the first coating 113 of the coated article 101 or 201 and the substrate 103 or 203, measured after the corresponding coated article is maintained in an 85% relative humidity, 85 ℃ environment for 16 hours, may be: 0B or higher, 1B or higher, 2B or higher, 3B or higher, 4B or higher, 5B or higher, 6B or higher. In aspects, the adhesion between the first coating 113 of the coated article 101 or 201 and the substrate 103 or 203 measured after the corresponding coated article is maintained in an 85% relative humidity, 85 ℃ environment for 16 hours may be in the following range: 0B to 6B,1B to 5B,2B to 4B,3B to 4B, or any range or subrange therebetween.

In aspects, the coated article 101 and/or 201 can withstand a 85 ℃ environment of 85% relative humidity for 16 hours without visually visible delamination or visually visible cracking. As used herein, "visually visible delamination" refers to separation (e.g., bubbling, lifting, curling) of a coating from a substrate or from another coating that is visible to the naked eye. As used herein, "visually visible cracking" refers to cracking (e.g., breaking, cracking, separating into pieces) of a coating that is visible to the naked eye.

In aspects, the substrate 103 or 203 can comprise a glass-based substrate or a ceramic-based substrate, wherein one or more portions of the substrate can comprise a compressive stress region. In aspects, the compressive stress region may be created by chemically strengthening the substrate. Chemical strengthening may include an ion exchange process in which ions in the surface layer are replaced or exchanged with larger ions having the same valence or oxidation state. Without wishing to be bound by theory, chemical strengthening of the substrate may achieve a small (e.g., less than about 10mm or less) parallel plate spacing because compressive stress from the chemical strengthening may counteract bending-induced tensile stress on the outermost surface of the substrate (e.g., first major surface 205 in fig. 4). The compressive stress region may extend into a portion of the substrate to a depth known as the compression depth. As used herein, the depth of compression refers to the depth at which the stress in the chemically strengthened substrate described herein changes from compressive to tensile. The depth of compression (SCALP) can be measured by a surface stress meter or a scattered light polarizer, depending on the ion exchange treatment and thickness of the article being measured, wherein the values recorded herein are obtained using SCALP-5 manufactured by Edania glass company. When stress is generated in the substrate by exchanging potassium ions into the substrate, a surface stress meter (for example, FSM-6000 (the folding industry limited company (japan)) is used to measure the compression depth. Compressive stress (including surface CS) is measured by a surface stress meter (FSM) using, for example, a commercial instrument manufactured by the folding company, such as FSM-6000, unless otherwise specified. Surface stress measurement relies on accurate measurement of Stress Optical Coefficient (SOC), which is related to the birefringence of glass. The SOC was measured according to protocol C (method for glass discs) described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient (Standard test method for measuring glass stress-optical coefficient)", which is incorporated herein by reference in its entirety, unless otherwise indicated. When stress is generated by exchanging sodium ions into the substrate and the measured article is thicker than about 75 μm, the depth of compression and Center Tension (CT) are measured using SCALP. Depth of compression and CT were measured by SCALP when stress was created in the substrate by exchanging both potassium and sodium ions into the glass and the measured article was thicker than about 75 μm. Without wishing to be bound by theory, the exchange depth of sodium may represent the compression depth, while the exchange depth of potassium ions may represent the change in the magnitude of the compressive stress (but not the change in stress from compression to tension). A refractive near field (RNF; RNF method) described in U.S. patent No. 8,854,623 entitled "Systems and methods for measuring a profile characteristic of a glass sample (system and method for measuring distribution characteristics of glass samples)" can also be used to obtain a graph representing stress distribution. When the RNF method is used to obtain a graph representing the stress distribution, the maximum central tension value provided by the SCALP is used in the RNF method. The graph representing stress distribution obtained by RNF is force balanced and calibrated with the maximum center tension value provided by the SCALP measurement. As used herein, "depth of layer" (DOL) refers to the depth of ion (e.g., sodium, potassium) exchange into a substrate. In the present disclosure, when the center tension cannot be directly measured by the SCALP (when the article being measured is thinner than about 75 μm), the maximum center tension can be approximated by dividing the product of the maximum compressive stress and the compressive depth by the difference between the substrate thickness and twice the compressive stress, where the compressive stress and the compressive depth are measured by the FSM.

In aspects, the substrate 103 or 203 can be chemically strengthened to form a first compressive stress region extending from the first major surface 105 or 205 to a first compressive depth. In aspects, the substrate 103 or 203 can be chemically strengthened to form a second compressive stress region extending from the second major surface 107 or 207 to a second compressive depth. In other aspects, the first compressive stress region and/or the second compressive stress region may include a plurality of ion-exchanged metal ions that generate compressive stress in the corresponding compressive stress region. In other aspects, the first depth of compression (e.g., from the first major surface 105) and/or the second depth of compression (e.g., from the second major surface 107) may be, in percent of the substrate thickness 109 or 222: about 1% or greater, about 5% or greater, about 10% or greater, about 30% or less, about 25% or less, or about 20% or less. In other aspects, the first compression depth and/or the second compression depth may be in the following ranges, as a percentage of the substrate thickness 109 or 222: about 1% to about 30%, about 5% to about 25%, about 10% to about 20%, or any range or subrange therebetween. In aspects, the first compression depth and/or the second compression depth may be: about 1 μm or greater, about 10 μm or greater, about 50 μm or greater, about 200 μm or less, about 150 μm or less, or about 100 μm or less. In some embodiments, the first compression depth and/or the second compression depth may be in the following ranges: about 1 μm to about 200 μm, about 10 μm to about 150 μm, about 50 μm to about 100 μm, or any range or subrange therebetween. In aspects, the first compression depth may be greater than, less than, or substantially equal to the second compression depth. By providing a glass-based substrate and/or a ceramic-based substrate comprising a first depth of compression and/or a second depth of compression in the range of about 1% to about 30% of the first thickness, good impact resistance and/or good puncture resistance may be achieved.

In aspects, the substrate 103 or 203 can include a first depth of layer of one or more alkali metal ions associated with a first compressive stress region and/or a second depth of layer of one or more alkali metal ions associated with a second compressive stress region. In aspects, the first layer depth and/or the second layer depth may be, in percent of the substrate thickness 109 or 222: about 1% or greater, about 5% or greater, about 10% or greater, about 15% or greater, about 20% or greater, about 35% or less, about 30% or less, about 25% or less, or about 22% or less. In aspects, the first layer depth and/or the second layer depth may be in the following ranges, as a percentage of the substrate thickness 109 or 222: about 1% to about 35%, about 5% to about 30%, about 10% to about 25%, about 15% to about 22%, about 20% to about 22, or any range or subrange therebetween. In aspects, the first layer depth and/or the second layer depth may be: about 1 μm or greater, about 10 μm or greater, about 50 μm or greater, about 200 μm or less, about 150 μm or less, or about 100 μm or less. In aspects, the first layer depth and/or the second layer depth may be in the following ranges: about 1 μm to about 200 μm, about 10 μm to about 150 μm, about 50 μm to about 100 μm, or any range or subrange therebetween.

In an aspect, the first compressive stress region may include a maximum first compressive stress. In an aspect, the second compressive stress region may include a maximum second compressive stress. In other aspects, the maximum first compressive stress and/or the maximum second compressive stress may be: about 300 megapascals (MPa) or greater, about 400MPa or greater, about 500MPa or greater, about 700MPa or greater, about 1,500MPa or less, about 1,200MPa or less, about 1,000MPa or less, or about 900MPa or less. In other aspects, the maximum first compressive stress and/or the maximum second compressive stress may be in the following ranges: about 300MPa to about 1,500MPa, about 400MPa to about 1,200MPa, about 500MPa to about 1,000MPa, about 700MPa to about 900MPa, or any range or subrange therebetween. Providing a maximum first compressive stress and/or a maximum second compressive stress in the range of about 300MPa to about 1500MPa (or about 400MPa or greater) may achieve good impact and/or puncture resistance.

In aspects, the first compressive stress region may extend from the first surface region 225 of the first portion 223 and/or the third surface region 235 of the second portion 233, which may include the first compressive depth, the first depth of layer, and/or the maximum first compressive stress as discussed above. In aspects, the second compressive stress region may extend from the second surface region 227 of the first portion 223 and/or the fourth surface region 237 of the second portion 233, which may include the second depth of compression, the second depth of layer, and/or the maximum second compressive stress as discussed above. In aspects, the central portion 281 may be chemically strengthened to form a first central compressive stress region extending from the first central surface region 215 to a first compressive depth and/or a second central compressive stress region extending from the second central surface region 217 to a second compressive depth. In other aspects, the first center depth of compression as a percentage of the center thickness 212 and/or the second center depth of compression as a percentage of the center thickness 212 may be within one or more of the ranges of the first depth of compression and/or the second depth of compression as a percentage of the substrate thickness discussed above. In other aspects, the first central compressive stress region may include a first central layer depth of one or more alkali metal ions associated with the first central compressive stress region, and/or the second central compressive stress region may include a second central layer depth of one or more alkali metal ions associated with the second central compressive stress region. In other aspects, the first center layer depth as a percentage of the center thickness 212 and/or the second center layer depth as a percentage of the center thickness 212 may be within one or more of the ranges of the first layer depth and/or the second layer depth as a percentage of the substrate thickness discussed above. In even other aspects, the first central compressive stress region may comprise a maximum first central compressive stress and/or the second central compressive stress region may comprise a maximum second central compressive stress, which may be within one or more of the ranges discussed above with respect to the maximum first compressive stress and/or the maximum second compressive stress.

In other aspects, the central tension region may include a maximum central tensile stress. In aspects, the maximum central tensile stress may be: about 50MPa or more, about 100MPa or more, about 200MPa or more, about 250MPa or more, about 750MPa or less, about 600MPa or less, about 500MPa or less, about 450MPa or less, about 400MPa or less, about 350MPa or less, or about 300MPa or less. In aspects, the maximum central tensile stress may be in the following range: about 50MPa to about 750MPa, about 50MPa to about 600MPa, about 100MPa to about 500MPa, about 200MPa to about 450MPa, about 250MPa to about 350MPa, about 250MPa to about 300MPa, or any range or subrange therebetween.

In aspects, the coated article 101 or 201 can be folded about the folding axis 102 in the direction 108 (e.g., see fig. 1-2) to form the coated article 301 in a folded configuration (e.g., see fig. 3-4). As shown, the coated article may include a single fold axis to allow the coated article to include a double fold (bifold), wherein, for example, the coated article may be folded in half. In other aspects, the coated article may include two or more fold axes, which may allow the coated article to include a tri-fold or other multi-fold structure.

Fig. 3-4 schematically illustrate exemplary aspects of a coated article 301 in a folded configuration in accordance with aspects of the present disclosure. As shown in fig. 4, the second major surface 207 of the substrate 203 is on the inside of the bend and the second coating 123 is on the outside of the bend, for example by causing the coated article 201 as shown in fig. 2 to fold in direction 108. If the display device is mounted on the second major surface 107 or 207 of the substrate 103, the user will view the device containing the coated article through the second coating 123, the first coating 113, and the substrate 103 or 203, and will thus view from the side of the first major surface 105 of the substrate 103 (e.g., from the side of the first contact surface 115 of the first coating 113, from the side of the third contact surface 125 of the second coating 123). Alternatively, the display device may be mounted on the third contact surface of the second coating such that the display device faces the first major surface and/or the first central surface area; the user will view the device containing the coated article through the second coating, the first coating, and the substrate, and will thus view from the side of the second major surface of the substrate. Although not shown, as discussed above, there may be a second recess opposite the first recess such that the second central surface region is recessed from the second major surface rather than being coplanar with the second major surface. Although not shown, as discussed above, the second central surface region may define a recess from the second major surface recess, while there may be no recess as shown in fig. 2 and 4.

Although not shown, the coated article may be folded such that the second coating 123 is on the inside of the folded coated article while the second major surface 107 or 207 of the substrate 103 or 203 is on the outside of the folded coated article. Likewise, if the display device is mounted on the second major surface 107 or 207 of the substrate 103, the user will view the device containing the coated article through the second coating 123, the first coating 113, and the substrate 103 or 203, and will thus view from the side of the first major surface 105 of the substrate 103 (e.g., from the side of the first contact surface 115 of the first coating 113, from the side of the third contact surface 125 of the second coating 123). Although not shown, as discussed above, there may be a second recess opposite the first recess such that the second central surface region is recessed from the second major surface rather than being coplanar with the second major surface. Although not shown, as discussed above, the second central surface region may define a recess from the second major surface recess, while there may be no recess as shown in fig. 2 and 4.

As used herein, "foldable" includes fully folded, partially folded, bent, folded, or multi-folded functions. As used herein, the terms "failure" and the like refer to cracking, breaking, delamination, or crack propagation. A foldable substrate (e.g., substrate, coating, coated article) achieves or has a parallel plate spacing "X" if it resists failure when the substrate is held at the parallel plate spacing "X" for 24 hours at about 60 ℃ and about 90% relative humidity.

As used herein, a parallel plate apparatus 401 (see fig. 4) is employed to measure the "parallel plate spacing" of a foldable substrate (e.g., substrate 103 or 203, first coating 113, second coating 123, coated article 101 or 201) in a test configuration and procedure as follows, the parallel plate apparatus 401 (see fig. 4) comprising a pair of parallel rigid stainless steel plates 403 and 405 comprising a first rigid stainless steel plate 403 and a second rigid stainless steel plate 405. When measuring the "parallel plate spacing" of the coated article 301 (as shown in fig. 4), the coated article 301 is placed between a pair of parallel rigid stainless steel plates 403 and 405 such that the second coating 123 (e.g., the third contact surface 125) is on the outside of the bend (e.g., facing and/or contacting the stainless steel plates 403 and 405) while the substrate 103 or 203 (e.g., the second major surface 107) is on the inside of the bend (e.g., facing itself). The spacing between the parallel plates is reduced at a rate of 50 μm/sec until the parallel plate spacing 407 is equal to the "parallel plate spacing" to be tested. The parallel plates were then maintained at the "parallel plate spacing" to be tested for 24 hours at about 60 ℃ and about 90% relative humidity. As used herein, a "minimum parallel plate spacing" is the minimum parallel plate spacing that a foldable substrate (e.g., substrate 103 or 203, first coating 113, second coating 123, coated article 101 or 201) can withstand without failure under the conditions and configurations described above.

In aspects, the coated article 101 or 201, the first coating 113, and/or the second coating 123 can achieve the following parallel plate spacing: 100mm or less, 50mm or less, 20mm or less, or 10mm or less. In other aspects, the coated article 101 or 201, the first coating 113, and/or the second coating 123 can achieve the following parallel plate spacing: 10 millimeters (mm), or 7mm, or 5mm, 4mm, 3mm, 2mm, or 1mm. In aspects, the coated article 101 or 201, the first coating 113, and/or the second coating 123 can include the following parallel plate spacing: about 10mm or less, about 7mm or less, about 5mm or less, about 4mm or less, about 1mm or more, about 2mm or more, or about 3mm or more. In aspects, the coated article 101 or 201, the first coating 113, and/or the second coating 123 can include the following parallel plate spacing ranges: about 1mm to about 10mm, about 2mm to about 10mm, about 3mm to about 7mm, about 3mm to about 5mm, about 3mm to about 4mm, or any range or subrange therebetween.

In aspects, the coated article 101 or 201 can withstand cyclic bending testing. As used herein, cyclic bending test includes: the test apparatus containing the material to be tested is placed in a parallel plate apparatus 401 (see fig. 4) and the coated article containing the coating is bent (as described above for the parallel plate test of the coated article 101 or 201) to achieve a predetermined parallel plate spacing between the stainless steel plates 403, 405, a predetermined number of times at 23 ℃ at 50% relative humidity. In aspects, the coated article 101 or 201 can withstand 2000 bending cycles at a parallel plate spacing of 3 millimeters. In other aspects, the coated article 101 or 201 can withstand 20,000 bending cycles at a parallel plate spacing of 3 millimeters. In even other aspects, the coated article 101 or 201 withstands 200,000 bending cycles at a parallel plate spacing of 3 millimeters. In aspects, the coated article 101 or 201 can withstand 2000 bending cycles at a parallel plate spacing of 4 millimeters. In other aspects, the coated article 101 or 201 can withstand 20,000 bending cycles at a parallel plate spacing of 4 millimeters. In even other aspects, the coated article 101 or 201 withstands 200,000 bending cycles at a parallel plate spacing of 4 millimeters.

The coated article may have an impact resistance defined by the ability of the second coating 123 to bond with the first coating 113 and/or the coated article 101 or 201, thereby avoiding failure at a drop height (e.g., 5 centimeters (cm) or greater, 8cm or greater, 10cm or greater, 12cm or greater, 15cm or greater) when measured according to the "drop test". As used herein, the "pen down test" is performed such that a sample of the coated article is tested in the following manner: the load (i.e., the pen falling from a certain height) is impacted against the outer surface of the coating and/or coated article (e.g., the third contact surface 125 of the second coating 123 in fig. 1-2) as constructed in the parallel plate test. During the test, the laminate containing the coated article 101 or 201 was placed on an aluminum plate (6063 aluminum alloy, surface roughness polished with 400 sandpaper). No strip was used on the side of the sample on the aluminum plate.

In the pen down test, the pen used was BIC Easy Glide Pen, fine (thin nib, easy-to-slide pen), containing a tungsten carbide ball tip of 0.7mm (0.68 mm) diameter, including a cap weighing 5.73 grams (g). The ballpoint pen is maintained at a predetermined height relative to the outer surface of the coated and/or coated laminate (e.g., the third contact surface 125 of the second coating 123 in fig. 1-2). The pen down test uses a catheter to guide a ballpoint pen to the outer surface of the coated article and places the catheter in contact with the outer surface of the coated article such that the longitudinal axis of the catheter is substantially perpendicular to the outer surface of the coated article. The catheter had an outer diameter of 1 inch (2.54 cm), an inner diameter of 9/16 inch (1.4 cm), and a length of 90 cm. For each test, an acrylonitrile butadiene ("ABS") spacer was used to maintain the ballpoint pen at a predetermined height. After each drop, the catheter is repositioned relative to the outer surface of the sample to be tested, thereby directing the ballpoint pen to a different impact location on the outer surface of the sample to be tested. It is to be understood that the pen down test can be used with any coating and/or coated article of aspects of the present disclosure.

For the pen down test, the ballpoint pen is caused to fall with the pen cap attached to the top end (i.e., the end opposite the nib) so that the ball point can interact with the outer surface of the coating (e.g., the third contact surface 125 of the second coating 123 in fig. 1-2). In the drop sequence according to the drop test, one drop is made at an initial height of 1cm, followed by successive drops in 0.5cm increments (up to 20 cm), and then after 20cm, in 2cm increments until the sample to be tested fails. After each drop, any observable evidence of cracking, failure, or other damage to the coated article present, as well as the specific predetermined height of the pen down, is recorded. Using the pen down test, multiple samples can be tested according to the same drop sequence to produce a set with improved statistical accuracy. For the pen down test, the ballpoint pen was replaced with a new pen after each five drops and for each new coated article to be tested. Furthermore, unless otherwise indicated, all strokes were performed at random locations at or near the center of the coated article, and no strokes were performed at or on the edges of the coated article.

For the purposes of the pen down test, "failure" refers to the formation of a visible mechanical defect in the sample. The mechanical defect may be a crack or plastic deformation (e.g., surface indentation). The crack may be a surface crack or a through crack. Cracks may form on the inner or outer surface of the sample. The crack may extend through all or a portion of the second coating 123, the first coating 113, and/or the coated article 101 or 201. The visible mechanical defect has a minimum size of 0.2 mm or more. As used herein, the pen-down threshold height corresponds to the maximum pen-down height at which the coated article can withstand without failure. In aspects, the first coating 113 and/or the coated article 101 or 201 can withstand (for the coated article) the following drop heights above the third contact surface 125 of the second coating 123: 1cm or higher, 3cm or higher, 5cm or higher, 7cm or higher, 8cm or higher, 9cm or higher, 10cm or higher, 11cm or higher, 12cm or higher, 13cm or higher, 14cm or higher, 15cm or higher, 16cm or higher, 17cm or higher, 18cm or higher, 19cm or higher, and/or 20cm.

For a coated article comprising one or more depressions (e.g., depressions 211), for a coated article comprising a substrate thickness of 30 μm or greater, the coated article 201 can withstand the following drop heights on the portion of the third contact surface 125 corresponding to the depressions 211: 3cm or higher, 5cm or higher, 8cm or higher, 10cm or higher, 12cm or higher, 13cm or higher, 14cm or higher, 15cm or higher, 16cm or higher, 17cm or higher, or 20cm or higher. For a coated article comprising one or more depressions (e.g., similar to fig. 2), for a substrate thickness of 30 μm or greater, the coated article can withstand the following drop heights on portions of the third contact surface 125 (e.g., the first portion 223, the second portion 233) that do not correspond to the depressions: 3cm or more, 5cm or more, 8cm or more, 10cm or more, or 15cm or more.

In an aspect, the first pen down threshold height of the coated article 101 or 201 above the third contact surface 125 of the second coating 123 can be: about 3cm or more, about 5cm or more, about 8cm or more, about 10cm or more, about 12cm or more, about 15cm or more, or about 17cm or more. In other aspects, the first pen-down threshold height will be greater than the second pen-down threshold height of another substrate without a coating (e.g., first coating 113, second coating 123) consistent with substrate 103 or 203. In even other aspects, the first pen-down threshold height will be about 3cm or more, about 5cm or more, about 6cm or more, about 7cm or more, about 8cm or more, about 9cm or more, or about 10cm or more greater than the second pen-down threshold height.

Aspects of the present disclosure may include consumer electronics. The consumer electronic product may include a front surface, a back surface, and side surfaces. The consumer electronic product may also include an electronic component at least partially within the housing. The electronic components may include a controller, a memory, and a display. The display may be located on or adjacent to the front surface of the housing. The consumer electronic product may include a cover substrate disposed over the display. In aspects, at least one of the housing or the cover substrate includes a coated article as discussed throughout this disclosure. The display may include: a Liquid Crystal Display (LCD), an electrophoretic display (EPD), an Organic Light Emitting Diode (OLED) display, or a Plasma Display Panel (PDP). In aspects, the consumer electronic product may be a portable electronic product, such as: smart phones, tablets, wearable devices, or notebook computers.

The coated articles and/or coatings disclosed herein can be incorporated into another article, such as an article (or display article) having a display screen (e.g., consumer electronics products including mobile phones, tablets, computers, navigation systems, and wearable devices (e.g., watches), etc.), architectural articles, transportation articles (e.g., vehicles, trains, aircraft, marine vessels, etc.), electrical articles, or any article that can benefit from partial transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles incorporating any of the coated articles as disclosed herein are shown in fig. 5 and 6. In particular, fig. 5 and 6 show a consumer electronic device 500 that includes a housing 502 having a front surface 504, a back surface 506, and side surfaces 508. The consumer electronic device 500 may comprise: an electronic assembly (not shown) located at least partially or entirely within the housing, the electronic assembly including at least a controller, a memory, and a display 510 located at or adjacent a front surface of the housing. The consumer electronic device 500 may include a cover substrate 512 positioned at or above the front surface of the housing so as to be positioned above the display. In aspects, at least one of the housing 502 covering the substrate 512 or a portion thereof may comprise any of the coated articles disclosed herein.

Method aspects of manufacturing a coated article 101 or 201 according to aspects of the present disclosure will be discussed with reference to the flowchart in fig. 7 and the exemplary method steps shown in fig. 8-13. Although fig. 8-13 show a substrate 203, it is to be understood that the exemplary method steps may be applicable to other substrate scenarios (e.g., substrate 103 as shown in fig. 1). Referring to the flowchart of fig. 7, the method may begin at step 701. In aspects, step 701 may include providing a substrate. In other aspects, the substrate may be similar to substrate 103 of fig. 1 including substrate thickness 109 or substrate 203 of fig. 2 including substrate thickness 222. In other aspects, the substrate 103 or 203 may be provided by purchasing or any other means to obtain the substrate or by forming the substrate. In other aspects, the substrate may include a glass-based and/or ceramic-based substrate. In other aspects, the glass-based substrate may be provided by forming through various ribbon forming processes, such as: slit drawing, down drawing, fusion down drawing, up drawing, nip roll, redraw or float. In even other aspects, the substrate may be chemically strengthened and include a compression depth (e.g., first compression depth, second compression depth), a compression stress (e.g., first maximum compression stress, second maximum compression stress), and/or a layer depth (e.g., first layer depth, second layer depth) that fall within one or more of the corresponding ranges discussed above.

After step 701, as shown in fig. 8, the method may proceed to step 703, where a first liquid 803 is disposed on the first major surface 205 of the substrate 203. In aspects, as shown, disposing the first liquid 803 may include dispensing the first liquid 803 from a container 801 (e.g., a tube, flexible conduit, micropipette, or syringe). In aspects, as shown, the first liquid 803 can also be disposed on the first central surface region 215. In other aspects, as shown, the first liquid 803 can occupy and/or fill the recess 211. In other aspects, although not shown, disposing the first liquid 803 may also include pulling the applicator over the free surface of the first liquid 803 to achieve a uniform free surface corresponding to the uniform first contact surface 115 (see fig. 1-2). In other aspects, although not shown, depositing the first liquid 803 may include using a blade (e.g., a scalpel or a roller coated blade) to achieve a predetermined thickness. The first liquid 803 may conform to the contours of the transition surface region as well as other details of the substrate.

In aspects, the first liquid 803 can include a cycloaliphatic epoxide. In other aspects, the cycloaliphatic epoxide may comprise the following weight percent (wt%) of the first liquid 803: 0 wt% or more, about 2 wt% or more, about 4 wt% or more, about 60 wt% or more, about 70 wt% or more, about 80 wt% or more, about 85 wt% or more, 100 wt% or less, about 95 wt% or less, about 90 wt% or less, about 10 wt% or less, or about 8 wt% or less, or about 6 wt% or less. In other aspects, the wt% of cycloaliphatic epoxide in the first liquid 803 can be in the following range: 0 wt% to 100%,0 wt% to about 80 wt%, 0 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 4 wt% to about 6 wt%, or any range or subrange therebetween. In other aspects, the weight% of cycloaliphatic epoxide in the first liquid 803 can be about 60 weight% or more, for example, in the following ranges: about 60 wt% to 100 wt%, about 70 wt% to 100 wt%, about 80 wt% to about 95 wt%, about 85 wt% to about 90 wt%, or any range or subrange therebetween. An exemplary aspect of the cycloaliphatic epoxide in the first liquid 803 is 4-epoxycyclohexyl carboxylate (e.g., celloxide 2021P (available from Daicel corporation)).

In aspects, the first liquid 803 can include a POSS (e.g., GPOSS), which can include a glycidol functional group. In aspects, POSS (e.g., GPOSS) can comprise the following weight percent of the first liquid 803: 0 wt% or more, about 5 wt% or more, about 10 wt% or more, about 60 wt% or more, about 65 wt% or more, about 70 wt% or more, 100 wt% or less, about 90 wt% or less, about 80 wt% or less, about 75 wt% or less, about 20 wt% or less, or about 15 wt% or less. In aspects, the weight% of POSS (e.g., GPOSS) in the first liquid 803 can be in the following range: from 0 wt% to 100 wt%, from 0 wt% to about 90 wt%, from 0 wt% to about 80 wt%, from 0 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 10 wt%, or any range or subrange therebetween. In aspects, the weight% of POSS (e.g., GPOSS) in the first liquid 803 can be about 60 weight% or more, e.g., in the following ranges: about 60 wt% to 100 wt%, about 60 wt% to about 90 wt%, about 60 wt% to about 80 wt%, about 65 wt% to about 75 wt%, about 70 wt% to about 75 wt%, or any range or subrange therebetween.

In aspects, the first liquid 803 can comprise an amine-containing polymer. In other aspects, the amine-containing polymer may be a polymer in which one or more ends of the polymer have amine functionality. In even other aspects, the amine functionality at one or more ends of the polymer may be different from the normal end functionality of the polymer. Throughout this disclosure, the "normal terminal functional group" of a polymer refers to a functional group that may be present at the end of the polymer during the polymerization process. For example, the normal terminal functional group of the polyethylene would be an olefin (e.g., allyl), the normal terminal functional group of the polyamide would be an amine and/or carboxylic acid, and the normal terminal functional group of the poly (dimethylsiloxane) would be a silane. In aspects, the amine-containing polymer can be a siloxane (e.g., a polysiloxane). In aspects, the first functional group and/or the second functional group may be the same as the functional group at the normal end of the polymer. In aspects, the first functional group and/or the second functional group may be different from the normal terminal functional group of the polymer. In other aspects, the first functional group may be different from the normal terminal functional group of the polymer, and the second functional group may be different from the normal terminal functional group of the polymer. For example, the polymer may be poly (dimethylsiloxane) having a first functional group comprising an amine and a second functional group comprising an amine. Exemplary aspects of polymers having amine functionality at one or more ends of the polymer include: poly (dimethylsiloxane) having amine functionality at its ends (e.g., DMS-a11 from Gelest corporation) and poly (oxypropylene) having amine functionality at its ends (e.g., jeffamine D-400, jeffamine D-2000, jeffamine T-403, etc. from Huntsman corporation). In even other aspects, the normal terminal functional group of the amine-containing polymer can be an amine. In other aspects, the amine-containing polymer can be, based on the weight% of the first liquid 803: 0 wt% or more, about 20 wt% or more, about 22 wt% or more, about 35 wt% or less, about 30 wt% or less, or about 27 wt% or less. In other aspects, the amine-containing polymer can be in the following range, expressed as weight% of the first liquid 803: 0 wt% to about 35 wt%, about 20 wt% to about 30 wt%, about 22 wt% to about 27 wt%, or any range or subrange therebetween.

In aspects, the first liquid 803 can include a curing catalyst. As used herein, a curing catalyst refers to a compound that contains nitrogen bonded to two or more non-hydrogen atoms and that is incapable of functioning as a linking agent. In other aspects, the curing catalyst may include: secondary amines, tertiary amines, pyridines and/or imidazoles. Exemplary aspects of tertiary amines include: 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylamine, tetramethylguanidine, and 2,4, 6-tris (dimethylaminomethyl) phenol. In other aspects, the composition may comprise a curing catalyst in the following amounts: 0 wt% or more, about 0.3 wt% or more, about 0.5 wt% or more, about 0.7 wt% or more, about 2 wt% or more, about 1.1 wt% or less, about 1 wt% or less, or about 0.8 wt% or less. In other aspects, the composition may include a curing catalyst in the following ranges: from 0 wt% to about 2 wt%, from about 0.3 wt% to about 1.1 wt%, from about 0.3 wt% to about 1 wt%, from about 0.5 wt% to about 0.8 wt%, from about 0.7 wt% to about 0.8 wt%, or any range or subrange therebetween. Without wishing to be bound by theory, the curing catalyst may improve properties (e.g., hardness, adhesion, pencil hardness) of the coating (wherein the first and/or second functional groups of the linking agent comprise amine functional groups). In aspects, the first liquid 803 can be substantially free of amine and/or free of amine.

In aspects, the first liquid 803 can include an oxetane (i.e., an oxetane-containing molecule). An exemplary aspect of the oxetane-containing molecule can be TMPO. In other aspects, the oxetane-containing molecules can be, based on weight% of the first liquid 803: 0 wt% or more, about 2 wt% or more, about 4 wt% or more, about 6 wt% or more, about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, or about 8 wt% or less. In other aspects, the oxetane-containing molecules can be in the following range, based on the weight% of the first liquid 803: from 0 wt% to about 20 wt%, from about 2 wt% to about 15 wt%, from about 4 wt% to about 10 wt%, from about 6 wt% to about 8 wt%, or any range or subrange therebetween. In aspects, the first liquid 803 may be substantially free of oxetane-containing molecules and/or may be free of oxetane-containing molecules, such as when the first liquid 803 comprises an amine-containing polymer.

In aspects, the first liquid 803 can include a photoinitiator. In other aspects, the photoinitiator may be in weight percent of the first liquid 803: 0 wt% or more, about 0.1 wt% or more, about 0.2 wt% or more, about 0.5 wt% or more, about 5 wt% or less, about 4 wt% or less, about 2 wt% or less, about 1.5 wt% or less, or about 1 wt% or less. In other aspects, the photoinitiator may be in the following range, expressed as weight% of the first liquid 803: from 0 wt% to about 5 wt%, from about 0.1 wt% to about 4 wt%, from about 0.2 wt% to about 2 wt%, from about 0.2 wt% to about 1.5 wt%, from about 0.5 wt% to about 1 wt%, or any range or subrange therebetween. In aspects, the first liquid 803 may be substantially free of photoinitiator and/or may be free of photoinitiator, such as when the first liquid 803 is cured by heating.

In aspects, the first coating 803 may be substantially free of solvent. As used herein, the first liquid 803 is "substantially solvent free" or "substantially solvent free" if it contains 2 wt% or less solvent. As used herein, a liquid is "solvent-free" or "solvent-free" if it contains 0.5 wt% or less solvent. As used herein, "solvent" excludes the components discussed above, for example: functionalized oligomeric silsesquioxanes, cycloaliphatic epoxides, oxetane-containing molecules, catalysts (e.g., curing catalysts), photoinitiators, amine-containing polymers, combinations thereof, and/or products thereof. Providing a substantially solvent-free or substantially solvent-free liquid may increase its cure rate, which may reduce processing time. Furthermore, providing a substantially solvent-free or solvent-free composition may reduce (e.g., reduce, eliminate) the use of rheology modifiers and increase the compositional homogeneity, which may increase the optical clarity (e.g., transmittance) of the resulting coating. Furthermore, the solvent-free composition may reduce the incidence of visually observable defects (e.g., bubbles from volatile gases due to any solvent evaporation) in the resulting coating. In aspects, the first liquid 803 may be substantially free of nanoparticles (e.g., silica nanoparticles).

Examples M-S presented in Table 2 apply to exemplary compositions for the first liquid. As shown in Table 2, examples M-S may include cycloaliphatic epoxides. Embodiments M-R may include GPOSS. For examples M-S, the first liquid contains a first plurality of molecules comprising epoxy groups and/or glycidyl groups. Examples M-O may be free of cycloaliphatic epoxide. Examples M-O may include amine-containing polymers. Examples M and P-R may be free of amine-containing polymers. Embodiments P-S may be free of GPOSS (or other POSSs). Examples M-N and P may include curing catalysts, for example, when the corresponding examples include amine-containing polymers. Examples M-N and Q-S may be amine free. Examples M-N and P-S may include oxetane-containing molecules, for example, when the corresponding examples are free of amines. Examples M, O-P and S may include photoinitiators. Examples M-N and P-R may be free of photoinitiators.

Table 2: composition of the first liquid and/or the second liquid

After step 703, as shown in fig. 9-10, the method may proceed to step 705, which includes partially curing the first liquid 803 to form a partially cured coating 1113 (see fig. 11). As used herein, "partially cured" means that the epoxy and/or glycidyl functional groups react to less than 70%. Throughout the present disclosure, raman spectroscopy can be used to determine the strength of epoxide or glycidox ring deformation (e.g., 921cm ^-1 ) To monitor the extent of reaction of the epoxy functional groups. It is understood that Fourier Transform Infrared (FTIR) spectroscopy may also be employed to measure the extent of reaction of the epoxy functional groups. For example, the degree of reaction of the epoxy and/or glycidyl functional groups of the partially cured first liquid at the end of step 705 may be: about 20% or greater, about 40% or greater, about 50% or greater, about 70% or less, about 65% or less, or about 60% or less. In aspects, the degree of reaction of the epoxy and/or glycidyl functional groups of the partially cured first liquid at the end of step 705 can be in the following range: about 20% to about 70%, about 40% to about 65%, about 50% to about 60%, or any range or subrange therebetween. Partial curing of the first liquid may enhance adhesion between the resulting first and second coatings, for example, by effecting interactions (e.g., hydrogen bonding, covalent bonding, or other interactions (e.g., dipole-dipole interactions)) between the coatings to be formed during curing of the second liquid (see step 709 discussed below).

In aspects, as shown in fig. 9, the partial curing of the first liquid 803 in step 705 may include heating the first liquid 803 at a first temperature for a first period of time. In other aspects, as shown, the first liquid 803 may be heated by placing the first liquid 803 and the substrate 203 in an oven 901 maintained at a first temperature for a first period of time. In other aspects, the first temperature may be: about 100 ℃ or greater, about 110 ℃ or greater, about 120 ℃ or greater, about 130 ℃ or greater, about 140 ℃ or greater, about 250 ℃ or less, about 200 ℃ or less, about 180 ℃ or less, about 170 ℃ or less, or about 160 ℃ or less. In other aspects, the first temperature may be in the following range: about 100 ℃ to about 250 ℃, about 110 ℃ to about 200 ℃, about 120 ℃ to about 180 ℃, about 130 ℃ to about 170 ℃, about 140 ℃ to about 160 ℃, or any range or subrange therebetween. In other aspects, the first time period may be: about 10 minutes or more, about 15 minutes or more, about 20 minutes or more, about 25 minutes or more, about 90 minutes or less, about 60 minutes or less, about 45 minutes or less, or about 35 minutes or less. In other aspects, the first period of time may be the following range: about 10 minutes to about 90 minutes, about 15 minutes to about 60 minutes, about 20 minutes to about 45 minutes, about 25 minutes to about 35 minutes, or any range or subrange therebetween.

In aspects, as shown in fig. 10, the partial curing of the first liquid 803 in step 705 may include impinging the first liquid 803 with radiation 1005 from a radiation source 1003. In even other aspects, the radiation 1005 may include wavelengths to which the photoinitiator is sensitive. In even other aspects, the irradiation may include impinging on substantially all (e.g., the entire) of the layer in which the first liquid 803 is present. In even other aspects, the radiation 1005 may include ultraviolet radiation and/or visible light radiation. In even other aspects, the radiation 1005 may include a range of light wavelengths: about 10nm to about 400nm, about 100nm to about 400nm, about 200nm to about 400nm, about 10nm to about 300nm, about 100nm to about 300nm, about 200nm to about 300nm, about 10nm to about 200nm, about 100nm to about 200nm, or any range or subrange therebetween. In even other aspects, the radiation may include a range of light wavelengths: about 315nm to about 400nm, about 280nm to about 315nm, about 100nm to about 280nm, or 122nm to about 200nm. In even other aspects, the wavelength of the light beam may be in the following range: about 300nm to about 1000nm, about 350nm to about 900nm, about 400 to about 800nm, about 500nm to about 700nm, or any range or subrange therebetween. In other aspects, the wavelength of the radiation may be: about 365nm, about 415nm, or about 590nm. In even other aspects, the radiation source 1003 may include: light Emitting Diodes (LEDs), organic Light Emitting Diodes (OLEDs), lasers, incandescent bulbs, and/or fluorescent bulbs (e.g., cold Cathode Fluorescent Lamps (CCFLs)). In other aspects, the total energy density of the radiation (e.g., UV radiation) impinging the first liquid 803 in step 705 may be: about 0.1 joule per square centimeter (J/cm) ² ) Or higher, about 0.5J/cm ² Or higher, about 1J/cm ² Or higher, about 2J/cm ² Or higher, about 10J/cm ² Or less, about 8J/cm ² Or less, about 6J/cm ² Or less, or about 4J/cm ² Or lower. In other aspects, the total energy density of the radiation (e.g., UV radiation) impinging the first liquid 803 in step 705 may be in the following range: about 0.1J/cm ² To about 10J/cm ² About 0.5J/cm ² To about 8J/cm ² About 1J/cm ² To about 6J/cm ² About 2J/cm ² To about 4J/cm ² Or any range or subrange therebetween. As used herein, total energy density means: the total energy of the radiation from the current step that corresponds to each surface area (corresponding to the first contact surface 115 of the first coating 113, see fig. 1-2) impinges (e.g., impinges) on) the first liquid. For example, the step of partially curing the first liquid, the total energy density from the LED radiation source continuously emitting UV radiation at a predetermined power for a predetermined period of time is equal to the predetermined power times the predetermined time divided by the surface area of the first liquid. In other aspects, the period of time for which the first liquid 803 is partially cured by irradiating the first liquid 803 may be: about 10 seconds or more, about 30 seconds or more, about 1 minute or more, about 2 minutes or more, about 20 minutes or less, about 10 minutes or less, about 8 minutes or less, or about 5 minutes or less. In other aspects, the period of time for which the first liquid 803 is partially cured by irradiating the first liquid 803 may be in the following range: from about 10 seconds to about 20 minutes, About 30 seconds to about 10 minutes, about 1 minute to about 8 minutes, about 2 minutes to about 5 minutes, or any range or subrange therebetween. In an aspect, the total radiant energy emitted from the radiation source 1003 during step 705 may be: about 5 joules (J) or more, about 10J or more, about 20J or more, about 50J or less, about 40J or less, or about 30J or less. In aspects, the total radiant energy emitted from the radiation source 1003 during step 705 may be in the following range: about 5J to about 50J, about 10J to about 40J, about 20J to about 30J, or any range or subrange therebetween.

In aspects, as a result of the partial curing of the first liquid 803 in step 705, a partially cured coating 1113 may be produced at the end of step 705 (see fig. 11). In other aspects, as shown in fig. 11, the partially cured coating 1113 can include a maximum first thickness 119 within one or more of the ranges discussed above with respect to the maximum first thickness 119 of the first coating 113. In other aspects, as shown in fig. 11, the partially cured coating 1113 can include a minimum first thickness 219 within one or more of the ranges discussed above with respect to the minimum first thickness 219 of the first coating 113. In even other aspects, as shown, the maximum first thickness 119 can be greater than the minimum first thickness by a first distance 208 by which the first central surface region 215 is recessed from the first major surface 205.

After step 705, the method may proceed to step 707, as shown in fig. 11, to dispose a second liquid 1103 on the partially cured coating 1113. In aspects, as shown, disposing the second liquid 1103 can include dispensing the second liquid 1103 from a container 1103 (e.g., a tube, flexible catheter, micropipette, or syringe). In aspects, as shown, the second liquid 1103 can contact the first contact surface 115 of the partially cured coating 1113. In aspects, as shown, the second liquid 1103 can be disposed over the first major surface 205 and/or the first central surface region 215 of the substrate 203, such as on the partially cured coating 1113, which partially cured coating 1113 is in turn disposed on the first major surface 205 and/or the first central surface region 215 of the substrate 203. In other aspects, although not shown, disposing the second liquid 1103 can also include pulling the applicator on the free surface of the second liquid 1103 to achieve a uniform free surface corresponding to the uniform third contact surface 125 (see fig. 1-2). In other aspects, although not shown, depositing the second liquid 1103 can include using a blade (e.g., a scalpel or a roller coated blade) to achieve a predetermined thickness.

In aspects, the second liquid 1103 can include one or more of the compositions discussed above with respect to the first liquid 803, including the exemplary compositions presented in table 2. Additionally or alternatively, the second liquid 1103 may be free of amine-containing polymers and/or amines. Additionally or alternatively, the nanoparticles contained by the second liquid 1103 may be: about 0.1 wt% or more, about 1 wt% or more, about 2 wt% or more, about 10 wt% or less, about 8 wt% or less, or about 5 wt% or less. In aspects, the nanoparticles contained by the second liquid 1103 may be, in weight percent of the second liquid 1103: about 0.1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 2 wt% to about 5 wt%, or any range or subrange therebetween. An exemplary aspect of the nanoparticles of the second liquid 1103 are silica nanoparticles. An exemplary aspect of alicyclic epoxides is 1,1' -bis (2, 3-epoxycyclohexane) (e.g., celloxide 8010 (available from Daicel corporation)).

After step 707, the method may proceed to step 721, as shown in fig. 12, to heat the second liquid 1103 and the partially cured coating 1113 at a third temperature for a third period of time. In aspects, steps 721 and 709 (discussed in the next paragraph) can be used to fully cure the second liquid 1103 (forming the second coating 123) and the partially cured coating 1113 (forming the first coating 113). In aspects, as shown, the partially cured coating 1113 and the second liquid 1103 can be heated by placing the partially cured coating 1113, the second liquid 1103, and the substrate 203 in an oven 901 maintained at a third temperature for a third period of time. In other aspects, the third temperature may be: about 100 ℃ or higher, about 110 ℃ or higher, about 120 ℃ or higher, about 150 ℃ or lower, about 140 ℃ or lower, or about 130 ℃ or lower. In other aspects, the third temperature may be in the following range: about 100 ℃ to about 150 °, about 110 ℃ to about 140 ℃, about 120 ℃ to about 130 ℃, or any range or subrange therebetween. In other aspects, the third time period may be: about 5 minutes or more, about 8 minutes or more, about 10 minutes or more, about 60 minutes or less, about 30 minutes or less, or about 20 minutes or less. In other aspects, the third time period may be in the following range: about 5 minutes to about 60 minutes, about 8 minutes to about 30 minutes, about 10 minutes to about 20 minutes, or any range or subrange therebetween. Heating the second liquid at the third temperature prior to the second temperature heating may remove any solvent present in the second liquid and/or allow any air bubbles to leave the second liquid.

After step 707 or step 721, as shown in fig. 12-13, the method may proceed to step 709, such that the partially cured coating 1113 and the second liquid 1103 are cured to form the second coating 123 disposed on the first coating 113. As used herein, "fully cured" refers to a degree of reaction of the epoxy and/or glycidyl functional groups of 70% or greater, as measured as discussed above. Having the first liquid (corresponding to the first coating) only partially cured prior to disposing the second liquid (corresponding to the second coating) may increase adhesion therebetween, such as by increasing bonding and other interactions therebetween as a result of subsequent curing of the second liquid to form the second coating disposed on the first coating. In addition, partial curing of the first liquid reduces the overall processing time and prevents the resulting first coating from becoming brittle due to excessive curing.

In an aspect, as shown in fig. 12, step 709 can include heating the partially cured coating 1113 and the second liquid 1103 to form the second coating 123 disposed on the first coating 113. In other aspects, as shown, the partially cured coating 1113 and the second liquid 1103 can be heated by placing the partially cured coating 1113, the second liquid 1103, and the substrate 203 in an oven 901 maintained at a second temperature for a second period of time. In an aspect, the second temperature may be: about 100 ℃ or higher, about 120 ℃ or higher, about 150 ℃ or higher, about 160 ℃ or higher, about 170 ℃ or higher, about 250 ℃ or lower, about 220 ℃ or lower, about 200 ℃ or lower, about 190 ℃ or lower, or about 180 ℃ or lower. In aspects, the second temperature may be in the following range: about 100 ℃ to about 250 ℃, about 120 ℃ to about 220 ℃, about 150 ℃ to about 200 ℃, about 160 ℃ to about 190 ℃, about 170 ℃ to about 180 ℃, or any range or subrange therebetween. In an aspect, the second time period may be: about 1.5 hours or more, about 2 hours or more, about 2.5 hours or more, about 5 hours or less, about 4.5 hours or less, or about 4 hours or less, or about 3.5 hours or less. In an aspect, the second period of time may be in the following range: about 1.5 hours to about 5 hours, about 2 hours to about 4.5 hours, about 2.5 hours to about 4 hours, about 2.5 hours to about 3.5 hours, or any range or subrange therebetween. In an aspect, the second temperature in step 709 may be greater than the first temperature in step 705. In an aspect, the second time period in step 709 may be twice or longer than the first time period in step 705.

In an aspect, as shown in fig. 13, step 709 can include impinging the partially cured coating 1113 and the second liquid 1103 with radiation 1005 from the radiation source 1003 to form a second coating 123 disposed on the first coating 113. In other aspects, the wavelength of the radiation source 1003 and/or the radiation 1005 may be in one or more of the ranges or options discussed above with reference to the impinging of the first liquid 803 in step 705. In even other aspects, the wavelength of the radiation source 1003 and/or the radiation 1005 may be the same as used to impinge the first liquid 803 in step 705. In other aspects, the total energy density of the radiation (e.g., UV radiation) impinging the second liquid 1103 in step 709 may be: about 1 Joule per square centimeter (J/cm) ² ) Or higher, about 2J/cm ² Or higher, about 4J/cm ² Or higher, about 6J/cm ² Or higher, about 30J/cm ² Or less, about 15J/cm ² Or less, about 10J/cm ² Or less, or about 8J/cm ² Or lower. In other aspects, the total energy density of the radiation (e.g., UV radiation) impinging the second liquid 1103 can be in the following range: about 1J/cm ² To about 30J/cm ² About 1J/cm ² To about 15J/cm ² About 2J/cm ² To about 15J/cm ² About 4J/cm ² To about 15J/cm ² About 4J/cm ² To about 10J/cm ² About 6J/cm ² To about 10J/cm ² About 6J/cm ² To about 8J/cm ² Or any range or subrange therebetween. In other aspects, the period of time for which the second liquid 1103 is caused to solidify by irradiating the second liquid 1103 may be: about 30 seconds or more, about 1 minute or more, about 2 minutes or more, about 4 minutes or more, about 30 minutes or less, about 20 minutes or less, about 10 minutes or less, or about 8 minutes or less. In other aspects, the period of time for partially curing the second liquid 709 by irradiating the second liquid 1103 in step 709 may be in the range of: about 30 seconds to about 30 minutes, about 30 seconds to about 20 minutes, about 1 minute to about 10 minutes, about 2 minutes to about 8 minutes, about 4 minutes to about 8 minutes, or any range or subrange therebetween. In an aspect, the total radiant energy emitted from the radiation source 1003 during step 709 may be: about 5 joules (J) or more, about 10J or more, about 20J or more, about 50J or less, about 40J or less, or about 30J or less. In an aspect, the total radiant energy emitted from the radiation source 1003 during step 709 may be in the following range: about 5J to about 50J, about 10J to about 40J, about 20J to about 30J, or any range or subrange therebetween.

In an aspect, after step 703, as shown in fig. 9-10, the method can follow arrow 704 through step 715, which includes curing the first liquid 803 to form the first coating 113. In aspects, as shown in fig. 9, the curing of the first liquid 803 in step 715 may include heating the first liquid 803, e.g., placing the first liquid 803 and the substrate 203 in an oven 901 maintained at a first temperature for a first period of time. In other aspects, the first time period and/or the first temperature may be within one or more corresponding ranges of the second temperature or second time period discussed above with reference to step 711. In an aspect, as shown in fig. 10, step 715 can include impinging the first liquid 803 with radiation 1005 from the radiation source 1003 to form the first coating 113. In other aspects, the wavelength of the radiation source 1003 and/or the radiation 1005 may be in one or more of the ranges or options discussed above with reference to the impinging of the first liquid 803 in step 705. In other aspects, the total radiated energy density and/or time period in step 715 may be within one or more of the corresponding ranges discussed above with reference to fig. 13 in step 711.

After step 715, as shown in fig. 11, the method may proceed to step 717, including disposing a second liquid 1103 on the first coating 113. Step 717 may be similar or identical to that discussed above with reference to step 707.

After step 717, as shown in fig. 12-13, the method may proceed to step 719, which includes curing the second coating 1103 to form the second coating 123 disposed on the first coating 113. In an aspect, as shown in fig. 12, step 719 can include heating the second liquid 1103, for example, by placing the second liquid 1103 in an oven 901 maintained at a second temperature for a second period of time. In other aspects, the second temperature and/or the second time period may be within one or more of the corresponding ranges discussed above with reference to fig. 12 in step 709. In aspects, as shown in fig. 13, step 719 can include irradiating the second liquid 1103 with radiation 1005 from the radiation source 1003 to form a second coating 123 disposed on the first coating 113. In other aspects, the wavelength of the radiation source 1003 and/or the radiation 1005 may be in one or more of the ranges or options discussed above with reference to step 705 or step 715 impinging the first liquid 803. In even other aspects, the wavelength of the radiation source 1003 and/or the radiation 1005 may be the same as that used to strike the first liquid 803 in step 715. In other aspects, the total radiated energy density and/or time period in step 719 may be within one or more of the corresponding ranges discussed above with reference to fig. 13 in step 711.

In aspects, step 705 or 715 may include heating the first liquid 803 and step 709 or 719 may include heating the second liquid 1103. In aspects, step 705 or 715 may include irradiating the first liquid 803 and step 709 or 719 may include irradiating the second liquid 1103. In aspects, step 705 or 715 may include irradiating the first liquid 803 and step 709 or 719 may include heating the second liquid 1103. In aspects, step 705 or 715 may include heating the first liquid 803 and step 709 or 719 may include irradiating the second liquid 1103.

After step 709 or step 719, the method may proceed to step 711, including assembling the coated article (e.g., coated article 101 or 201). In other aspects, step 711 can include including the coated article 101 or 201 in an electronic device (e.g., a consumer electronic device as shown in fig. 5-6). After step 709, step 711 or step 719, the method may include completing at step 713, which may then complete the method of manufacturing the coated article 101 or 201. In aspects, the coated article and/or the second coating can include pencil hardness in one or more of the ranges discussed above (e.g., as-formed state, after being maintained at 85% relative humidity, 85 ℃ environment for 16 hours). In aspects, the coated article can include a viscosity in one or more of the ranges discussed above (e.g., as-formed state, after a 16 hour hold at 85% relative humidity, 85 ℃ environment). In aspects, the coating may include tensile strength, ultimate elongation, elastic modulus (e.g., young's modulus), and/or coating thickness within one or more ranges of the corresponding properties of the coating discussed above. In aspects, the coating and/or coated article may include refractive index, transmittance, haze, and/or yellowness index within one or more of the ranges discussed above with respect to the corresponding properties. In aspects, the coating may be substantially free of visible crystals at 100 times magnification. In aspects, the coating and/or coated article can achieve parallel plate spacing in one or more of the ranges discussed above with respect to parallel plate spacing.

In aspects, the method may begin at step 701 and then proceed sequentially through steps 703, 705, 707, 709, 711, and 713, as discussed above with reference to the flowchart in fig. 7. In aspects, step 702 may conform from step 709 to step 713, for example, if the method is completed at the end of step 709 (e.g., the coated article does not require further assembly). In aspects, step 704 may correspond from step 703 to step 715, for example, if the first coating is fully cured (in first step 715) rather than partially cured (as in step 705). In aspects, step 706 may conform from step 719 to step 713, for example, if the method is completed at the end of step 719 (e.g., the coated article does not require further assembly). In an aspect, arrow 708 may be consistent with adding step 721 between step 707 and step 709, for example if the second liquid 1103 is heated at a third temperature for a third period of time before forming the second coating 123 disposed on the first coating 113 in step 709. Coated articles according to aspects of the present disclosure may be manufactured in combination with any of the above options.

In aspects, one of the coatings described above (e.g., the first coating 113, the second coating 123) can include a polymer-based portion that includes a polymer. In other aspects, the polymer-based moiety can be a cured product of a composition comprising: functionalized oligomeric silsesquioxanes (e.g., POSS, GPOSS), oxetanes (i.e., oxetane-containing molecules), and one or more of the following: amine-terminated polymers (e.g., difunctional, trifunctional), curing catalysts, photoinitiators, or combinations thereof. In even other aspects, the polymer-based moiety and/or composition may comprise the following amounts of functionalized oligomeric silsesquioxanes: about 60 wt% or more, about 70 wt% or more, about 90 wt% or less, or about 80 wt% or less. In even other aspects, the polymer-based moiety can include the following amounts of functionalized oligomeric silsesquioxanes: about 60 wt% to about 90 wt%, about 70 wt% to about 80 wt%, or any range or subrange therebetween. Exemplary aspects of the functional groups that functionalize the oligomeric silsesquioxanes include glycidyl or epoxycyclohexyl functional groups. The functionalized oligomeric silsesquioxanes may be POSS and/or GPOSS. In even other aspects, the polymer-based moiety and/or composition may comprise the following amounts of oxetanes: about 5 wt% or more, about 7 wt% or more, about 10 wt% or less, or about 9 wt% or less. In even other aspects, the polymer-based moiety may include the following amounts of oxetanes: about 5 wt% to about 10 wt%, about 7 wt% to about 9 wt%, or any range or subrange therebetween. An exemplary aspect of the oxetane is trimethylol propane oxetane. In even other aspects, the polymer-based moieties and/or compositions may comprise difunctional amine-terminated polymers in the following amounts: about 15 wt% or more, about 18 wt% or more, about 20 wt% or more, about 25 wt% or less, about 24 wt% or less, or about 23 wt% or less. In even other aspects, the polymer-based moieties and/or compositions may comprise difunctional amine-terminated polymers in the following amounts: about 15 wt% to about 25 wt%, about 18 wt% to about 24 wt%, about 20 wt% to about 23 wt%, or any range or subrange therebetween. Exemplary aspects of difunctional amine-terminated polymers include amine-terminated poly (propylene oxide) and amine-terminated poly (dimethylsiloxane). In even other aspects, the polymer-based moieties and/or compositions may comprise trifunctional amine-terminated polymers in the following amounts: about 5 wt% or more, about 7 wt% or more, about 10 wt% or more, about 15 wt% or less, about 13 wt% or less, or about 12 wt% or less. In even other aspects, the polymer-based moieties and/or compositions may comprise trifunctional amine-terminated polymers in the following range of amounts: about 5 wt% to about 15 wt%, about 7 wt% to about 13 wt%, about 10 wt% to about 12 wt%, or any range or subrange therebetween. An exemplary aspect of the trifunctional amine-terminated polymer is a trifunctional amine-terminated polyether. In even other aspects, the polymer-based part and/or composition may contain the following amounts of curing catalyst: about 0.1 wt% or more, about 0.5 wt% or more, about 1 wt% or more, about 3 wt% or less, about 2 wt% or less, or about 1.5 wt% or less. In even other aspects, the polymer-based part and/or composition may contain curing catalysts in the following range amounts: about 0.1 wt% to about 3 wt%, about 0.5 wt% to about 2 wt%, about 1 wt% to about 1.5 wt%, or any range or subrange therebetween. An exemplary aspect of the curing catalyst is 2,4, 6-tris (dimethylaminomethyl) phenol. In even other aspects, the polymer-based fraction and/or composition may comprise the following amounts of photoinitiators: about 0.1 wt% or more, about 0.5 wt% or more, about 1 wt% or more, about 5 wt% or less, about 4 wt% or less, or about 3 wt% or less. In even other aspects, the polymer-based fraction and/or composition may comprise the following range of amounts of photoinitiator: about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 1 wt% to about 3 wt%, or any range or subrange therebetween. In other aspects, the composition may be irradiated to cure the composition to form the polymer-based moiety. In even other aspects, the polymer-based moieties and/or compositions can be substantially solvent-free, substantially nanoparticle-free, and/or substantially alicyclic epoxide-free. In other aspects, the polymer-based portion can have a pencil hardness of about 3H or greater in the as-formed state. Examples T-V in table 3 correspond to exemplary ranges of compositions that can be cured to form polymer-based moieties.

In aspects, one of the coatings described above (e.g., the first coating 113, the second coating 123) can include a polymer-based portion that includes a polymer. In other aspects, the polymer-based moiety can be a cured product of a composition comprising: alicyclic epoxides, oxetanes (i.e., oxetane-containing molecules), and one or more of the following: functionalized oligomeric silsesquioxanes (e.g., POSS, GPOSS), nanoparticles, photoinitiators, or combinations thereof. In even other aspects, the polymer-based moieties and/or compositions may comprise the following amounts of cycloaliphatic epoxide: about 75 wt% or more, about 77 wt% or more, about 80 wt% or more, about 90 wt% or less, about 88 wt% or less, or about 85 wt% or less. In even other aspects, the polymer-based moieties and/or compositions may comprise the following range of amounts of cycloaliphatic epoxide: about 75 wt% to about 90 wt%, about 77 wt% to about 88 wt%, about 80 wt% to about 85 wt%, or any range or subrange therebetween. In even other aspects, the polymer-based moiety and/or composition may comprise the following amounts of functionalized oligomeric silsesquioxanes: about 3 wt% or more, about 4 wt% or more, about 10 wt% or less, or about 8 wt% or less. In even other aspects, the polymer-based moiety can include the following amounts of functionalized oligomeric silsesquioxanes: about 3 wt% to about 10 wt%, about 4 wt% to about 8 wt%, or any range or subrange therebetween. Exemplary aspects of the functional groups that functionalize the oligomeric silsesquioxanes include glycidyl or epoxycyclohexyl functional groups. In even other aspects, the polymer-based moiety and/or composition may comprise the following amounts of oxetanes: about 5 wt% or more, about 7 wt% or more, about 10 wt% or less, or about 9 wt% or less. In even other aspects, the polymer-based moiety may include the following amounts of oxetanes: about 5 wt% to about 10 wt%, about 7 wt% to about 9 wt%, or any range or subrange therebetween. An exemplary aspect of the oxetane is trimethylol propane oxetane. In even other aspects, the polymer-based fraction and/or composition may comprise the following amounts of nanoparticles: about 0.1 wt% or more, about 1 wt% or more, about 2 wt% or more, about 5 wt% or less, about 4 wt% or less, or about 3 wt% or less. In even other aspects, the polymer-based fraction and/or composition may comprise nanoparticles in the following range of amounts: about 0.1 wt% to about 5 wt%, about 1 wt% to about 4 wt% or less, about 2 wt% to about 3 wt%, or any range or subrange therebetween. An exemplary aspect of the nanoparticle is a silica nanoparticle. In even other aspects, the polymer-based fraction and/or composition may comprise the following amounts of photoinitiators: about 0.1 wt% or more, about 0.5 wt% or more, about 1 wt% or more, about 5 wt% or less, about 4 wt% or less, or about 3 wt% or less. In even other aspects, the polymer-based fraction and/or composition may comprise the following range of amounts of photoinitiator: about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, about 1 wt% to about 3 wt%, or any range or subrange therebetween. In other aspects, the composition may be irradiated to cure the composition to form the polymer-based moiety. In even other aspects, the polymer-based fraction and/or composition may be substantially solvent-free, substantially amine-free, and/or substantially free of curing catalyst. In other aspects, the polymer-based portion can have a pencil hardness of about 3H or greater in the as-formed state. Examples W-X in table 3 correspond to exemplary ranges of compositions that can be cured to form polymer-based moieties.

Table 3: composition range (wt.%)

Examples

The various aspects are further illustrated by the following examples. Tables 4-12 present information on compositions (e.g., liquids) that may be used to form the first coating 113 and/or the second coating 123 (e.g., as part of the coated article 101 or 201). Tables 4-8 present information regarding the coating and the composition used to form the coating. The substrates used to measure the properties reported in tables 4-8 are glass-based substrates (e.g., composition 1, in mole%, nominally: 69.1 SiO) ₂ 、10.2Al ₂ O ₃ 、15.1Na ₂ O、0.01K ₂ O、5.5MgO、0.09SnO ₂ ) Having a substrate thickness of 30 μm and being similar to the substrate 103 shown in fig. 1.

Examples 1-17 included the reactants presented in tables 4-5 (in wt%) that were used to form compositions (e.g., coatings). 2021P and 8010 are cycloaliphatic epoxides. "2021P" refers to Celloxide 2021P available from Daicel. "8010" refers to Celloxide 8010, available from Daicel, as a 67 weight percent mixture in toluene. GPOSS, EP0408 and EP0418 are functionalized oligomeric silsesquioxanes which are functionalized by means of glycidyl groups or epoxy groups. In tables 4-5, "GPOSS" refers to EP0409, which is purchased from Mixed plastics Co. "EP0408" refers to EP0408, which is available from Mixed plastics Co. "EP0418" refers to EP0418 from Mixed plastics. As used in tables 4-5, PDMS refers to DMS-a11 from Gelest corporation, where "GPOSS/PDMS/GPOSS" refers to PDMS that incorporates GPOSS at either end of the PDMS, which corresponds to about 25 wt.% PDMS and 75 wt.% GPOSS. "DMP", "SI-300" and "SIS" are curing catalysts. "DMP" refers to 2,4, 6-tris (dimethylaminomethyl) phenol available from Sigma Aldrich, T58203. "SI300" refers to SI-300 manufactured by Sanshen chemical company (Sanshin Chemical Industry). "SIS" refers to SI-S manufactured by Sanshen chemical company. "SI300/SIS" refers to a 100:3 weight ratio of SI300 to SIS mixture with 45 weight percent gamma-butyrolactone (GBL).

In tables 4-5, "SNP" refers to silica nanoparticles with a median particle diameter of 20nm available from Nanopol C764 of Evonick, inc., having a 50 weight percent mixture of methoxypropyl acetate ("MPA"). D400 and T403 are polymeric linkers having amine functionality at the polymer ends. "D400" refers to diaminopoly (propylene glycol) of Jeffamine D-400 available from Huntsman corporation, having a number average molecular weight (Mn) of about 430 daltons. "T403" refers to trimethylolpropane tris [ amine-terminated poly (propylene glycol) ] of Jeffamine T-403 available from Huntsman, inc., having a number average molecular weight (Mn) of about 440 daltons. "TMPO" is an oxetane molecule, i.e., trimethylol propane oxetane (TMPO). OM250, OM432, and UV6976 are cationic photoinitiators. "OM250" refers to Omnicat 250 available from IGM resins as a 75 weight percent blend in propylene carbonate. "OM432" refers to Omnicat 432 available from IGM resins as 45 weight percent propylene carbonate. "UV6976" refers to 50% by weight of Cyracure UVI-6976, propylene carbonate available from Dow. MPA (defined above), GBL (defined above) and toluene are solvents.

In tables 4-5, the solvents in the listed components are listed separately. For example, SNPs are 50 wt% silica nanoparticles and 50 wt% MPA, and table 5 lists the amount of silica nanoparticles in a SNP under "SNP" and the amount of MPA in a SNP under "MPA". Thus, it is clear whether the composition is substantially free of solvent and/or free of solvent. For example, examples 1-12, 14 and 17 were substantially free of solvent, while examples 4-5 and 8 were free of solvent. Examples 1 and 6-17 comprise about 60 wt.% or more (e.g., about 75 wt.% or more) of the cycloaliphatic epoxide; examples 1, 6-15 and 17 contain 80 wt% or more of alicyclic epoxide; and examples 2-5 contained less than 10 wt.% cycloaliphatic epoxide (e.g., 0 wt.%). Examples 1-17 include epoxy and/or glycidyl functional groups that react during the curing process to form ether linkages between molecules (e.g., monomers). Examples 4-5 include amine functionality in the form of an amine-containing polymer (e.g., PDMS contains about 20 wt% of example 5, D400 in example 4, T403 in example 5) and epoxy and/or glycidyl functionality that will react during the curing process to form at least some ether groups that bind to the amine groups. Examples 2-5, 9-12, and 14-18 contained about 60 wt.% or more of functionalized oligomeric silsesquioxanes (e.g., GPOSS), while examples 1, 6-8, and 13 contained about 20 wt.% or less of functionalized oligomeric silsesquioxanes (e.g., GPOSS). Examples 2, 4-6 and 9-17 contained oxetane molecules, whereas examples 1, 3 and 7-8 did not. Examples 1-3 and 6-17 contained about 5 wt% or less cationic photoinitiator, while examples 4-5 did not. Examples 4-5 contain a curing catalyst.

Table 4: composition ranges of reactants (wt.%)

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Table 5: composition ranges of reactants (wt.%)

Examples	9	10	11	12	13	14	15	16	17
										8010	84	81	82	80.5	81	89	82.5	77.5	88
TMPO	8.5	8	8	8	8	9	8	8	9
										EP0408	4	8	8	8	0	0	0	0	0
EP0418	0	0	0	0	0	8	4	8	0
										SNP	0	0	0	0	4	0	0	0	0
SI300/SIS	1.8	1.5	0	0	1.5	1.5	1.8	1.5	0
										UV6976	0	0	1	0	0	0	0	0	0
OM432	0	0	0	1.7	0	0	0	0	1.4
										Toluene (toluene)	0	0	0	0	0	0	2	3.5	0
MPA	0	0	0	0	4	0	0	0	0
										GBL	1.7	1.5	0	0	1.5	1.5	1.7	1.5	0
Propylene carbonate	0	0	1	1.8	0	0	0	0	1.6

Table 6 presents the curing conditions, as-formed hardness, as-formed adhesion, and pen down heights for examples 1, 3-5, and 9-16. Examples 1, 4-11, 13 and 16 were cured using only thermal curing and examples 3, 12 and 14-15 were cured using UV curing. For examples 12 and 14-15, a temperature treatment (e.g., 120 ℃ for 10 minutes) was performed after UV curing. Table 6 sets forth the wavelength of light (e.g., emitted from an LED, lamp, or laser) during UV curing. As used herein, "as-formed state" refers to a property measured without storage at extreme temperatures and/or elevated relative humidity. Examples 3-4 and 9-16 included pencil hardness of 2H or higher in the as-formed state. Examples 3, 9-12 and 14 included pencil hardness of 5H or higher in the as-formed state, but examples 3, 11-12 and 14 included adhesion of 0B in the as-formed state. Thus, the cost of good hardness would be adhesion. Examples 1, 4, 9-10, 13 and 15-16 included a bond in the as-formed state of 3B or higher. Thus, examples 4, 9-10 and 16 included both pencil hardness in the as-formed state of 3H or more and adhesion in the as-formed state of 3H or more. It is to be understood that examples 1, 9-12, 13 and 16 may employ radiation curing instead of or in combination with heating (e.g., thermal curing); in addition, examples 3, 12 and 14-15 may be cured using heat (e.g., heat curing) instead of or in combination with radiation.

Example 3 included a maximum amount of POSS (98 wt% GPOSS), a as-formed pencil hardness of 5H, and a as-formed bond of 0B. Reducing the amount of POSS and adding TMPO (e.g., examples 4-5) increases the as-formed bond. Providing GPOSS (examples 4-5) increased pencil hardness in the as-formed state compared to example 1 (0 wt% POSS). Example 13 demonstrates that the addition of silica nanoparticles can increase pencil hardness in the as-formed state while maintaining adhesion in the as-formed state of 5B, as compared to example 1 (0 wt% silica nanoparticles). Examples 9-11, 13 and 15-16 included pen down heights of 2cm or more. Examples 9-10 and 16 included pen down heights of 3cm or greater. Examples 9-10 included pen down heights of 5cm or greater. Examples 9-10 included less than about 10 wt.% POSS (e.g., about 4 wt.% to about 8 wt.%), less than about 10 wt.% TMPO (e.g., about 8 wt.%); examples 9-10 had the highest drop height and pencil hardness in the as-formed state and adhesion in the as-formed state of 4B.

Table 6: properties of the coating

Table 7: pencil hardness and adhesion of bilayer coatings

Tables 7-8 present the compositions and curing conditions used to form the bilayer coating. The thicknesses in tables 7-8 refer to the initial coating thickness for the corresponding liquid. Examples 18-25 used only thermal curing, while examples 26-28 used radiation in combination with heat to cure the liquid. Examples 18-22 included pencil hardness of 3H or higher in the as-formed state and adhesion of 1B or higher (e.g., 4B or higher) in the as-formed state. Examples 18-22 included the same as-formed adhesion but had a higher as-formed pencil hardness than example 1 (properties in table 6). Thus, the bilayer coating overcomes the significant tradeoff between pencil hardness and adhesion exhibited by the single layer coating.

For examples 18-22, the pencil hardness after 16 hours of holding at 85 ℃ in an 85% relative humidity ("RH") environment was equal to or greater than the pencil hardness in the as-formed state. For examples 18-19, the bond dropped to 0B after 16 hours of holding at 85 ℃ in an 85% relative humidity environment. However, examples 20-22 included 4B or higher adhesion after 16 hours at 85℃in an 85% relative humidity environment. Comparative examples 18-19 and examples 20-22, the thickness drop of the second coating (1.5 μm vs.25 μm) correlated with greater adhesion after 16 hours at 85 ℃ in an 85% relative humidity environment. Example 22 reduced the time of the first curing step compared to example 20; however, examples 20 and 22 have substantially the same adhesion value and pencil hardness value. Thus, the curing time (and the degree of curing) of the first curing step can be reduced without reducing the adhesion value and pencil hardness value.

Table 8 presents the pen down heights for examples 23-28 with the compositions and curing conditions set forth therein. The pen down height recorded in table 8 is the median of at least 7 samples. In examples 23-25, the thickness of the first coating was varied with all other conditions remaining the same. Increasing the thickness of the first coating correlated with an increase in the drop height of examples 23-25, suggesting that the first coating absorbed and dissipated impact energy, which achieved an increase in the drop height.

Table 8: pen-down height of double-layer coating

In each of the curing steps of examples 26-28, the corresponding liquid was irradiated prior to heating. In examples 26-28, the thickness of the first coating was varied while all other conditions remained the same. Increasing the thickness of the first coating correlated with an increase in the drop height of examples 26-28, suggesting that the first coating absorbed and dissipated impact energy, which achieved an increase in the drop height. Examples 25 and 28 achieve a pen down height of 10cm or more. Example 25 achieves a 15cm pen down.

The above observations can be combined to provide a coated article comprising a first coating and a second coating, and a method of making the same. The coating disposed on the substrate can provide both high surface hardness and good impact resistance. For example, the second coating may provide a high surface hardness (e.g., a pencil hardness of about 3H or greater in the as-formed state, a pencil hardness of about 4H or greater or about 5H or greater after 16 hours in an 85 ℃ environment at 85% relative humidity). Providing high surface hardness can provide scratch resistance of the coated article. For example, the first coating can increase the impact resistance of the coated article (e.g., withstand a strike height of 10cm or greater, increasing the strike threshold height by about 5cm or greater relative to the same substrate without the coating), for example, by absorbing and/or dissipating impact energy. Providing a functionalized oligomeric silsesquioxane as part of the second coating may further increase the hardness of the resulting coating and/or coated article. Providing a coating on a substrate increases the durability of the coated article by, for example, filling in surface imperfections in the substrate and/or protecting the surface imperfections in the substrate from damage.

Providing a transition surface region (e.g., a first transition surface region and/or a second transition surface region) may reduce (e.g., minimize) optical distortion and/or visual visibility of thickness variation from substrate thickness to center thickness. Providing a smoothly shaped first transition region and/or second transition region may reduce optical distortion.

Providing a first polymer and/or a second coating that includes oxygen atoms in the backbone can increase the flexibility of the corresponding polymer and the resulting coating, which can increase ultimate elongation, durability, and/or impact resistance (e.g., drop height). Providing a first polymer and/or a second polymer portion having a glass transition temperature that falls outside of an operating range (e.g., about 0 ℃ to about 40 ℃, about-20 ℃ to about 60 ℃) may achieve consistent properties over the operating range. Providing a coating that is free of a photoinitiator (e.g., a thermally curable composition) may eliminate yellowing problems.

Directional terms used herein, such as up, down, left, right, front, back, top, bottom, are merely with reference to the drawings being drawn and are not intended to represent absolute orientations.

It will be appreciated that the various aspects disclosed may relate to particular features, elements, or steps described with respect to particular aspects. It will also be understood that although a particular feature, element, or step is described in connection with one aspect, different aspects may be interchanged or combined in various combinations or permutations not shown.

It is also to be understood that the terms "the," "an," or "one" as used herein mean "at least one," and should not be limited to "only one," unless explicitly stated to the contrary. Thus, for example, reference to "a" or "an" component includes aspects having two or more such components unless the text expressly indicates otherwise. Similarly, "plurality" is intended to mean "more than one".

As used herein, the term "about" means that the amounts, dimensions, formulations, parameters, and other variables and characteristics are not, nor need be, exact, but may be approximated and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding and measurement error and the like, among other factors known to those of skill in the art. Ranges may be expressed herein as from "about" another particular value, and/or to "about" another particular value, as a termination. When such a range is expressed, aspects include from, and/or to, a particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. Whether or not the numerical values or ranges of the present specification are expressed as "about," the numerical values or ranges of the endpoints are intended to include two aspects: one modified with "about" and one without "about". It will also be understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

The terms "substantially," "essentially," and variations thereof as used herein are intended to mean that the feature being described is the same or approximately the same as the value or description. For example, a "substantially planar" surface is intended to mean a planar or near-planar surface. Further, as defined above, "substantially similar" is intended to mean that the two values are equal or approximately equal. In aspects, "substantially similar" may mean that the values are within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

No method described herein is intended to be construed as requiring that its steps be performed in a specific order unless expressly stated otherwise. Thus, when a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically expressed in the claims or descriptions that the steps are limited to a specific order, it is not intended that such an order be implied.

While the transition word "comprising" may be used to disclose various features, elements, or steps of a particular aspect, it is understood that this implies alternative aspects including those described by "," consisting essentially of "," consisting of "the transition word. Thus, for example, implicit alternative aspects to a device containing a+b+c include aspects in which the device consists of a+b+c and aspects in which the device consists primarily of a+b+c. As used herein, unless otherwise indicated, the terms "comprising" and "including" and variations thereof are to be understood as synonyms and open-ended.

The features of the aspects and aspects described above are exemplary and may be provided alone or in any combination with any one or more features of the other aspects provided herein without departing from the scope of the present disclosure.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present disclosure without departing from the scope or spirit of the disclosure. Accordingly, this disclosure covers modifications and variations of this aspects provided they come within the scope of the appended claims and their equivalents.

Claims

1. A coated article, comprising:

a first coating disposed on the first major surface of the substrate, the first coating comprising a first polymer comprising a plurality of first monomers linked by ether groups formed by reaction of epoxy groups or glycidyl groups of the first monomers or linked by amine groups formed by reaction of epoxy groups or glycidyl groups with amine groups; and

A second coating layer disposed on the first coating layer, the second coating layer comprising a second polymer comprising a plurality of second monomers linked by ether groups formed by reaction of epoxy groups or glycidyl groups of the second monomers of the plurality of second monomers or linked by amine groups formed by reaction of epoxy groups or glycidyl groups with amine groups,

2. The coated article of claim 1, wherein the plurality of second monomers comprises a cycloaliphatic epoxide.

3. The coated article of any of claims 1-2, wherein the second coating comprises a second plurality of functionalized oligomeric silsesquioxanes, a first functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes being combined with a second functionalized oligomeric silsesquioxanes of the second plurality of functionalized oligomeric silsesquioxanes as part of the second polymer.

4. The coated article of any of aspects 1-3, wherein the first plurality of monomers comprises a cycloaliphatic epoxide.

5. The coated article of any of claims 1-4, wherein the first coating comprises a bond to the substrate of about 1B or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

6. The coated article of any of claims 1-5, wherein the as-formed bond between the first coating and the substrate is about 4B or greater.

7. The coated article of any of claims 1-6, wherein the second coating has a pencil hardness of about 4H or greater after 16 hours in an 85 ℃ environment at 85% relative humidity.

8. The coated article of any of claims 1-7, wherein the first coating comprises an elastic modulus in the range of about 1 megapascal to about 2,000 megapascals.

9. The coated article of any of claims 1-8, wherein the second coating comprises an elastic modulus in the range of about 100 megapascals to about 5,000 megapascals.

10. The coated article of any one of claims 1-9, wherein the substrate comprises a glass-based substrate or a ceramic-based substrate.

11. The coated article of any one of claims 1-10, wherein the coated article achieves a parallel plate spacing of 3 millimeters.

12. The coated article of any one of claims 1-10, wherein the coated article achieves a parallel plate spacing of about 1 millimeter to about 10 millimeters.

13. A method of forming a coated article, comprising:

partially curing the first liquid to form a partially cured coating;

14. The method of claim 13, wherein partially curing the first liquid comprises heating the first liquid at a first temperature ranging from about 100 ℃ to about 250 ℃ for a first period of time ranging from about 10 minutes to about 90 minutes.

15. The method of claim 14, wherein curing the partially cured coating and the second liquid comprises heating the partially cured coating and the second liquid at a second temperature ranging from about 100 ℃ to about 250 ℃ for a second period of time ranging from about 1.5 hours to about 5 hours.

16. The method of claim 13, wherein the partially curing of the first liquid comprises irradiating the first liquid, and the partially cured coating and the second liquid comprise irradiating the partially cured coating and the second liquid.

17. The method of any of claims 13-16, wherein curing the second coating comprises the second polymer comprising a plurality of second monomers linked by ether groups, and curing the second liquid to form the second coating comprises reacting epoxy groups or glycidyl groups of a second monomer of the plurality of second monomers, or the second polymer comprises a plurality of second monomers linked by amine groups formed by reacting epoxy groups or glycidyl groups with amine groups of a second monomer of the plurality of second monomers.

18. The method of claim 17, wherein the second coating comprises a second plurality of functionalized oligomeric silsesquioxanes, a first one of the second plurality of functionalized oligomeric silsesquioxanes being combined with a second one of the second plurality of functionalized oligomeric silsesquioxanes as part of the second polymer.

19. The method of any of claims 13-18, wherein the first coating comprises a first polymer comprising a plurality of first monomers linked by ether groups formed by reaction of epoxy groups or glycidyl groups of first monomers of the plurality of first monomers or linked by amine groups formed by reaction of epoxy groups or glycidyl groups with amine groups of first monomers of the plurality of first monomers.

20. The method of any one of claims 13-19, wherein the second liquid is substantially free of solvent and/or the first liquid is substantially free of solvent.