CN117255836A

CN117255836A - Coated article, method of making coated article, and method of making composition

Info

Publication number: CN117255836A
Application number: CN202280032348.1A
Authority: CN
Inventors: 邓华云; 贺明谦; 珍妮·金; 李灵珂; 李鑫; 李阳; 詹妮弗·林恩·里昂; 凯文·罗伯特·麦卡锡; 钮渭钧; 亚瑟·劳伦斯·华莱士; 王宏祥; 阿林·李·纬克尔; 张盈
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2021-04-08
Filing date: 2022-04-06
Publication date: 2023-12-19

Abstract

The coated article can include a coating disposed on the first major surface of the substrate. The coating comprises a plurality of functionalized oligomeric silsesquioxanes and a pen hardness of about 5H or greater. In aspects, the coating comprises a linking group that is terminated with a first functional group and a second functional group. In aspects, the coating comprises a silane coupling agent that adheres the coating to the first major surface. A method of making a coated article includes depositing a layer comprising a plurality of functionalized oligomeric silsesquioxanes on a first major surface of a substrate, and curing the layer to form the coating. The method of forming a composition includes reacting a plurality of functionalized oligomeric silsesquioxanes with a linking group that is terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group.

Description

Coated article, method of making coated article, and method of making composition

Technical Field

The present application claims priority from U.S. c. ≡119 U.S. provisional application No. 63/299052 filed on 1 month 13 of 2022, U.S. provisional application No. 63/277625 filed on 11 month 10 of 2021, and U.S. provisional application No. 63/172250 filed on 8 of 2021, the contents of each of which are hereby incorporated by reference in their entireties.

The present disclosure relates generally to coated articles, methods of making coated articles, and methods of making compositions, and more particularly, to coated articles and methods of making coated articles including pen hardness, and methods of making compositions comprising a plurality of functionalized oligomeric silsesquioxanes.

Background

Foldable substrates are commonly used in, for example, display applications such as liquid crystal displays (liquid crystal display; LCD), electrophoretic displays (EPD), organic light emitting diode displays (OLED), plasma displays (plasma display panel; PDP), and the like.

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

It is desirable to develop a foldable display and a foldable protective cover for mounting on the foldable display. The foldable display and the foldable cover should have good impact resistance and puncture resistance. At the same time, the foldable display and the foldable cover should have a small minimum bend radius (e.g., about 10 millimeters (mm) or less).

Accordingly, there is a need to develop coatings for display devices and/or foldable devices that have high transparency, low haze, lower minimum bend radius, and good impact and puncture resistance, as well as coated articles including coatings and substrates (e.g., glass-based substrates, ceramic-based substrates).

Disclosure of Invention

Described herein are compositions, coatings, and coated articles comprising a variety of functionalized oligomeric silsesquioxanes, and methods of making such compositions, coatings, and coated articles. The coated article may be used as a foldable substrate and the coating and/or coated article may be incorporated into a foldable display. A variety of functionalized oligomeric silsesquioxanes can provide good scratch resistance and/or high pen hardness (e.g., about 5H or greater, about 7H or greater, about 9H or greater). The provided plurality of functionalized oligomeric silsesquioxanes can react with the first functional group and/or the second functional group of the linking group (e.g., polymer). The degree of functionalization of the plurality of functionalized oligomeric silsesquioxanes may facilitate the binding of the polymer to two different ones of the plurality of functionalized oligomeric silsesquioxanes. Providing the coating on the substrate improves the durability of the coated article, for example by filling surface defects in the substrate and/or protecting the surface defects in the substrate from damage. In addition, the substrate may include a glass-based substrate and/or a ceramic-based substrate to enhance puncture resistance and/or impact resistance. In addition, the glass-based substrate and/or ceramic-based substrate may be chemically strengthened to further enhance the impact and/or puncture resistance of the coated article while promoting good bending properties.

The composition may comprise a linking group (e.g., a polymer) having functional groups at opposite ends of the polymer, wherein the functional groups react with the functionalized oligomeric silsesquioxane. The linking group may include a polymer that may reduce (e.g., prevent) aggregation of various functionalized oligomeric silsesquioxanes, may provide good optical properties (e.g., high transmittance, low haze), and as a coating, may provide good durability and/or good adhesion to the substrate. Providing a linking group (e.g., a polymer) that includes oxygen atoms in the backbone of the linking group can increase the flexibility of the linking group, the resulting composition, and the resulting coating, which can increase the ultimate elongation, durability, and/or impact resistance (e.g., pen drop height). Providing a linking group comprising a polymer having a number average molecular weight in the range of about 400 daltons to about 30,000 daltons can prevent aggregation of the functionalized oligomeric silsesquioxane attached thereto while reducing entanglement of the polymer, which can inhibit manufacturability of the resulting coating and/or coated article. Providing a low molar ratio of linking groups (e.g., polymer) to the various functionalized oligomeric silsesquioxanes (e.g., about 0.06 or less) can result in a polymer that binds to both functionalized oligomeric silsesquioxanes, which can achieve the benefits described above. Providing a polymer having a glass transition temperature outside the operating range of the coated article (e.g., outside the operating range of about-20 ℃ to about 60 ℃) may result in a coated article having consistent properties over the operating range. Providing a reactive diluent (e.g., a linking group that is not bonded to the functionalized oligomeric silsesquioxane prior to curing after the composition is disposed on a substrate) can be used to adjust the viscosity of the composition, which can facilitate uniform application and/or enable lower cost application techniques while reducing the overall cost of the composition and/or coating.

Providing a linking group comprising one or more amine and/or anhydride functional groups can provide a coating that has good adhesion to a substrate (e.g., about 4B or greater when formed, about 4B or greater after 10 days in a 50% relative humidity, 25 ℃ environment, and/or about 4B or greater after 10 days in a 95% relative humidity, 65 ℃ environment), whether or not a silane coupling agent is used. Providing a curing catalyst may increase the hardness of the resulting coating. Providing a composition comprising trimethylol propane oxetane can increase the hardness of the resulting coating. The coating may be hydrophobic, have a low dynamic coefficient of friction (i.e., about 0.8 or less, such as about 0.5 or less), good abrasion resistance, and/or function as an Easy To Clean (ETC) coating.

Forming the layer from a substantially solvent-free composition may increase its cure rate, which may reduce processing time. Furthermore, solvent-free compositions may reduce (e.g., reduce, eliminate) the use of rheology modifiers and increase composition uniformity, which may increase the optical clarity (e.g., transmittance) of the resulting coating. Providing a coating process that includes a solvent may enable a wide variety of compositions to be used to form a coating. In addition, the layer is cured by irradiating the layer for a short time to form a coating layer, which can improve the processing efficiency and reduce the manufacturing cost. Furthermore, the solvent-free composition may reduce the incidence of visual defects (e.g., bubbles generated by volatile gases upon evaporation of any solvent) in the resulting coating. Providing the composition with additional functionalized oligomeric silsesquioxane to form the layer may further increase the hardness of the resulting coating and/or coated article. Providing a composition that does not contain a photoinitiator (e.g., a thermosetting composition) may not present yellowing problems. Providing a silane coupling agent can increase the adhesion of the coating to a substrate (e.g., glass-based substrate, polymer-based substrate). In addition, the coating may include high light transmittance (e.g., about 90% or greater), low haze (e.g., about 0.5% or less), and/or low yellowing index (e.g., about 0.6 or less). Providing a composition that is substantially free and/or free of nanoparticles (e.g., silica nanoparticles, alumina nanoparticles) may reduce handling problems (e.g., agglomeration, aggregation, phase separation) of the composition, 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 resulting coating and/or coated article, and reduce mechanical properties (e.g., hardness, modulus, strain) of the resulting coating and/or coated article, as compared to a corresponding composition, coating and/or coated article that includes a plurality of functionalized oligomeric silsesquioxanes without nanoparticles (e.g., silica nanoparticles, alumina nanoparticles).

Some example aspects of the disclosure are described below, but it should be understood 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 first major surface; and

a coating disposed on the first major surface, the coating comprising a plurality of functionalized oligomeric silsesquioxanes, a first functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes bound to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes through a linking group that is terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group,

wherein the coating comprises a pen hardness of about 5H or greater.

Aspect 2 the coated article of aspect 1, further comprising a silane coupling agent that adheres the coating to the first major surface.

Aspect 3. The coated article of aspect 2, wherein the silane coupling agent is selected from the group consisting of: (3-triethoxysilyl) propylsuccinic anhydride, (3-mercaptopropyl) trimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

Aspect 4 the coated article of any one of aspects 1-3, wherein the coating comprises an adhesion to the substrate of about 1B or greater after 10 days in a 95% relative humidity, 65 ℃ environment.

Aspect 5. A coated article comprising a substrate, comprising:

a substrate comprising a first major surface;

a coating disposed on the first major surface comprising a plurality of functionalized oligomeric silsesquioxanes, the plurality of functionalized oligomeric silsesquioxanes comprising a first functionalized oligomeric silsesquioxane and a second functionalized oligomeric silsesquioxane; and

a silane coupling agent adhering the coating to the first major surface, the silane coupling agent selected from the group consisting of: (3-triethoxysilyl) propylsuccinic anhydride, (3-mercaptopropyl) trimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane,

wherein the coating comprises an adhesion to the substrate of about 1B or greater after 10 days in a 65 ℃ environment at 95% relative humidity, and the coating comprises a pen hardness of about 5H or greater.

Aspect 6 the coated article of aspect 5, wherein the first functionalized oligomeric silsesquioxane is bound to a second functionalized oligomeric silsesquioxane by a linking group that is terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group.

Aspect 7 the coated article of any one of aspects 4-6, wherein the adhesion of the coating to the substrate after 10 days in a 95% relative humidity, 65 ℃ environment is about 3B or greater.

Aspect 8 the coated article of any one of aspects 1-4 or 6, comprising an endpoint, wherein the first functional group is the same as the second functional group.

Aspect 9 the coated article of any one of aspects 1 to 4, 6 or 8, comprising an endpoint, wherein the first functional group is selected from the group consisting of: alcohol, acrylate, epoxide and urea groups, and the second functional group is selected from the group consisting of: alcohols, acrylates, epoxides, and ureido groups.

Aspect 10 the coated article of any one of aspects 1 to 4, 6 or 8, comprising an endpoint, wherein the first functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides, and/or the second functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides.

Aspect 11 the coated article of aspect 10, wherein the first functional group and/or the second functional group comprises an amine.

Aspect 12 the coated article of aspect 11, the first functional group and/or the second functional group comprising an aminopropyl functional group.

Aspect 13. The coated article of aspect 10, wherein the first functional group and/or the second functional group comprises an epoxide.

Aspect 14. The coated article of aspect 10, wherein the first functional group and/or the second functional group comprises an anhydride.

Aspect 15 the coated article of any one of aspects 13-14, wherein the coating further comprises a curing catalyst comprising a tertiary amine or imidazole.

Aspect 16 the coated article of aspect 15, wherein the curing catalyst comprises 2,4, 6-tris (dimethylaminoethyl) phenol.

Aspect 17 the coated article of any one of aspects 15-16, wherein the coating comprises the curing catalyst in an amount of about 0.3wt% to about 1.1 wt%.

Aspect 18 the coated article of any one of aspects 13-17, wherein the coating further comprises a trimethylolpropane oxetane in an amount of about 5wt% to about 30 wt%.

Aspect 19 the coated article of aspect 18, wherein the ratio of the amount of weight percent of the linking group to the amount of weight percent of trimethylolpropane oxetane is in the range of about 1 to about 3.3.

Aspect 20 the coated article of any one of aspects 13-19, wherein the linking group comprises a plurality of linking groups, the ratio of the plurality of linking groups on a molar basis to the plurality of functionalized oligomeric silsesquioxanes on a molar basis being in the range of about 0.6 to about 1.0.

Aspect 21 the coated article of any one of aspects 1-4, 6, or 8-19, comprising an endpoint, wherein the linking group comprises a plurality of linking groups, the ratio of the plurality of linking groups on a molar basis to the plurality of functionalized oligomeric silsesquioxanes on a molar basis being about 0.06 or less.

Aspect 22 the coated article of any one of aspects 1-4, 6, or 8-21, comprising an endpoint, wherein the coating comprises the linking group in an amount of about 15wt% to about 50 wt%.

Aspect 23 the coated article of any one of aspects 1 to 4, 6 or 8 to 22, comprising an endpoint wherein the backbone of the linking group comprises an oxygen atom.

Aspect 24 the coated article of any one of aspects 1-4, 6, or 8-22, comprising an endpoint, wherein the linking group comprises a polymer.

Aspect 25 the coated article of aspect 24, wherein the first functional group and/or the second functional group is different from the normal terminal functional group of the polymer.

Aspect 26 the coated article of any one of aspects 24-25, wherein the polymer is substantially free of urethane, acrylate, and/or polycarbonate.

Aspect 27 the coated article of any one of aspects 24-26, wherein the polymer comprises oxygen atoms in the backbone of the polymer. Oxygen atoms are present in the various monomers of the polymer.

Aspect 28 the coated article of any one of aspects 24-27, wherein the polymer comprises poly (dimethylsiloxane) and/or poly (propylene oxide).

Aspect 29 the coated article of any one of aspects 24-28, wherein the polymer comprises a number average molecular weight in the range of about 400 daltons to about 30,000 daltons.

Aspect 30 the coated article of any one of aspects 1-29, wherein the plurality of functionalized oligomeric silsesquioxanes comprises a plurality of functionalized polyhedral oligomeric silsesquioxanes (POSS), the first functionalized oligomeric silsesquioxanes comprises a first functionalized POSS of the plurality of functionalized POSS, and the second functionalized oligomeric silsesquioxanes comprises a second functionalized POSS of the plurality of functionalized POSS.

Aspect 31 the coated article of any one of aspects 1-30, wherein the first functionalized oligomeric silsesquioxane and/or the second functionalized oligomeric silsesquioxane is functionalized with a epoxypropyl functional group or an epoxycyclohexyl functional group.

Aspect 32 the coated article of aspect 31, wherein the glycidoxypropyl functional group comprises a 3-glycidoxypropyl functional group.

Aspect 33 the coated article of any one of aspects 1-32, wherein the pen hardness of the coating is about 9H.

Aspect 34 the coated article of any one of aspects 1-33, wherein the coating comprises an average transmittance of about 90% or more on average over light wavelengths in the range of 400 nm to 700 nm.

Aspect 35 the coated article of aspect 34, wherein the average transmittance of the coating is in the range of about 92 percent to about 94 percent.

Aspect 36 the coated article of any one of aspects 1-35, wherein the coating comprises a haze of about 0.5% or less.

Aspect 37 the coated article of aspect 36, wherein the haze of the coating is in the range of about 0.1% to about 0.3%.

Aspect 38 the coated article of any one of aspects 1-37, wherein the coating is substantially free of visible crystals at 100-fold magnification.

Aspect 39 the coated article of any one of aspects 1-38, wherein the coating is substantially free of fluorine-based compounds.

Aspect 40 the coated article of any one of aspects 1-39, wherein the coating further comprises silica nanoparticles and/or alumina nanoparticles.

Aspect 41 the coated article of any one of aspects 1-39, wherein the coating is free of nanoparticles.

Aspect 42 the coated article of any one of aspects 1-41, wherein the coating further comprises a third functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes directly bonded to a fourth functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes.

Aspect 43 the coated article of any one of aspects 1-42, wherein a contact angle of deionized water on the coating is in a range of about 65 ° to about 110 °.

Aspect 44 the coated article of aspect 43, wherein the contact angle is in the range of about 90 ° to about 105 °.

Aspect 45 the coated article of any one of aspects 1-44, wherein the dynamic coefficient of friction of the coating is in the range of about 0.3 to about 0.8.

Aspect 46 the coated article of aspect 45, wherein the dynamic coefficient of friction is in the range of about 0.3 to about 0.5.

Aspect 47 the coated article of any one of aspects 1-46, wherein the coating comprises a yellowing index of about 0.6 or less.

Aspect 48 the coated article of aspect 47, wherein the yellowing index of the coating is in the range of about 0.45 to about 0.55.

Aspect 49 the coated article of any one of aspects 1-48, wherein the coated article withstands 10 days without visible delamination or visible cracking in a 95% relative humidity, 65 ℃ environment.

Aspect 50 the coated article of any one of aspects 1-49, wherein the coating comprises a Young's modulus (Young's modulus) of about 500 megapascals or greater.

Aspect 51. The coated article of aspect 50, wherein the young's modulus of the coating is in the range of about 800MPa to about 2,000 MPa.

Aspect 52 the coated article of any one of aspects 1-51, wherein the coating comprises a tensile strength of about 2 megapascals or greater.

Aspect 53 the coated article of any one of aspects 1-52, wherein the coating comprises a final elongation of about 3% or greater.

Aspect 54 the coated article of aspect 53, wherein the final elongation of the coating is in the range of about 4% to about 20%.

Aspect 55 the coated article of any one of aspects 1-54, wherein the coating comprises a third major surface facing the first major surface and a fourth major surface opposite the third major surface, the thickness of the coating defined between the third major surface and the fourth major surface being in the range of about 1 micron to about 200 microns.

Aspect 56 the coated article of aspect 55, wherein the coating thickness is in the range of about 3 microns to about 30 microns.

Aspect 57 the coated article of any one of aspects 1-56, wherein the substrate comprises a glass-based substrate and/or a ceramic-based substrate.

Aspect 58 the coated article of any one of aspects 1-57, wherein the substrate comprises a substrate thickness measured between the first major surface and a second major surface opposite the first major surface. The substrate thickness is in the range of about 25 microns to about 300 microns.

Aspect 59 the coated article of aspect 58, wherein the coated article achieves a parallel plate distance in the range of about 3 millimeters to about 10 millimeters.

Aspect 60 the coated article of aspect 58, wherein the coated article achieves a parallel plate distance of 4 millimeters.

Aspect 61 the coated article of any one of aspects 58-60, wherein the coated article can withstand a pen drop height of 15 centimeters.

Aspect 62. A method of making a coated article, comprising:

depositing a layer comprising a plurality of functionalized oligomeric silsesquioxanes on a first major surface of a substrate, a first functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes being bound to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes through a linking group that is terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group; and

The layer is cured to form a coating.

Aspect 63. The method of aspect 62, wherein the first functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides, and the second functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides.

Aspect 64 the method of aspect 63, wherein the first functional group and/or the second functional group comprises an amine.

Aspect 65 the method of aspect 64, wherein the first functional group and/or the second functional group comprises an aminopropyl functional group.

Aspect 66 the method of any one of aspects 62-65, wherein the first functional group is the same as the second functional group.

Aspect 67 the method of any one of aspects 62 to 66, wherein the plurality of functionalized oligomeric silsesquioxanes comprises another functionalized oligomeric silsesquioxanes that are not bound to the linking group, the first major surface, or another functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes prior to curing.

Aspect 68 the method of any one of aspects 62-67, wherein the layer comprises a reactive diluent. The reactive diluent reacts with another functionalized oligomeric silsesquioxane of the plurality of functionalized silsesquioxanes during curing.

Aspect 69 the method of aspect 68, wherein the reactive diluent comprises a third functional group and a fourth functional group, and the linking group is bound to the mono-functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes through the third functional group.

Aspect 70. A method of making a coated article, comprising:

depositing a layer on the first major surface of the substrate, the layer comprising a plurality of functionalized oligomeric silsesquioxanes and a linking group, the linking group comprising a reactive diluent; and

curing the layer to form a coating, wherein the linking group reacts with the plurality of functionalized oligomeric silsesquioxanes to bind a first functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes, the linking group including a third functional group bound to the first functionalized oligomeric silsesquioxanes and a fourth functional group bound to the second functionalized oligomeric silsesquioxanes.

Aspect 71 the method of any one of aspects 69 to 70 wherein the third functional group is selected from the group consisting of: acid alcohol, acrylate, anhydride, alcohol, epoxide, isocyanate, and urea groups, and/or the fourth functional group is selected from the group consisting of: acid alcohols, acrylic esters, anhydrides, alcohols, epoxides, isocyanates, and ureido groups.

Aspect 72 the method of any one of aspects 69 to 71 wherein the third functional group is the same as the fourth functional group.

Aspect 73 the method of any one of aspects 68-72, wherein the reactive diluent comprises three or more reactive functional groups.

Aspect 74 the method of any one of aspects 68-73, wherein the layer comprises the reactive diluent in an amount of about 15wt% to about 50 wt%.

Aspect 75 the method of any one of aspects 62-74, wherein curing the layer comprises affecting the layer with radiation, the layer further comprising a photoinitiator.

Aspect 76. The method of aspect 75, wherein the photoinitiator comprises a cationic photoinitiator.

Aspect 77. The method of aspect 75, wherein the photoinitiator comprises a free radical photoinitiator.

Aspect 78 the method of any one of aspects 75 to 77, wherein affecting the material with radiation comprises using a total energy density of about 2 joules per square centimeter (J/cm) ² ) To about 15J/cm ² Ultraviolet light in the range affects the material.

Aspect 79 the method of any one of aspects 62-78, wherein depositing the layer comprises depositing particles on the first major surface.

Aspect 80. A method of making a coated article, comprising:

Depositing a layer on a first major surface of a substrate, the layer comprising a plurality of functionalized oligomeric silsesquioxanes and a linking group, the linking group terminating with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group, the first functional group and the second functional group each selected from the group consisting of amine and anhydride functional groups; and

curing the layer to form a coating, wherein the linking group reacts with the plurality of functionalized oligomeric silsesquioxanes to bind a first functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes.

Aspect 81 the method of aspect 80, wherein the coating further comprises a curing catalyst comprising a tertiary amine and an imidazole.

Aspect 82. The method of aspect 81, wherein the curing catalyst comprises 2,4, 6-tris (dimethylaminoethyl) phenol.

Aspect 83 the method of any one of aspects 81-82, wherein the layer comprises the curing catalyst in an amount of about 0.3wt% to about 1.1 wt%.

Aspect 84 the method of any one of aspects 80-83, wherein the coating further comprises trimethylolpropane oxetane in an amount of about 5wt% to about 30 wt%.

Aspect 85 the method of aspect 84, wherein the ratio of the amount of wt% of the linking group to the amount of wt% of the trimethylolpropane oxetane is in the range of about 1 to about 3.3.

Aspect 86 the method of any one of aspects 80-85, wherein the linking group comprises a plurality of linking groups, the ratio of the plurality of linking groups on a molar basis to the plurality of functionalized oligomeric silsesquioxanes on a molar basis being in the range of about 0.6 to about 1.0.

Aspect 87 the method of any of aspects 62-74 or 80-86, comprising an endpoint, wherein the layer comprises a viscosity in the range of about 0.01 pa-sec to about 6 pa-sec.

Aspect 88 the method of any one of aspects 62-74 or 80-87, comprising an endpoint, wherein depositing the layer comprises spin coating.

Aspect 89 the method of any of aspects 62-74 or 80-88, comprising an endpoint, wherein depositing the layer comprises pulling an applicator rod through the first major surface.

Aspect 90 the method of any one of aspects 62 to 74 or 80 to 89, comprising an endpoint wherein curing the layer comprises heating the layer.

Aspect 91 the method of aspect 90, wherein heating the layer comprises heating the layer at a temperature in the range of about 60 ℃ to about 150 ℃ for a period in the range of about 30 minutes to about 8 hours.

Aspect 92 the method of aspect 90, wherein heating the layer comprises heating the layer at a temperature in the range of about 75 ℃ to about 250 ℃ for a period in the range of about 15 minutes to about 4 hours.

Aspect 93 the method of aspect 90, wherein heating the layer comprises heating the layer at a temperature in the range of about 100 ℃ to about 175 ℃ for a period in the range of about 15 minutes to about 120 minutes.

Aspect 94 the method of any one of aspects 62-93, wherein the plurality of functionalized oligomeric silsesquioxanes comprises a plurality of functionalized polyhedral oligomeric silsesquioxanes (POSS), the first functionalized oligomeric silsesquioxanes comprises a first functionalized POSS of the plurality of functionalized POSS, and the second functionalized oligomeric silsesquioxanes comprises a second functionalized POSS of the plurality of functionalized POSS.

Aspect 95 the method of any one of aspects 62 to 94, wherein the first functionalized oligomeric silsesquioxane and/or the second functionalized oligomeric silsesquioxane is functionalized with a epoxypropyl functional group or an epoxycyclohexyl functional group.

Aspect 96 the method of aspect 95, wherein the glycidoxypropyl functional group comprises a 3-glycidoxypropyl functional group.

Aspect 97 the method of any of aspects 62-96, wherein the backbone of the linking group comprises an oxygen atom.

Aspect 98 the method of any one of aspects 62-97, wherein the linking group comprises a polymer.

The method of aspect 99, aspect 98, wherein the polymer comprises oxygen atoms in the backbone of the polymer, and the oxygen atoms are present in monomers of the polymer.

Aspect 100 the method of any one of aspects 98-99, wherein the first functional group and/or the second functional group is different from the normal terminal functional group of the polymer.

Aspect 101 the method of any one of aspects 98-100, wherein the polymer comprises poly (dimethylsiloxane) and/or poly (propylene oxide).

Aspect 102 the method of any one of aspects 98-101, wherein the polymer comprises a number average molecular weight in a range of about 400 daltons to about 30,000 daltons.

Aspect 103 the method of any one of aspects 98-102, wherein the polymer is substantially free of urethane, acrylate, and/or polycarbonate.

Aspect 104 the method of any one of aspects 62-103, wherein the coating is substantially free of fluorine-based compounds.

Aspect 105 the method of any one of aspects 62 to 104, wherein the coating further comprises silica nanoparticles and/or alumina nanoparticles.

Aspect 106 the method of any one of aspects 62 to 104, wherein the coating is free of nanoparticles.

Aspect 107 the method of any one of aspects 62 to 106, wherein the coating further comprises a third functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes that is directly bound to a fourth functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes.

Aspect 108 the method of any one of aspects 62-107, further comprising depositing a silane coupling agent on the first major surface prior to depositing the layer.

The method of aspect 109, wherein the silane coupling agent comprises a mercapto-functional silane.

The method of any one of aspects 62 to 109, wherein the layer further comprises a silane coupling agent.

Aspect 111 the method of aspect 108 or aspect 110, wherein the silane coupling agent is selected from the group consisting of: (3-triethoxysilyl) propylsuccinic anhydride, (3-mercaptopropyl) trimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

Aspect 112 the method of aspect 108 or aspect 110, wherein the silane coupling agent comprises a compound selected from the group consisting of: epoxide and amine functional groups.

Aspect 113 the method of aspect 108 or aspect 112, wherein the coating comprises an adhesion to the substrate of about 1B or greater after 10 days in a 95% relative humidity, 65 ℃ environment.

Aspect 114 the method of aspect 113, wherein the adhesion of the coating to the substrate is about 3B or greater after 10 days in a 95% relative humidity, 65 ℃ environment.

Aspect 115 the method of any one of aspects 62-114, wherein the coating comprises a pen hardness of about 5H or greater.

Aspect 116. The method of aspect 115, wherein the pen hardness of the coating is about 9H.

Aspect 117 the method of any one of aspects 62-116, wherein the coating comprises an average transmittance of about 90 percent or higher on average over light wavelengths in the range of 400 nanometers to 700 nanometers.

Aspect 118 the method of aspect 117, wherein the average light transmittance is in the range of about 92 to about 94 percent.

Aspect 119 the method of any one of aspects 62-118, wherein the coating comprises a haze of about 0.5% or less.

Aspect 120 the method of aspect 119, wherein the haze is in the range of about 0.1% to about 0.3%.

Aspect 121 the method of any one of aspects 62-120, wherein the coating is substantially free of visible crystals at 100-fold magnification.

Aspect 122 the method of any of aspects 62-121, wherein a contact angle of deionized water on the coating is in a range of about 65 ° to about 110 °.

Aspect 123 the method of aspect 122, wherein the contact angle is in the range of about 90 ° to about 105 °.

Aspect 124 the method of any one of aspects 62-123, wherein the dynamic coefficient of friction of the coating is in the range of about 0.3 to about 0.8.

Aspect 125 the method of aspect 124, wherein the dynamic coefficient of friction is in the range of about 0.3 to about 0.5.

Aspect 126 the method of any one of aspects 62-125, wherein the coating comprises a yellowing index of about 0.6 or less.

Aspect 127 the method of any one of aspects 62-126, wherein the coated article withstands 10 days without visible delamination or visible cracking in a 95% relative humidity, 65 ℃ environment.

Aspect 128 the method of any one of aspects 62-127, wherein the coating comprises a young's modulus of about 500 megapascals or more.

Aspect 129 the method of any of aspects 62-128, wherein the coating comprises a tensile strength of about 2 megapascals or greater.

Aspect 130 the method of any one of aspects 62-129, wherein the coating comprises a final elongation of about 3% or greater.

Aspect 131 the method of any one of aspects 62-130, wherein the coating comprises a third major surface facing the first major surface and a fourth major surface opposite the third major surface, the thickness of the coating defined between the third major surface and the fourth major surface being in the range of about 1 micron to about 200 microns.

Aspect 132 the method of aspect 131, wherein the coating thickness is in the range of about 3 microns to about 30 microns.

Aspect 133 the method of any one of aspects 62-132, wherein the substrate comprises a glass-based substrate and/or a ceramic-based substrate.

Aspect 134 the method of aspect 133, wherein the coated article achieves a parallel plate distance in the range of about 3 millimeters to about 10 millimeters.

Aspect 135. The method of aspect 133, wherein the coated article achieves a parallel plate distance of 4 millimeters.

Aspect 136 the method of any one of aspects 133-135, wherein the coated article can withstand a pen drop height of 15 centimeters.

Aspect 137. A method of forming a composition comprising:

reacting a plurality of functionalized oligomeric silsesquioxanes with a linking group terminating with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group,

wherein a first functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes has a functionalized moiety that reacts with the first functional group of the linking group and a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes has a functionalized moiety that reacts with the second functional group of the linking group.

Aspect 138 the method of aspect 137, wherein the linking group comprises a plurality of linking groups, the ratio of the plurality of polymers on a molar basis to the plurality of functionalized oligomeric silsesquioxanes on a molar basis being about 0.06 or less.

Aspect 139 the method of aspect 137, wherein the composition comprises the linking group in an amount of about 15wt% to about 50 wt%.

Aspect 140 the method of aspect 137, wherein the linking group comprises a plurality of linking groups, the ratio of the plurality of linking groups on a molar basis to the plurality of functionalized oligomeric silsesquioxanes on a molar basis being in the range of about 0.6 to about 1.0.

The method of any one of aspects 137-140, wherein the reaction is substantially solvent-free.

The method of any one of aspects 137-140, wherein the reaction further comprises a solvent selected from the group consisting of: butyl acetate, propyl acetate, and acetonitrile.

Aspect 143 the method of aspect 142, further comprising removing the solvent after the reacting.

The method of any one of aspects 137-143, wherein the composition is substantially visually transparent.

Aspect 145 the method of any of aspects 137-144, wherein the plurality of functionalized oligomeric silsesquioxanes comprises a plurality of functionalized polyhedral oligomeric silsesquioxanes (POSS), the first functionalized oligomeric silsesquioxanes comprises a first functionalized POSS of the plurality of functionalized POSS, and the second functionalized oligomeric silsesquioxanes comprises a second functionalized POSS of the plurality of functionalized POSS.

Aspect 146 the method of any one of aspects 137-145, wherein the first functionalized oligomeric silsesquioxane and/or the second functionalized oligomeric silsesquioxane is functionalized with epoxypropyl functionality.

Aspect 147 the method of aspect 146, wherein the glycidoxypropyl functional group comprises a 3-glycidoxypropyl functional group.

The method of any one of aspects 137-147, wherein the first functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides, and the second functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides.

Aspect 149 the method of aspect 148, wherein the first functional group and/or the second functional group comprises an amine.

Aspect 150 the method of aspect 149, wherein the first functional group and/or the second functional group comprises an aminopropyl functional group.

Aspect 151 the method of any one of aspects 137-147, wherein the first functional group and/or the second functional group comprises an epoxide.

The method of any of aspects 137-147 wherein the first functional group and/or the second functional group comprises an anhydride.

The method of any one of aspects 137-152, wherein the coating further comprises a curing catalyst comprising a tertiary amine and an imidazole.

Aspect 154 the method of aspect 153, wherein the curing catalyst comprises 2,4, 6-tris (dimethylaminoethyl) phenol.

Aspect 155 the method of any one of aspects 152-154, wherein the composition comprises the curing catalyst in an amount of about 0.3wt% to about 1.1 wt%.

The method of any one of aspects 151 to 155, wherein the coating further comprises trimethylolpropane oxetane in an amount of about 5wt% to about 30 wt%.

Aspect 157 the method of aspect 156, wherein the ratio of the amount of wt% of the linking group to the amount of wt% of the trimethylolpropane oxetane is in the range of about 1 to about 3.3.

Aspect 158 the method of aspects 137-157, wherein the first functional group is selected from the group consisting of: acid alcohol, acrylate, anhydride, alcohol, epoxide, isocyanate, and urea groups, and the second functional group is selected from the group consisting of: acid alcohols, acrylic esters, anhydrides, alcohols, epoxides, isocyanates, and ureido groups.

Aspect 159 the method of any one of aspects 137-158, wherein the first functional group is the same as the second functional group.

The method of any one of aspects 137-159, wherein the backbone of the linking group comprises an oxygen atom.

Aspect 161 the method of any of aspects 137-159 wherein the linking group comprises a polymer.

Aspect 162 the method of aspect 161, wherein the first functional group and/or the second functional group is different from the normal terminal functional group of the polymer.

Aspect 163 the method of any of aspects 161-162, wherein the polymer is substantially free of urethane, acrylate, and/or polycarbonate.

Aspect 164 the method of any one of aspects 161-162 wherein the polymer includes oxygen atoms in the backbone of the polymer and the oxygen atoms are present in monomers of the polymer.

Aspect 165 the method of any one of aspects 161-164, wherein the polymer comprises poly (dimethylsiloxane) and/or poly (propylene oxide).

Aspect 166 the method of any one of aspects 161 through 165, wherein the polymer comprises a number average molecular weight in the range of about 400 daltons to about 30,000 daltons.

Aspect 167 the method of any of aspects 137-166, wherein the coating is substantially free of fluorine-based compounds.

Aspect 168 the method of any of aspects 137-167, wherein the coating further comprises silica nanoparticles and/or alumina nanoparticles.

Aspect 169 the method of any one of aspects 137-167, wherein the coating is free of nanoparticles.

Aspect 170 the method of any one of aspects 137-169, wherein the coating further comprises a third functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes that is directly bound to a fourth functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes.

Throughout this disclosure, the drawings serve to emphasize certain aspects. Thus, unless expressly indicated otherwise, it should not be assumed that the relative sizes of the various regions, portions and substrates illustrated in the drawings are proportional to their actual relative sizes.

Drawings

The foregoing and other features and advantages of aspects of the disclosure will be better understood upon reading the following detailed description with reference to the drawings in which:

FIGS. 1-3 are schematic views of an example coated article in a flat configuration according to aspects, wherein the schematic view of a folded configuration may be presented as shown in FIG. 4;

FIG. 4 is a schematic illustration of an example coated article of aspects of the present disclosure in a folded configuration, wherein the schematic illustration of a flat configuration may be presented as shown in FIGS. 1-3;

FIGS. 5-7 are cross-sectional views of a testing apparatus for determining a minimum parallel plate distance along line 5-5 of FIG. 4 for an example modified coated article;

Fig. 8-10 schematically illustrate reactions of materials used to form coatings and/or coated articles according to aspects of the present disclosure;

FIG. 11 is a schematic plan view of an example consumer electronic device in accordance with aspects;

FIG. 12 is a schematic perspective view of the example consumer electronic device of FIG. 11;

FIG. 13 is a flow chart illustrating an example method of manufacturing a coating and/or coated article according to aspects of the present disclosure; and

fig. 14-19 schematically illustrate steps in a method of manufacturing a coated article according to aspects of the present disclosure.

Detailed Description

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

The compositions and/or coatings of aspects of the present disclosure may be used in, for example, the coated articles 101, 201, 301, 401, 601, and/or 701 shown in fig. 1-3 and 5-7, respectively. However, it should be understood that the compositions, coatings, and/or coated articles are not limited to such applications and may be used in other applications. Unless otherwise indicated, discussion of features of aspects of a composition, coating, or coated article applies equally to corresponding features of any aspect of the present disclosure. For example, the same part numbers throughout the disclosure may indicate that, in some aspects, the identified features are identical to each other and that discussion of the identified features of one aspect may apply equally to the identified features of any other aspect of the disclosure unless otherwise indicated.

Aspects of the present disclosure may include compositions. The composition may include a variety of functionalized oligomeric silsesquioxanes. As used herein, functionalized oligomeric silsesquioxanes are meant to include at least two species represented as RSiO _1.5 There are three oxygen atoms in which the other monomer to which it is bound shares each oxygen atom, and R is a functional group that "functionalizes" the oligomeric silsesquioxane to form a functionalized oligomeric silsesquioxane, although R of one monomer need not be the same as R of the other monomer. In aspects, RSiO in functionalized oligomeric silsesquioxanes _1.5 The number of monomers 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 number of monomers may be an integer in the range of 4 to 50, 4 to 30, 4 to 20, 6 to 16, 6 to 12, 8 to 10, or any range or subrange therebetween. For example, the leftmost compounds of FIGS. 8-10 show functionalized oligomeric silsesquioxanesExamples are shown.

In aspects, in addition to RSiO discussed above _1.5 The functionalized oligomeric silsesquioxane may further include any number of RSiO in addition to monomer units ₂ Monomers, where R may also be at RSiO ₂ Monomers and RSiO _1.5 One or both of the monomers may vary. In other aspects, RSiO ₂ The monomer may be a terminal monomer, meaning that it is linked to only one other monomer. For simplicity, these "terminal monomers" will be referred to as RSiO ₂ Wherein it is understood that terminal RSiO ₂ The monomers may be referred to as 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 of a single-ended monomer may be the same as or different from another (e.g., one, all) R of the same single-ended monomer. In other aspects, RSiO ₂ The monomer may be bonded to two other monomers. For example, RSiO ₂ Monomers can be bound to another RSiO ₂ And RSiO _1.5 Monomers or two RSiO _1.5 And (3) a monomer. For simplicity, "non-terminal RSiO ₂ Monomer "may refer to RSiO ₃ 、RSiO ₂ 、R ₂ SiO ₃ Or R is ₂ SiO ₂ Wherein a single "non-terminal RSiO ₂ "first R of monomers may be the same single" non-terminal RSiO ₂ The other (e.g., one, all) R of the monomers "are the same or different. In other aspects, RSiO ₂ The number of monomers may be less than or equal to RSiO _1.5 Number of monomers. For example, when RSiO ₂ The number of monomers was 4 and RSiO _1.5 When the number of monomers is 4 or greater, a ladder-functional oligomeric silsesquioxane may be formed wherein RSiO _1.5 Each of the monomers is combined with two other rsios _1.5 Monomer and RSiO _1.5 Monomers or an RSiO ₂ And (3) monomer connection. In even other aspects, the leftmost compound of fig. 8 may include a ladder-functionalized oligomeric silsesquioxane, e.g., when block 803 has Si atoms bound to R groups and Si atoms bound to non-terminal endsRSiO ₂ R2 radical of a monomer, RSiO _1.5 The R3 group of the monomer, and block 803 includes three or more additional rsios that may be terminal or non-terminal _1.5 Monomer and two other RSiO ₂ And (3) monomer.

In other aspects, the functionalized oligomeric silsesquioxane may include 1 to 3 rsios ₂ Monomers (e.g., 1, 2, 3). In even other aspects, an adjacent pair of rsios _1.5 The monomers may be connected to each other by two or more non-overlapping paths, wherein each path includes at least one pair of RSiO other than adjacent pairs _1.5 The first path is connected to the second path without passing through an adjacent pair of monomers. For example, an open cage functionalized oligomeric silsesquioxane may include an adjacent pair of rsios connected to each other by two or more non-overlapping pathways _1.5 Monomers, and the first path is connected to the second path without passing through an adjacent pair of monomers, while the silsesquioxane further includes 1 to 3 RSiO' s ₂ And (3) a monomer. In even other aspects, the leftmost compound of fig. 8 may include an open-cage functionalized oligomeric silsesquioxane, e.g., when block 803 brings one or more of the illustrated Si atoms into RSiO _1.5 Monomers such that RSiO ₂ The total number of monomers is 1 to 3, and adjacent pair of RSiO _1.5 The cells are connected to each other by two or more non-overlapping paths, and the first path is connected to the second path without passing through an adjacent pair of cells.

In aspects, the functionalized oligomeric silsesquioxane may be prepared from RSiO _1.5 Monomer composition. As used herein, polyhedral oligomeric silsesquioxane (POSS) refers to a polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane) defined by RSiO _1.5 Functionalized oligomeric silsesquioxanes of monomeric composition. Exemplary aspects of the functionalized POSS may include 6, 8, 10, or 12 rsios _1.5 Monomers, although other aspects are possible. For example, from 8 RSiO _1.5 The functionalized oligomeric silsesquioxanes of monomer composition are octahedral functionalized POSS (e.g., polyoctahedral silsesquioxanes). As shown in fig. 9-10, the leftmost compound is a functionalized POSS, i.e., an octahedral functionalized POSS.

In aspects, the functionalized oligomeric silsesquioxanes may be prepared fromThe condensation reaction of the silane forms. As used herein, the condensation reaction produces an R2O byproduct, where R may include any of the R units discussed below and may further include hydrogen (e.g., having a hydroxyl group or a water byproduct). For example, silanes (e.g. R ₃ OSi) can react to form terminal RSiO ₂ And (3) a monomer. For example, terminal RSiO ₂ The monomer being capable of reacting with another RSiO ₂ Monomers (e.g. terminal, non-terminal) react to form RSiO _1.5 Monomers, because the oxygen atom of one monomer forms a bond with the silicon atom of another monomer, produce condensation byproducts. It should be understood that RSiO _1.5 The silsesquioxane monomers are different from the siloxane monomers, which may include M-type siloxane monomers (e.g., R ₃ SiO _0.5 ) D-type siloxane monomers (e.g. R ₂ SiO ₂ ) And/or a silicon-type siloxane monomer (SiO) ₂ )。

The functionalized oligomeric silsesquioxane may be functionalized with one or more functional groups. As used herein, the functional groups of the functionalized oligomeric silsesquioxane may exclude hydrogen, bisphenol, and/or fluorine containing functional groups. In aspects, the functional groups of the functionalized oligomeric silsesquioxane may exclude isocyanates, olefins, and/or alkynes. In aspects, the functional groups for the functionalized oligomeric silsesquioxanes may include epoxides, epoxypropyl, oxiranes, thiols, anhydrides, isocyanates, acrylates, and methacrylates. In other aspects, the functional group for the functionalized oligomeric silsesquioxane may be a epoxypropyl functional group or an epoxycyclohexyl functional group. Throughout this disclosure, functionalized POSS functionalized by epoxypropyl groups is referred to as GPOSS. Exemplary aspects of glycidoxy functional groups include glycidoxylamine, glycidoxyalkyl (e.g., glycidoxypropyl), glycidoxylether (e.g., glycidoxy), glycidoxysiloxane (e.g., glycidoxypropyl), and combinations thereof (e.g., glycidoxypropyl dimethylsiloxy). Commercially available examples of GPOSS include 3-epoxypropyloxypropyl functionalized POSS (e.g., EP0408 (Hybrid Plastics), EP0409 (Hybrid Plastics)), 3-epoxypropyloxypropyl functionalized POSS (e.g., 560624 (Sigma Aldrich)), and 3-epoxypropyloxypropyl dimethylsiloxy (e.g., 593869 (Sigma Aldrich)). For example, the compounds on the left side in fig. 9-10 are GPOSS, i.e., 3-epoxypropyloxypropyl functionalized POSS. Exemplary aspects of epoxy functionality include epoxy, alkyl epoxy (e.g., epoxyethyl, epoxypropyl), and cycloalkyl epoxy (e.g., epoxycyclohexyl). Commercially available examples of epoxy functionalized POSS include (3, 4-epoxycyclohexyl) ethyl functionalized POSS (e.g., 560316 (Sigma Aldrich)). Exemplary aspects of thiols include mercaptoalkyl (e.g., mercaptopropyl), such as commercially available 3-mercaptopropyl functionalized POSS (e.g., 560375 (Sigma Aldrich), TH1550 (Hybrid Polymers), TH1555 (Hybrid Polymers), exemplary aspects of anhydrides include maleic anhydride, succinic anhydride, acetic anhydride, and alkyl anhydrides (e.g., acetic anhydride, propionic anhydride), exemplary aspects of isocyanates include isocyanates, alkyl isocyanates (e.g., isocyanatomethyl, isocyanatohexyl), cycloalkyl isocyanates (e.g., isophorone isocyanate, isocyanatocyclohexyl), and combinations thereof, exemplary aspects of acrylates include acrylates, alkyl acrylates (e.g., propenyl propyl, propenyl isobutyl), and cycloalkyl acrylates (propenyl cyclohexyl), commercially available examples of acrylate functionalized POSS include propenyl propyl functionalized POSS (e.g., MA0736 (Hybrid Polymers 070), and propenyl isobutyl functionalized POSS (e.g., MA 1 (Hybrid Polymers)). Methacrylates include methacrylates, alkyl methacrylates (e.g., methyl propenyl methyl, methyl propyl), cycloalkyl methacrylates (e.g., methyl allyl) and allyl (e.g., methyl) and allyl (methyl) esters (e.g., 6 s) of allyl (meth) functional groups (MA 0716) of these esters) Methylpropenyl propyl functional POSS (e.g., 534633 (Sigma Aldrich), MA0702 (Hybrid Polymers), MA0735 (Hybrid Polymers), MA0719 (Hybrid Polymers)) and (propylmethylpropenyl) cyclopentyl functional POSS (e.g., 560340 (Sigma Aldrich)). Exemplary aspects of olefins include allyl, vinyl, alkyl vinyl (e.g., vinyl propyl), cyclic olefins (e.g., cyclohexenyl), aromatics (e.g., vinyl phenyl), siloxane vinyl (e.g., vinyl siloxy), and combinations thereof (e.g., vinyl diphenyl siloxy, (cyclohexenyl) ethyl dimethyl siloxy). Commercially available aspects of olefin-functionalized POSS include allyl-functionalized POSS (e.g., OL1118 (Hybrid Polymers), vinyl diphenylsiloxy (e.g., 527300 (Sigma Aldrich)), vinyl-functionalized POSS (e.g., 475424 (Sigma Aldrich)), 560367 (Sigma Aldrich), OL1170 (Hybrid Polymers), OL1123 (Hybrid Polymers)), trivinylsiloxy-functionalized POSS (527327 (Sigma Aldrich)), and 2- (4-cyclohexenyl) ethyldimethylsiloxy-functionalized POSS (e.g., 593974 (Sigma Aldrich)). Providing a linking group comprising one or more amine and/or anhydride functionalities can provide a coating that has good adhesion to a substrate (e.g., about 4B or more when formed; about 4B or more after 10 days in a 50% relative humidity, 25 ℃ environment, and/or about 4B or more after 10 days in a 95% relative humidity, 65 ℃ environment), regardless of whether silane coupling agents are used.

As shown in fig. 8-10, the functionalized oligomeric silsesquioxane may be indicated as an R group (e.g., R, R, R3) by the functionalized position. As used herein, a functionalized oligomeric silsesquioxane is functionalized by at least one of the functional groups listed in the previous paragraph. In aspects, the functionalized oligomeric silsesquioxanes (e.g., functionalized POSS) may comprise two or more R groups comprising the functional groups listed in the previous paragraph for the functionalized oligomeric silsesquioxanes. In other aspects, substantially each R group of the functionalized oligomeric silsesquioxane may include the functional groups listed in the previous paragraph for the functionalized oligomeric silsesquioxane. In even other aspects, all R groups including the functional groups listed in the preceding paragraph may include the same functional groups. In even other aspects, the functionalized oligomeric silsesquioxane may be functionalized with two or more different functional groups as listed in the previous paragraph. In other aspects, referring to fig. 8, the functionalized oligomeric silsesquioxane may be functionalized with a first functional group (R) selected from those listed in the previous paragraph and a second functional group (R2) selected from those listed in the previous 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, referring to fig. 8, the third functional group (R3) of the functionalized oligomeric silsesquioxane may include hydrogen or alkyl, cycloalkyl, alcohol, or amine functional groups, without including one of the functional groups listed in the previous paragraph.

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

Compositions, coatings, and coated articles of aspects of the present disclosure can include a linking group (e.g., a polymer). In aspects, as an intermediate compound, as shown in fig. 8, the linking group includes a first functional group (e.g., X) at a first end and a second functional group (e.g., X) at a second end opposite the first end. In other aspects, as shown in fig. 9, the first functional group and the second functional group (e.g., the first functional group X and the second functional group X) may be the same. In other aspects, the second functional group may be different from the second functional group. In other aspects, as shown in fig. 8-10, the linking group may comprise a polymer. Providing a polymer that includes a first functional group at a first end and a second functional group at a second end opposite the first end may reduce (e.g., prevent) aggregation of a plurality of functionalized oligomeric silsesquioxanes, which may provide good optical properties (e.g., high light transmittance, low haze), and as a coating, good durability and/or good adhesion to a substrate.

As used herein, the first functional group and/or the second functional group may exclude hydrogen, bisphenol, and/or fluorine-containing functional groups. In aspects, the first functional group and/or the second functional group may exclude isocyanates, alkenes, and/or alkynes. In aspects, the first functional group and/or the second functional group may include acid alcohols, anhydrides, amides, amines, chlorides, cyanides, epoxides, thiols, magnesium halides, with the exclusion of fluorine and/or olefins. In other aspects, the first functional group and/or the second functional group may include an acid alcohol, an anhydride, an amide, and/or an amine. In even other aspects, the first functional group can include an amine. In yet other aspects, the first functional group and the second functional group may each comprise an amine. Exemplary aspects of amine functionality include aminopropyl. Exemplary aspects of the amine include primary alkylamines (e.g., aminopropyl), secondary alkylamines (e.g., methylaminopropyl, ethylaminoisobutyl), primary cycloalkylamines (e.g., aminocyclohexyl, hexamethylenediamine, trimethylhexamethylenediamine, isophoronediamine, 4' -methylene-bis [ 2-methylcyclohexylamine ], 4,7, 10-trioxa-1, 13-tridecanediamine), secondary cycloalkylamines (e.g., methylaminocyclohexyl), and combinations thereof. In yet other aspects, the first functional group and/or the second functional group may comprise an anhydride. Exemplary aspects of the acid anhydride include maleic anhydride, succinic anhydride, acetic anhydride, methylhexahydrophthalic anhydride, and alkyl anhydrides (e.g., acetic anhydride, propionic anhydride). In other aspects, the first functional group and/or the second functional group may comprise an epoxide. Exemplary aspects of epoxides include epoxides, alkyl epoxides (e.g., epoxyethyl, epoxypropyl), and cycloalkyl epoxides (e.g., epoxycyclohexyl). For the purpose of the first functional group and/or the second functional group, epoxypropyl groups are considered to be a class of epoxides. Exemplary aspects of the acid alcohol include carboxyl groups, alkylcarboxyl groups (e.g., propionic acid, stearic acid), cycloalkylcarboxyl groups (e.g., carboxycyclohexyl groups), aromatic carboxyl groups (e.g., benzoic acid), and combinations thereof. Exemplary aspects of the alcohols include hydroxyl, alkyl alcohols (e.g., ethoxy), cycloalkyl alcohols (e.g., hydroxycyclohexyl), geminal diols (e.g., methyl glycol), and ortho diols (e.g., 1, 2-ethyl glycol), and combinations thereof. Exemplary aspects of the amide include amides, alkylamides (amidopropyl) and cycloalkylamides (e.g., amidocyclohexyl) and combinations thereof. Exemplary aspects of the chloride include chloride, acid chloride (e.g., acyl chloride), alkyl chloride (e.g., chloropropyl), and combinations thereof. Exemplary aspects of cyanide include cyano, alkyl cyanide (e.g., cyanopropyl), cycloalkyl cyanide (cyanocyclohexyl), and combinations thereof. Exemplary aspects of thiols include thiols, mercaptoalkyl groups (e.g., mercaptopropyl groups), mercaptocycloalkyl groups (e.g., mercaptocyclohexyl groups), and combinations thereof. Exemplary aspects of magnesium halides (e.g., grignard reagent) include magnesium bromide and magnesium chloride. Exemplary aspects of olefins include allyl, vinyl, alkyl vinyl (e.g., vinyl propyl), cyclic olefins (e.g., cyclohexenyl), aromatics (e.g., vinyl phenyl), siloxane vinyl (e.g., vinyl siloxy), and combinations thereof (e.g., vinyl diphenyl siloxy, (cyclohexenyl) ethyl dimethyl siloxy). It is to be appreciated that the first functional group and/or the second functional group can include a variety of functional groups, e.g., the amine can include a variety of amine functionalities (e.g., diamine, triamine).

In aspects, the linking group (e.g., polymer) can include another functional group in addition to the first functional group and the second functional group. In other examples, the linking group may include a polymer comprising a branched polymer having more than two ends, such as a star polymer or a dendrimer. In other aspects, the number of functional groups on the polymer may be substantially equal to the number of chain ends (e.g., the number of arms in a star polymer or a dendritic polymer, i.e., the number of branches in a branched polymer plus 2).

Throughout this disclosure, the "normal terminal functional group" of a polymer refers to a functional group that may be present at one end of the polymer during the polymerization process. For example, the normal terminal functional group of the polyethylene is an olefin (e.g., allyl), the normal terminal functional group of the polyamide is an amine and/or carboxylic acid, and the normal terminal functional group of the polydimethylsiloxane is a silane. In aspects, the first functional group and/or the second functional group may be the same as the normal terminal functional group 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 can be different from the normal terminal functional group of the polymer and the second functional group can be different from the normal terminal functional group of the polymer. For example, the polymer may be polydimethylsiloxane having a first functional group comprising an amine and a second functional group comprising an amine.

The polymer may include a glass transition (Tg) temperature. As used herein, glass transition temperature, storage modulus over a range of temperatures, storage modulus (e.g., on a glass platform), and loss modulus (e.g., on a glass platform) are measured using kinetic analysis (Dynamic Mechanical Analysis; DMA) by an instrument such as DMA850 from TA Instruments. The sample for DMA analysis contained a membrane fixed by a tension clamp. As used herein, storage modulus refers to the in-phase component of a polymer or polymer-based material's response to a dynamic test. Throughout this disclosure, the elastic modulus of a polymer or polymer-based material refers to the storage modulus of the polymer or polymer-based material, as, without wishing to be bound by theory, the in-phase component of the response is attributed to the elastic portion of the viscoelastic material. As used herein, loss modulus refers to the heterogeneous component of the response to a polymer or polymer-based material during dynamic testing. Without wishing to be bound by theory, the loss modulus may correspond to the viscous portion of the viscoelastic material. As used herein, the glass transition temperature corresponds to the maximum value of tan δ, which is the ratio of the loss modulus to the storage modulus. In aspects, the glass transition temperature is outside the operating range of the coated article (e.g., outside the operating range of about-20 ℃ to about 60 ℃). In aspects, the glass transition temperature of the polymer-based portion can 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 polymer may be in the range of 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 polymer may be about 60 ℃ or greater, about 80 ℃ or greater, about 100 ℃ or greater, about 200 ℃ or less, about 160 ℃ or less, or about 120 ℃ or less. In aspects, the glass transition temperature of the polymer may be in the range of 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 polymer-based fraction having a glass transition temperature outside of the operating range (e.g., about 0 ℃ to about 40 ℃, about-20 ℃ to about 60 ℃) may result in consistent properties over the operating range.

In aspects, the polymer may include one or more of a polyamide-based polymer, a polyimide-based polymer, a silicone-based polymer, an acrylate-based polymer, an epoxy-based polymer, a thiol-containing polymer, a polycarbonate, or a polyurethane-based polymer. In even other aspects, the silicone-based polymer may comprise a silicone elastomer. Exemplary aspects of the silicone elastomer include PP2-OE50 available from Gelest and LS 8941 available from NuSil. In even other aspects, the polymer may include one or more of the following that are optically transparent: acrylic (e.g., polymethyl methacrylate (PMMA)), epoxy, silicone, and/or polyurethane. Examples of epoxides include bisphenol-based epoxy resins, phenolic-based epoxides, cycloaliphatic-based epoxides, and glycidoxylamine-based epoxides. In other aspects, the polymer may include one or more of a polyolefin, a polyamide, a halogen-containing polymer (e.g., polyvinyl chloride or a fluoropolymer), a polyether, a cellulose derivative, an elastomer, a urethane, a phenol resin, a parylene, a polyethylene terephthalate (PET), or a Polyetheretherketone (PEEK). Exemplary aspects of the polyolefin include low molecular weight polyethylene (LDPE), high molecular weight polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene (PP). Exemplary aspects of fluoropolymers include Polytetrafluoroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), perfluoroalkoxy (PFA) (e.g., perfluoroalkoxyethylene), fluorinated Ethylene Propylene (FEP) polymers, and Ethylene Tetrafluoroethylene (ETFE) polymers. Exemplary aspects of elastomers include rubbers (e.g., polybutadiene, polyisoprene, chloroprene rubber, butyl rubber, nitrile rubber) and block copolymers (e.g., styrene-butadiene, high impact polystyrene, dichlorophosphazene polymers). Exemplary aspects of linking groups including polymers include amine-terminated polydimethylsiloxanes, polycaprolactone, and amine-terminated poly (propylene glycol).

The polymer may include a number average molecular weight (Mn). As used herein, the number average molecular weight is calculated for a polymer by summing the product of the molecular weight and the fraction of polymer having that molecular weight. Throughout this disclosure, the molecular weight of the polymer is measured using high pressure liquid chromatography. In aspects, the polymer may include a number average molecular weight (Mn) of about 300 daltons or more, about 400 daltons or more, about 700 daltons or more, about 1,000 daltons or more, about 2,000 daltons or more, about 100,000 daltons or less, about 60,000 daltons or less, about 30,000 daltons or less, about 20,000 daltons or less, about 10,000 daltons or less, or about 5,000 daltons or less. In aspects, the polymer may include a number average molecular weight (Mn) in the range of about 300 daltons to about 100,000 daltons, about 400 daltons to about 50,000 daltons, about 400 daltons to about 30,000 daltons, about 700 daltons to about 20,000 daltons, about 1,000 daltons to about 10,000 daltons, about 2,000 daltons to about 5,000 daltons, or any range or subrange therebetween. Providing a polymer comprising a molecular weight in the range of about 400 daltons to about 30,000 daltons may prevent agglomeration of the functionalized oligomeric silsesquioxane attached thereto while reducing entanglement of the polymer, which may inhibit manufacturability of the resulting coating and/or coated article.

In aspects, a linking group (e.g., a polymer) can include an oxygen atom in the backbone of the linking group. As used herein, an atom is present in the backbone of a linking group (e.g., a polymer) and the longest chain of covalently bound atoms in the linking group (e.g., a polymer) comprises an oxygen atom when any functional group at one or more ends of the linking group (e.g., a polymer) is not included. In other aspects, the linking group comprises a polymer comprising oxygen atoms in the backbone of the polymer, and the oxygen atoms are present in multiple monomers of the polymer. Exemplary aspects of such polymers include polyethylene oxide, poly (propylene oxide), poly (hydroxyethyl methacrylate), polylactic acid, poly (caprolactone), polyglycolic 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). Exemplary aspects of linking groups that are not polymers include difunctional hexane carboxylates (e.g., celloxide 2021P (Daicel)), 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., pent erythritol epoxypropyl ether), and trifunctional ginseng (4-hydroxyphenyl) methane (e.g., ginseng (4-hydroxyphenyl) methane triglycidyl ether). In aspects, the linking group (e.g., polymer) may be substantially free of aromatic groups in the monomer unit. In aspects, the linking group (e.g., polymer) may be substantially free of fluoride, urethane, isocyanate, acrylate, and/or polycarbonate. Providing a linking group comprising oxygen atoms in the backbone of the polymer may increase the flexibility of the linking group, which may increase the final elongation, durability, and/or impact resistance (e.g., pen height) of the resulting composition and resulting coating.

The composition may comprise a first functionalized oligomeric silsesquioxane bound to a second functionalized oligomeric silsesquioxane through a linking group (e.g., a polymer) that is terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group. As shown on the right side of fig. 8-10, the linking group may comprise a polymer that is bound to the first functionalized oligomeric silsesquioxane by a bond between a first functional group at a first end of the polymer and a functional group of the functionalized first functionalized oligomeric silsesquioxane. Further, as shown, the polymer may be bound to the second functionalized oligomeric silsesquioxane by a bond between a second functional group at the second end of the polymer and a functional group of the functionalized second functionalized oligomeric silsesquioxane. For example, as shown in fig. 9, the composition can be formed by reacting R groups of a functionalized oligomeric silsesquioxane (e.g., a first functionalized oligomeric silsesquioxane (e.g., a functionalized POSS), a second functionalized oligomeric silsesquioxane (e.g., a functionalized POSS)) with functional groups X at the ends of the polymer (e.g., a first functional group X at the first end, a second functional group X at the second end) to bind the first functionalized oligomeric silsesquioxane (e.g., a functionalized POSS) to the first end of the polymer and the second functionalized oligomeric silsesquioxane (e.g., a functionalized POSS) to the second end. For example, as shown in fig. 10, the composition can be formed by reacting a glycidoxypropyl functional group (e.g., 3-glycidoxypropyl functional group) of a functionalized oligomeric silsesquioxane (e.g., functionalized POSS, GPOSS) with a first functional group comprising an amine (e.g., aminopropyl) at a terminal end (e.g., first terminal end, second terminal end) of a polymer (e.g., PDMS) to bind the first functionalized oligomeric silsesquioxane (e.g., functionalized POSS, GPOSS) to the first terminal end of the polymer and bind the second functionalized oligomeric silsesquioxane (e.g., functionalized POSS, GPOSS) to the second terminal end of the polymer.

In aspects, substantially all of the linking groups (e.g., polymers) can be bound to both functionalized oligomeric silsesquioxanes. In aspects, the composition may include a third functionalized oligomeric silsesquioxane that is not bound to a linking group (e.g., a polymer) in addition to the first functionalized oligomeric silsesquioxane and the second functionalized oligomeric silsesquioxane that are bound to a linking group (e.g., a polymer). In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes based on the total weight of the plurality of functionalized oligomeric silsesquioxanes and the polymer can be about 20% or more, about 40% or more, about 60% or more, about 80% or more, about 90% or more, about 99% or less, about 97% or less, about 95% or less, or about 93% or less. In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes to the total weight of the plurality of functionalized oligomeric silsesquioxanes and the polymer may be in a range of about 20% to about 99%, about 40% to about 97%, about 60% to about 95%, about 80% to about 93%, about 90% to about 97%, about 90% to about 95%, or any range or subrange therebetween. Providing a low molar ratio of polymer to the plurality of functionalized oligomeric silsesquioxanes (e.g., about 0.06 or less) may result in a polymer that binds to both functionalized oligomeric silsesquioxanes, which may achieve the benefits described herein. The degree of functionalization of the plurality of functionalized oligomeric silsesquioxanes may facilitate the binding of the polymer to two different functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes.

In aspects, the ratio of the number of attachment groups comprising the polymer (e.g., on a molar basis) to the number of functionalized oligomeric silsesquioxanes (e.g., on a molar basis) can be about 0.0005 or greater, about 0.001 or greater, about 0.005 or greater, about 0.01 or greater, about 0.02 or greater, about 0.08 or less, about 0.06 or less, or about 0.05 or less, or about 0.04 or less, or about 0.03 or less. In aspects, the ratio of the number of attachment groups comprising the polymer (e.g., on a molar basis) to the number of functionalized oligomeric silsesquioxanes (e.g., on a molar basis) can be in a range of about 0.0005 to about 0.08, about 0.001 to about 0.06, about 0.005 to about 0.05, about 0.01 to about 0.04, about 0.02 to about 0.03, or any range or subrange therebetween.

In aspects, the ratio of the number of linking groups (e.g., non-polymeric linking groups) (e.g., on a molar basis) to the number of functionalized oligomeric silsesquioxanes (e.g., on a molar basis) can be about 0.6 or greater, about 0.7 or greater, about 1 or less, about 0.9 or less, or about 0.8 or less. In aspects, the ratio of the number of linking groups (e.g., non-polymeric linking groups) (e.g., on a molar basis) to the number of functionalized oligomeric silsesquioxanes (e.g., on a molar basis) can be in the range of about 0.6 to about 1, about 0.6 to about 0.9, about 0.6 to about 0.8, about 0.7 to about 0.8, or any range or subrange therebetween.

In aspects, the wt% of the linking groups (e.g., the plurality of linking groups) based on the total weight of the plurality of functionalized oligomeric silsesquioxanes and the linking groups can include about 10% or more, about 15% or more, about 20% or more, about 25% or more, about 50% or less, about 45% or less, about 40% or less, or about 30% or less. In aspects, the wt% of the linking groups (e.g., the plurality of linking groups) relative to the total weight of the plurality of functionalized oligomeric silsesquioxanes and linking groups can be in a range of about 10% to about 50%, about 15% to about 45%, about 20% to about 40%, about 25% to about 30%, or any range or subrange therebetween. Providing a linking group can be used to adjust the viscosity of the composition, which can facilitate uniform application and/or enable lower cost application techniques while reducing the overall cost of the composition and/or coating. Providing a linking group within one or more of the above-mentioned ranges may reduce the overall cost of producing the coated article, for example by reducing the amount of the various functionalized oligomeric silsesquioxanes used.

In aspects, the linking group can include a reactive diluent. As used herein, a reactive diluent in a composition is a substance that reduces the viscosity of the composition and that can react with another substance in the composition. Reactive diluents are in contrast to solvents, which do not react with another substance in the composition. In aspects, the composition may further comprise a reactive diluent. The reactive diluent may include a third functional group at a first end and a fourth functional group at a second end opposite the first end. In other aspects, the third functional group and/or the fourth functional group may include one or more of the functional groups discussed above with reference to the first functional group and/or the second functional group. In other aspects, the third functional group and/or the fourth functional group may be selected from the group consisting of: alcohols, acrylates and epoxides, and the second functional group is selected from the group consisting of acid alcohols, acrylates, anhydrides, alcohols, epoxides, isocyanates and ureido groups. As discussed above, any of the functional groups may include an alkyl, cycloalkyl, or aromatic version of the functional group; the functional group itself or a multiple functional group including the named functional group. In other aspects, the third functional group may be the same as the fourth functional group. In other aspects, the reactive diluent may include three or more reactive functional groups (e.g., a third functional group, a fourth functional group, and another functional group). Providing a reactive diluent (e.g., a linking group that is not bonded to the functionalized oligomeric silsesquioxane prior to curing after the composition is disposed on a substrate) can be used to adjust the viscosity of the composition, which can facilitate uniform application and/or enable lower cost application techniques while reducing the overall cost of the composition and/or coating. Furthermore, linking multiple functionalized oligomeric silsesquioxanes during curing may reduce the time and resources required to produce a coated article. Exemplary aspects of the linking groups that include reactive diluents (e.g., non-polymeric linking groups) include 1, 6-hexamethylenediamine, trimethylhexamethylenediamine, isophoronediamine, aminoethylpiperazine, 4 '-methylene-bis (2-methylcyclohexylamine), N' -bis (3-aminopropyl) ethylenediamine, diethylene glycol bis (3-aminopropyl) ether, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate, 3-ethyl-3-oxetane methanol, and methylhexahydrophthalic anhydride.

As used herein, TMPO refers to trimethylolpropane oxetane. In aspects, the composition may comprise TMPO. In other aspects, the composition can comprise TMPO in an amount of about 3wt% or greater, about 5wt% or greater, about 8wt% or greater, about 10wt% or greater, about 15wt% or greater, or about 30wt% or greater. In other aspects, the composition may comprise TMPO in a range of about 3wt% to about 50wt%, about 5wt% to about 30wt%, about 8wt% to about 25wt%, about 10wt% to about 20wt%, or any range or subrange therebetween. Providing TMPO of about 10wt% or more can improve the adhesion of the resulting coating after 10 days in a 95% relative humidity, 65 ℃ environment or 85% relative humidity, 85 ℃ environment. In other aspects, the ratio of the amount of wt% of linking groups to the amount of wt% of TMPO can be about 1 or higher, about 1.5 or higher, about 2 or higher, about 3.3 or lower, about 3 or lower, or about 2.5 or lower. In other aspects, the ratio of the amount of wt% of the linking group to the amount of wt% of the TMPO can be in the range of about 1 to about 3.3, about 1 to about 3, about 1.5 to about 2.5, about 2 to about 2.5, or any range or subrange therebetween. Providing a composition comprising trimethylol propane oxetane can increase the hardness of the resulting coating.

In aspects, the composition may comprise a silane coupling agent. In other aspects, the silane coupling agent may comprise an anhydride functionalized silane, an amine functionalized silane, a chloro functionalized silane, a cyano functionalized silane, an epoxy functionalized silane, a hydroxyl functionalized silane, a thiol functionalized silane, and combinations thereof. In even other aspects, the silane coupling agent may comprise an amine functional group. In other aspects, the silane coupling agent may comprise (3-triethoxysilyl) propyl succinic anhydride, (3-mercaptopropyl) trimethoxysilane and/or 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane. In even other aspects, the silane coupling agent may comprise an epoxy functional silane coupling agent. Exemplary aspects of epoxy functional silane coupling agents include 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl trimethoxysilane, 5, 6-epoxyhexyl triethoxysilane, 2- (2, 4-epoxycyclohexyl) ethyl trimethoxysilane, 2- (2, 4-epoxycyclohexyl) ethyl triethoxysilane, (3-epoxypropoxy propyl) trimethoxysilane, (3-epoxypropoxy propyl) triethoxysilane, (3-epoxypropoxy propyl) trimethoxysilane, and (3-epoxypropyl) triethoxysilane. In even other aspects, the silane coupling agent may comprise an amine functional silane coupling agent. Exemplary aspects of amine functional silanes include (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, (3-aminopropyl) methyldimethoxysilane, (3-aminopropyl) methyldiethoxysilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, 3- (m-aminophenoxy) propyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (6-aminohexyl) aminomethyltrimethoxysilane, N- (6-aminohexyl) aminoethyltriaethoxysilane, N-2-aminoethyl-11-aminoundecyltrimethoxysilane, aminoethylaminomethyltriethoxysilane, N-3- (aminopropropyloxy) aminopropyl trimethoxysilane, N-3- (aminopropropyloxy) propyltriethoxysilane, (3-diethylenetriamine) triethoxysilane, and (3-diethylenetriamine) triethoxysilane, 4-amino-3, 3-dimethylbutyl trimethoxysilane and 4-amino-3, 3-dimethylbutyl triethoxysilane. Exemplary aspects of the chloro-functional silanes include 3-chloropropyl trimethoxysilane and 3-chloropropyl triethoxysilane. Exemplary aspects of cyano-functional silanes include 3-isocyanatopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane. Exemplary aspects of hydroxy-functional silanes include N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine, N '-bis (2-hydroxyethyl) -N, N' -bis (triethoxysilylpropyl) ethylenediamine, N-bis (2-hydroxyethyl) -3-aminopropyl trimethoxysilane, N-bis (2-hydroxyethyl) -3-aminopropyl triethoxysilane, 2-bis (3-trimethoxysilylpropoxymethyl) butanol, and 2, 2-bis (3-triethoxysilylpropoxymethyl) butanol. Exemplary aspects of the thiol-functional silanes include 3-mercaptopropyl methyl-dimethoxysilane, 3-mercaptopropyl-methyl-diethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, and 11-mercaptoundecyltrimethyloxysilane. In other aspects, the composition may comprise about 0.1wt% or more, about 0.2wt% or more, about 0.5wt% or more, about 5wt% or less, about 2wt% or less, or about 1wt% or less of a silane coupling agent by weight (wt%). In other aspects, the composition may comprise a silane coupling agent in a weight percent (wt%) ranging from about 0.1wt% to about 5wt%, from about 0.1wt% to about 2wt%, from about 0.2wt% to about 1wt%, from about 0.5wt% to about 1wt%, or any range or subrange therebetween. Providing a silane coupling agent can increase the adhesion of the resulting coating to a substrate (e.g., glass-based substrate, ceramic-based substrate, polymer-based substrate) and improve the durability of the coating and/or coated article.

In aspects, the composition may be substantially free of nanoparticles. In aspects, the composition may be substantially free of silica nanoparticles. As used herein, a composition is substantially free of silica nanoparticles if the amount of silica nanoparticles is about 1wt% or less. In other aspects, the composition may be free of silica nanoparticles. As used herein, silica nanoparticles refer to particles comprising an effective diameter of at least 20nm and comprise silica. The silica nanoparticles may include solid particles or mesoporous particles. The silica nanoparticles can be larger (e.g., include a larger effective diameter) than one 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, silica nanoparticles may aggregate, especially at elevated temperatures, compromising the mechanical and/or optical properties of the composition or the resulting coating and/or coated article. Providing a composition that is substantially free and/or free of silica nanoparticles may reduce handling problems (e.g., agglomeration, aggregation, phase separation) of the composition, 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 resulting coating and/or coated article, and reduce mechanical properties (e.g., hardness, modulus, strain) of the resulting coating and/or coated article, as compared to a corresponding composition, coating and/or coated article that includes a plurality of functionalized oligomeric silsesquioxanes without nanoparticles.

In aspects, the composition may comprise nanoparticles. In other aspects, the nanoparticles may include silica nanoparticles, alumina nanoparticles, zirconia nanoparticles, titania nanoparticles, carbon black, and/or combinations thereof. In aspects, the composition may comprise silica nanoparticles and/or alumina nanoparticles. In other aspects, the wt% of silica nanoparticles and/or alumina nanoparticles in the composition can be about 5% or greater, about 10% or greater, about 15% or greater, about 20% or greater, about 50% or less, about 40% or less, about 30% or less, or about 25% or less. In other aspects, the wt% of the linking groups (e.g., the plurality of linking groups) can be in the range of about 5% to about 50%, about 10% to about 40%, about 15% to about 40%, about 20% to about 30%, about 20% to about 25%, or any range or subrange therebetween, based on the total weight of the plurality of functionalized oligomeric silsesquioxanes and linking groups. In other aspects, the silica nanoparticles and/or alumina nanoparticles can have an average effective diameter of about 20nm or greater, about 30nm or greater, about 100nm or less, or about 50nm or less. In other aspects, the average effective diameter is in the range of about 20nm to about 100nm, about 20nm to about 50nm, about 30nm to about 50nm, or any range or subrange therebetween. In other aspects, the silica nanoparticles and/or alumina nanoparticles may not be bound to one of the plurality of functionalized oligomeric silsesquioxanes in the composition. Providing nanoparticles can increase the hardness and/or impact resistance of the coated article.

In aspects, the functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes can be directly bound to only the linking group (e.g., polymer) or to only the linking group (e.g., polymer) and the silane coupling agent. In aspects, all of the functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes can be bound directly to only the linking group (e.g., polymer) or to only the linking group (e.g., polymer) and the silane coupling agent.

In aspects, the composition may comprise a catalyst. Without wishing to be bound by theory, the catalyst may increase the rate of curing (e.g., polymerization, reaction) and the catalyst may avoid permanent chemical changes due to curing. In aspects, the catalyst may comprise one or more platinum group metals, such as ruthenium, rhodium, palladium, osmium, iridium, and/or platinum. In aspects, the catalyst may comprise a platinum-based Karstedt's catalyst (Karstedt's catalyst) solution. Exemplary aspects of the platinum-based catalyst include chloroplatinic acid, platinum fumaric acid, colloidal platinum, metallic platinum, and/or platinum nickel nanoparticles.

In aspects, the composition may include a curing catalyst. As used herein, a curing catalyst refers to a compound that contains a nitrogen atom bound to two or more non-hydrogen atoms and is not functional as a linking group, in other aspects, the curing catalyst may contain a secondary amine, a tertiary amine, a pyridine, and/or an imidazole. Exemplary aspects of tertiary amines include 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylamine, tetramethylguanidine, and 2,4, 6-ginseng (dimethylaminomethyl) phenol. In other aspects, the composition may comprise a curing catalyst in an amount of about 0.3wt% or greater, about 0.5wt% or greater, about 0.7wt% or greater, about 1.1wt% or less, about 1wt% or less, or about 0.8wt% or less. In other aspects, the composition comprises a curing catalyst in the range of about 0.3wt% to about 1.1wt%, about 0.3wt% to about 1wt%, about 0.5wt% to about 0.8wt%, about 0.7wt% to about 0.8wt%, or any range or subrange therebetween. Without wishing to be bound by theory, the curing catalyst may improve properties of the coating (e.g., hardness, adhesion, pen hardness), wherein the first and/or second functional groups of the linking group comprise amine functional groups.

In aspects, the composition may comprise a photoinitiator. As used herein, a photoinitiator is a compound that is sensitive to one or more wavelengths that undergoes a reaction upon absorption of light including the one or more wavelengths to produce one or more free radical or ionic species that can initiate the reaction. In other aspects, the photoinitiator may be sensitive to one or more wavelengths of Ultraviolet (UV) light. In other aspects, the photoinitiator may comprise a cationic photoinitiator, which is a photoinitiator configured to initiate a cationic reaction (e.g., cationic polymerization). In other aspects, the composition may comprise a cationic photoinitiator and a free radical photoinitiator. Exemplary aspects of photoinitiators that are sensitive to UV light include, but are not limited to, benzoin ethers, benzophenone ketals, dialkoxyacetophenones, hydroxyalkyl phenyl ketones, aminoalkylphenyl ketones, acyl phosphine oxides, thioxanthones, hydroxyalkyl ketones, and thioxanthones. In other aspects, the photoinitiator may be sensitive to one or more wavelengths of visible light. Exemplary aspects of photoinitiators that are sensitive to visible light include, but are not limited to, 5, 7-diiodo-3-butoxy-6-fluorone, bis (4-methoxybenzoyl) diethylgermanium, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 3-methyl-4-aza-6-helical hydrocarbons, and boric acid thiocyanide. In other aspects, the photoinitiator may be sensitive to other components of the composition and/or to wavelengths at which the composition is substantially transparent. In other aspects, the photoinitiator can initiate a cationic reaction (e.g., cationic polymerization), such as triarylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, and bis (4-tetra-butylphenyl) iodonium perfluoro-1-butanesulfonate. In other aspects, the photoinitiator may include a radical photoinitiator configured to generate one or more radicals, such as acetophenone-based compounds (e.g., dimethoxyphenyl acetophenone), azobisisobutyronitrile (AIBN), and aromatic peroxides (e.g., benzoyl peroxide). Commercially available photoinitiators include, but are not limited to, irgacure product line from Ciba Specialty Chemical. In aspects, the composition may comprise about 0.1wt% or more, about 0.2wt% or more, about 0.5wt% or more, about 6wt% or less, about 4wt% or less, about 3wt% or less, about 2wt% or less, or about 1wt% or less of the photoinitiator by weight (wt%). In aspects, the composition may comprise a silane coupling agent in a weight percent (wt%) ranging from about 0.1wt% to about 6wt%, from about 0.1wt% to about 4wt%, from about 0.1wt% to about 3wt%, from about 0.1wt% to about 2wt%, from about 0.2wt% to about 1wt%, from about 0.5wt% to about 1wt%, or any range or subrange therebetween. In aspects, the composition may be substantially free of fluorine-based compounds. As used herein, the composition may be substantially free of fluorine-based compounds, while having trace amounts of fluorine in minor components of the composition (e.g., about 6wt% or less of the photoinitiator), corresponding to a total wt% of fluorine of about 0.25wt% or less. In other aspects, the composition may be free of fluorine-based compounds.

In aspects, the composition may comprise a solvent. As used herein, a "solvent" excludes components discussed above, such as functionalized oligomeric silsesquioxanes, linking groups comprising a first functional group at a first end and a second functional group at a second end opposite the first end, silane coupling agents, catalysts, photoinitiators, and combinations and/or products thereof. The solvent may include one or more of a polar solvent (e.g., water, alcohol, acetate, acetone, formic acid, dimethylformamide, acetonitrile, dimethylamine-benzenesulfonic acid, nitromethane, ethylene carbonate, propylene carbonate, poly (ether/ketone)) or a nonpolar solvent (e.g., pentane, 1, 4-dioxane, chloroform, methylene chloride, diethyl ether, hexane, heptane, benzene, toluene, xylene). Exemplary aspects of alcohols include methanol, ethanol, propanol, butanol, cyclohexanol, hexanol, octanol, ethylene glycol, and propylene glycol. Exemplary aspects of the acetate include ethyl acetate, propyl acetate, and butyl acetate. In other aspects, the solvent may comprise butyl acetate, propyl acetate, and/or acetonitrile. Providing a solvent may enable the formation of coatings using a wider range of compositions than would otherwise be possible.

In aspects, the composition may be substantially free of solvent. As used herein, a composition is "substantially solvent free" or "substantially solvent free" if the composition contains 2wt% or less solvent. As used herein, a composition is "solvent-free" or "solvent-free" if the composition contains 0.5wt% or less solvent. Providing a composition that is substantially solvent-free or substantially solvent-free may increase its cure rate, which may reduce processing time. Furthermore, providing a solvent-free or solvent-free composition may reduce (e.g., reduce, eliminate) the use of rheology modifiers and increase composition uniformity, which may increase the optical transparency (e.g., transmittance) of the resulting coating. Furthermore, the solvent-free composition may reduce the incidence of visual defects (e.g., bubbles generated by volatile gases upon evaporation of any solvent) in the resulting coating.

In aspects, the composition may be optically transparent. As used herein, a composition is substantially transparent at a predetermined wavelength if the composition comprises an average transmittance of 70% or more through a 1.0mm thick sample of the composition at the predetermined wavelength. As used herein, "optically transparent" or "optically clear" means that an average transmittance of 70% or more is included in the wavelength range of 400 nanometers (nm) to 700nm by a piece of 1.0mm thick material. As used herein, the average transmittance of a material is measured by averaging the wavelengths of light in the range of 400nm to 700nm through a piece of 1.0mm thick material, including measuring the transmittance at an integer wavelength of 400nm to 700nm and averaging the measurements. "transmittance" of a material refers to the average transmittance of the material, unless otherwise indicated. In aspects, an "optically transparent material" or "optically clear material" may have an average light transmittance of 75% or more, 80% or more, 85% or more, or 90% or more, 92% or more, 94% or more, 96% or more over a 1.0mm thick piece of material in the wavelength range of 400nm to 700 nm. The average transmittance in the wavelength range of 400nm to 700nm is calculated by averaging transmittance measurements at integer wavelengths of 400nm to 700 nm. In aspects, the composition may include an average light transmittance of about 80% or more, about 90% or more, about 92% or more, about 98% or less, about 96% or less, or about 94% or less over a wavelength range of 400nm to 700 nm. In aspects, the composition may include an average transmittance in the range of about 80% to about 98%, about 90% to about 96%, about 92% to about 94%, or any range or subrange therebetween, in the wavelength range of 400nm to 700 nm. In aspects, the composition may be visually transparent. As used herein, "visually transparent" means a material that appears clear and transparent by visual inspection of a 1mm sample of the composition.

The method of forming a composition may include reacting a plurality of functionalized oligomeric silsesquioxanes with a linking group (e.g., a polymer) terminated with a first functional group at a first end of the linking group (e.g., a polymer) and a second functional group at a second end of the linking group (e.g., a polymer) opposite the first end of the linking group (e.g., a polymer). As described above with reference to fig. 8-10, the linking group may comprise a polymer, and a first functional group at a first end of the polymer may react with a functional group that functionalizes the first functionalized oligomeric silsesquioxane to bind the first functionalized oligomeric silsesquioxane to the polymer. Likewise, a second functional group at a second end of a linking group (e.g., a polymer) can react with a functional group that functionalizes the second functionalized oligomeric silsesquioxane to bind the second functionalized oligomeric silsesquioxane to the linking group (e.g., polymer). In aspects, the ratio of the plurality of functionalized oligomeric silsesquioxanes on a molar basis to the plurality of linking groups comprising the polymer on a molar basis can be within one or more of the ranges discussed above for such ratio (e.g., about 0.06 or less, about 0.0005 to about 0.06). In other aspects, as shown in fig. 8-10, the reaction may occur under reaction conditions indicated by blocks 805, 905, and/or 1005. In aspects, the reaction may include heating, ultraviolet (UV) irradiation, and/or waiting a predetermined period of time. In other aspects, the reaction conditions may include heating the reactant at the first temperature (left side of fig. 8-10) for a first period of time. In even other aspects, the first temperature may be maintained by an electrical resistance heater, an oil bath, or a salt bath with which the reaction vessel is in contact. In even other aspects, the first temperature may be about 90 ℃ or greater, about 100 ℃ or greater, about 110 ℃ or greater, about 120 ℃ or greater, about 160 ℃ or less, about 140 ℃ or less. In even other aspects, the first temperature may be in a range of about 90 ℃ to about 160 ℃, about 100 ℃ to about 160 ℃, about 110 ℃ to about 140 ℃, about 120 ℃ to about 140 ℃, or any range or subrange therebetween. In even other aspects, the first period of time may be about 15 minutes or more, about 1 hour or more, about 2 hours or more, about 4 hours or more, about 6 hours or more, about 24 hours or less, about 18 hours or less, about 12 hours or less, or about 10 hours or less. In even other aspects, the first period of time may be in the range of about 15 minutes to about 24 hours, about 1 hour to about 16 hours, about 2 hours to about 16 hours, about 4 hours to about 12 hours, about 6 hours to about 10 hours, or any range or subrange therebetween. In aspects, the reactants can be combined with a catalyst.

In aspects, the particular reaction conditions indicated by blocks 805, 905 and/or 1005 may further comprise performing the reaction in the presence of a solvent. In other aspects, the solvent may include one or more of the solvents discussed above. In even other aspects, the solvent may include butyl acetate, propyl acetate, and/or acetonitrile. In other aspects, the amount of solvent weight percent (wt%) of the composition during the reaction can be about 5wt% or more, about 10wt% or more, about 15wt% or more, about 80wt% or less, about 60wt% or less, about 40wt% or less, or about 30wt% or less. In other aspects, the amount of weight percent (wt%) of the solvent of the composition during the reaction may be in the range of about 5wt% to about 80wt%, about 5wt% to about 60wt%, about 10wt% to about 40wt%, about 15wt% to about 30wt%, or any range or subrange therebetween. In other aspects, the solvent may be refluxed for a first period of time. In other aspects, after the reaction occurs, the solvent may be removed, for example using an elevated temperature and/or reduced pressure (e.g., vacuum, rotary evaporator). In even other aspects, the reduced pressure may be about 20 kilopascals or less, about 10kPa or less, about 5kPa or less, about 0.01kPa or more, about 0.1kPa or more, about 1kPa or more, or about 2kPa or more. In even other aspects, the reduced pressure may be in the range of about 0.01kPa to about 20kPa, about 0.1kPa to about 10kPa, about 1kPa to about 5kPa, about 2kPa to about 5kPa, or any range or subrange therebetween. In even other aspects, the elevated temperature may be about 35 ℃ or greater, about 45 ℃ or greater, about 50 ℃ or greater, about 80 ℃ or less, about 70 ℃ or less, or about 65 ℃ or less. In even other aspects, the elevated temperature may be in the range of about 35 ℃ to about 80 ℃, about 45 ℃ to about 70 ℃, about 50 ℃ to about 65 ℃, or any range or subrange therebetween. In other aspects, the composition may comprise a solvent. In aspects, the reaction may be substantially solvent-free and/or solvent-free.

In aspects, additional functionalized oligomeric silsesquioxanes may be added to the composition after the reaction occurs. In other aspects, the amount of additional functionalized oligomeric silsesquioxane added may be the same as, greater than, or less than the initial amount of functionalized oligomeric silsesquioxane present during the reaction. In other aspects, the amount of additional functionalized oligomeric silsesquioxanes in percent (e.g., wt%) of the initial amount of functionalized oligomeric silsesquioxanes added may be about 20% or more, about 50% or more, about 80% or more, about 90% or more, about 200% or less, about 150% or less, about 120% or less, or about 110% or less. In other aspects, the amount of additional functionalized oligomeric silsesquioxanes in a percentage (e.g., wt%) of the initial amount of functionalized oligomeric silsesquioxanes added may be in a range of about 20% to about 200%, about 20% to about 150%, about 50% to about 120%, about 80% to about 110%, about 90% to about 110%, or any range or subrange therebetween. In aspects, a silane coupling agent may be added to the composition after the reaction has occurred. In aspects, a photoinitiator may be added to the composition after the reaction occurs. In aspects, in aspects where the reaction occurs in a solvent, additional functionalized oligomeric silsesquioxane, silane coupling agent and/or photoinitiator may be added after the reaction occurs but before the solvent is removed.

In aspects, a solvent may be added to the composition after the reaction occurs. In other aspects, the solvent may include one or more of the solvents discussed above. In other aspects, the solvent may be added during the reaction removal after the solvent is present. In other aspects, the solvent may be added after being substantially solvent-free and/or solvent-free. In other aspects, the amount of solvent in the composition can be about 5wt% or more, about 10wt% or more, about 15wt% or more, about 85wt% or less, about 70wt% or less, about 50wt% or less, about 30wt% or less, or about 25wt% or less. In other aspects, the amount of solvent in the composition may be in the range of about 5wt% to about 85wt%, about 5wt% to about 70wt%, about 5wt% to about 50wt%, about 5wt% to about 30wt%, about 10wt% to about 30wt%, about 15wt% to about 25wt%, or any range or subrange therebetween. In aspects, the composition may be substantially solvent-free and/or solvent-free. The provision of a solvent in the composition allows for a wide range of methods of forming coatings with the composition. It should be understood that any of the above ranges for the components mentioned above may be incorporated in aspects of the present disclosure.

In aspects, the composition may comprise a viscosity. As used herein, the viscosity of a liquid is measured using a rotational rheometer (e.g., rheolabQC from Anton Par or Discovery Hybrid Rheometer (DHR-3) from TA Instruments) at 23 ℃ at a shear rate of about 0.83 1/second(s) (e.g., 50 revolutions per minute (rpm)). In other aspects, the composition may comprise a viscosity of about 0.01 Pa.s (Pa-s) or greater, about 1Pa-s or greater, about 5Pa-s or greater, about 10Pa-s or greater, about 1,000Pa-s or less, about 500Pa-s or less, about 100Pa-s or less, about 50Pa-s or less, or about 30Pa-s or less. In aspects, the composition may include a viscosity in the range of about 0.01Pa-s to about 1,000Pa-s, about 0.01Pa-s to about 500Pa-s, about 1Pa-s to about 100Pa-s, about 5Pa-s to about 50Pa-s, about 10Pa-s to about 30Pa-s, or any range or subrange therebetween. In even other aspects, the composition may comprise a viscosity of about 0.01Pa-s or greater, about 0.1Pa-s or greater, about 0.5Pa-s or greater, about 30Pa-s or less, about 10Pa-s or less, about 6Pa-s or less, or about 3Pa-s or less. In even other aspects, the composition may include a viscosity in the range of about 0.01Pa-s to about 30Pa-s, about 10Pa-s, about 0.01Pa-s to about 6Pa-s, about 0.1 to about 3Pa-s, about 0.5Pa-s to about 3Pa-s, or any range or subrange therebetween.

Example ranges of combinations in aspects of the present disclosure are presented in table 1. R1 and R10 are the broadest ranges in Table 1. Examples R2-R5, R8-R9, R11-R13 and R16 are solvent-free compositions, and R6-R7 and R14-R15 are solvent-containing compositions. R1-R3 and R6-R10 may comprise a photoinitiator, while R1, R3-R5 and R10-R16 may be free of photoinitiators. R1-R2, R6-R11 and R14-R16 may comprise a silane coupling agent, and R1, R3-R5, R10 and R12-R13 may be free of a silane coupling agent. R1-R4 and R8-R16 may comprise reactive diluents, while R5-R7, R9-R10 and R16 may be free of reactive diluents. R1, R9-R10 and R16 may comprise nanoparticles, while R1-R8 and R10-R15 may be free of nanoparticles. R10-R16 may comprise TMPO, while R1-R10 and R12 may be TMPO-free. R10-R16 may contain a curing catalyst, while R1-R10 and R12 may be free of curing catalysts. Again, it should be understood that other ranges or subranges discussed above for these components can be used in combination with any of the ranges presented in table 1. In aspects, the compositions are within one or more of the ranges in table 1, but prior to forming a coating, e.g., as part of a coated article described below, a functionalized oligomeric silsesquioxane, photoinitiator, silane coupling agent, and/or solvent may be added to the composition.

Table 1: composition ranges (wt%) of the composition

Fig. 1-3 schematically illustrate example aspects of a coated article 101, 201, or 301 in an expanded (e.g., planar configuration) state according to aspects of the present disclosure, while fig. 5-7 schematically illustrate example aspects of a coated article 401, 601, or 701 in a folded configuration according to aspects of the present disclosure. As shown in fig. 1 and 5 or fig. 3 and 7, the coated article 101 and 401 or 301 and 701 may include a substrate 103 (e.g., a foldable substrate). As shown in fig. 2 and 6, the coated articles 201 and 601 may include a substrate 203 (e.g., a foldable substrate). As shown in fig. 3 and 7, the coated articles 301 and 701 may further include a first portion 321 and a second portion 331. In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may comprise a glass-based substrate and/or a ceramic-based substrate having a pen hardness of 8H or more, e.g., 9H or more. As used herein, pen hardness is measured using ASTM D3363-20 with a standard lead grade pen. Providing the coating on the substrate improves the durability of the coated article, for example by filling surface defects in the substrate and/or protecting the surface defects in the substrate from damage. In addition, the substrate may include a glass-based substrate and/or a ceramic-based substrate to enhance puncture resistance and/or impact resistance.

In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may comprise a glass-based substrate. 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. The glass-based material (e.g., glass-based substrate) may include 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, such as via ion exchange of larger particles to smaller particles of the substrate surface as discussed below. However, other strengthening methods (e.g., thermal tempering or utilizing a mismatch in thermal expansion coefficients between portions of the substrate to create compressive stress and a central tensile region) may be utilized to form the strengthened substrate. Exemplary glass-based materials that may be lithium-free or lithium-containing include soda lime glass, alkali aluminosilicate glass, alkali borosilicate glass, alkali aluminoborosilicate glass, alkali phosphosilicate glass, and alkali aluminophosphosilicate glass. In aspects, the glass-based material can include an alkali metal-containing glass or an alkali metal-free glass, either of which can be lithium-free or lithium-containing. In aspects, the glass material may be alkali-free and/or contain low levels of alkali metals (e.g., about 10mol% or less of R ₂ O, where R is ₂ O includes Li ₂ O、Na ₂ O、K ₂ O or the broader list provided below). In one or more aspects, the glass-based material can include the following in mole percent (mol%): siO in the range of about 40mol% to about 80% ₂ Al in the range of about 5mol% to about 30mol% ₂ O ₃ B in the range of 0mol% to about 10mol% ₂ O ₃ ZrO in the range of 0mol% to about 5mol% ₂ P in the range of 0mol% to about 15mol% ₂ O ₅ TiO in the range of 0mol% to about 2mol% ₂ R in the range of 0mol% to about 20mol% ₂ O and RO in the range of 0mol% to about 15 mol%. As used herein, R ₂ O may 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 may refer to MgO, caO, srO, baO and ZnO. In aspects, the glass-based substrate may optionally further comprise each of the following in the range of 0mol% to about 2 mol%: na (Na) ₂ SO ₄ 、NaCl、NaF、NaBr、K ₂ SO ₄ 、KCl、KF、KBr、As ₂ O ₃ 、Sb ₂ O ₃ 、SnO ₂ 、Fe ₂ O ₃ 、MnO、MnO ₂ 、MnO ₃ 、Mn ₂ O ₃ 、Mn ₃ O ₄ 、Mn ₂ O ₇ . "glass-ceramic" includes materials produced via controlled crystallization of glass. In aspects, 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 (including β -quartz solid solutions, 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 of the present invention, MAS-system glass-ceramic substrates can be found in Li ₂ SO ₄ Strengthening in molten salt, whereby 2Li can occur ⁺ For Mg ²⁺ Is a function of the exchange of (a).

In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may comprise a ceramic-based substrate. As used herein, "ceramic-based" includes both ceramics and glass-ceramics, wherein the glass-ceramic has one or more crystalline phases and is non-crystallineA crystalline phase and a residual glass phase. Ceramic-based materials may be strengthened (chemically strengthened). In aspects, the ceramic-based material may be formed by heating a glass-based material to form ceramic (e.g., crystalline) portions. In other aspects, the ceramic-based material may include one or more nucleating agents that may promote the formation of one or more crystalline phases. 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 zirconium dioxide (ZrO ₂ ) Zircon (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 (minerals including alumina in combination with 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 earth metal nitride (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 nitride and silicon nitride and may have, 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 Wherein m, n and the resulting subscripts are non-negative integers). Exemplary aspects of carbides and carbon-containing 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 metal silicides (e.g. sodium silicide (NaSi)), alkali metal silicides (e.g. magnesium silicide (Mg) ₂ Si)), hafnium disilicide (HfSi) ₂ ) And platinum silicide (PtSi).

In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may comprise a polymer-based portion having a young's modulus of about 3 gigapascals (GPa) or greater. Exemplary aspects for the polymer-based first portion and/or polymer-based second portion materials include, but are not limited to, blends, nanoparticles, and/or fibrous 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), polyphthalamide (PPA), polyoxymethylene (POM), polylactic acid (PLA), polyimide (PI), polyhydroxybutyrate (PHB), polygalamic acid lactide (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, the first portion 321, and/or the second portion 331 (e.g., glass-based material, ceramic-based material) is measured using indentation according to ASTM E2546-15. In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may comprise an elastic modulus of about 10 gigapascals (GPa) or greater, about 50GPa or greater, about 60GPa or greater, about 70GPa or greater, about 100GPa or less, or about 80 or less. In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may include a modulus of elasticity in a range of about 10GPa to about 100GPa, about 50GPa to about 80GPa, about 60GPa to about 80GPa, about 70GPa to about 80GPa, or any range or subrange therebetween.

As shown in fig. 1 and 3, the substrate 103 may include a first major surface 105 and a second major surface 107 opposite the first major surface 105. As shown in fig. 1, the first major surface 105 may extend along the first plane 104. As further shown in fig. 1, the substrate 103 may include a second major surface 107 extending along the second plane 106. In aspects, as shown, the second plane 106 may be parallel to the first plane 104. As used herein, the substrate thickness 109 may be defined between the first and second major surfaces 105, 107 as the distance between the first and second planes 104, 106. Likewise, as shown in fig. 2, the substrate 203 may include a first major surface 205 that may extend along a first plane 204a and a second major surface 207 that may extend along a second plane 206 a. As shown in fig. 2, the substrate 203 may include a substrate thickness 209 defined between the first and second major surfaces 205, 207 as a distance between the first and second planes 204a, 206 a. In aspects, the substrate thickness 109 or 209 may be about 10 micrometers (μm) or greater, about 25 μm or greater, about 40 μm or greater, about 60 μm or greater, about 80 μm or greater, about 100 μm or greater, about 125 μm or greater, about 150 μm or greater, 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 209 may be in a range of about 10 μm to about 3mm, about 10 μm to about 2mm, 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, the substrate thickness 109 or 209 may be in a range of about 80 μm to about 2mm, about 80 μm to about 1mm, about 80 μm to about 500 μm, about 80 μm to about 300 μm, about 200 μm to about 2mm, about 200 μm to about 1mm, about 200 μm to about 500 μm, about 500 μm to about 2mm, about 500 μm to about 1mm, or any range or subrange therebetween. In aspects, the substrate thickness may be about 300 μm or less, such as about 10 μm to about 300 μm, 25 μm to about 300 μm, about 25 μm to about 200 μm, about 25 μm to about 180 μm, about 40 μm to about 160 μm, about 60 μm to about 160 μm, about 80 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 221 and a second portion 231. As shown, the first portion 221 may include a substrate thickness 209 between the first surface region 223 and the second surface region 225, and the second portion 231 may include a substrate thickness 209 between the third surface region 233 and the fourth surface region 235. Similarly, as shown, second surface region 225 and fourth surface region 235 may extend along second plane 206 a. In other aspects, as shown, the first surface region 223 and the third surface region 233 may extend along the first plane 204 a. In other aspects, the substrate 203 may include a central portion 281 positioned between the first portion 221 and the second portion 231. In even other aspects, the central portion 281 may include a first central surface region 213 positioned between the first surface region 223 and the third surface region 233 that is recessed a first distance 219 from the first plane 204a to define a first recess 234. In other aspects, central portion 281 may include a second central surface region 243 positioned between second surface region 225 and fourth surface region 235 that is recessed a second distance 249 from second plane 206a to define second recess 241. In even other aspects, the central portion 281 may include a central thickness 289 defined between the first and second central surface regions 213, 243 as, for example, a distance between the third plane 204b along which the first central surface region 213 may extend and the fourth plane 206b along which the second central surface region 243 may extend.

In aspects, the center thickness 289 may be about 10 μm or greater, about 25 μm or greater, about 80 μm or greater, about 100 μm or greater, about 1mm or less, about 500 μm or less, or about 200 μm or less. In aspects, the center thickness 289 may be in a range of from about 10 μm to about 1mm, from about 25 μm to about 500 μm, from about 100 μm to about 200 μm, from about 25 μm to about 100 μm, or any range or subrange therebetween. In aspects, the percentage of the center thickness 289 to the substrate thickness 209 may be 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 percentage of the center thickness 289 that is the substrate thickness 209 may be in a range of about 0.5% to about 20%, about 0.5% to about 13%, about 1% to about 10%, about 2% to about 8%, about 5% to about 8%, about 6% to about 8%, or any range or subrange therebetween.

In aspects, the second distance 249 may be greater than the first distance 219. In aspects, the first distance 219 may be greater than the second distance 249. In aspects, the first distance 219 and/or the second distance 249 may be less than the center thickness 289. In other aspects, the percentage of the first distance 219 and/or the second distance 249 to the substrate thickness 209 may be about 1% or greater, about 2% or greater, about 5% or greater, about 10% or greater, about 12% or greater, about 30% or less, about 25% or less, about 20% or less, about 18% or less, or about 15% or less. In other aspects, the first distance 219 and/or the second distance 249 may be in a range of about 1% to about 30%, about 1% to about 25%, about 2% to about 25%, about 5% to about 20%, about 10% to about 18%, about 12% to about 15%, or any range or subrange therebetween, as a percentage of the substrate thickness 209.

In aspects, as shown in fig. 2, the fourth major surface 117 of the coating 113 can contact the first surface region 223 and the third surface region 233. In other aspects, as shown, the coating 113 may extend across the first plane 204 a. For example, as shown in fig. 2, the coating 113 can fill the first recess 234 between the first portion 321 and the second portion 331, and/or the coating 113 (e.g., the fourth major surface 117) can contact the first central surface region 213.

In aspects, as shown in fig. 2, the polymer-based portion 291 may fill at least a portion of the second recess 241. For example, the polymer-based portion 291 may include a polymer thickness between the fifth major surface 293 and the sixth major surface 295, which may be equal to the second distance 249. In an aspect, as shown, the fifth major surface 293 of the polymer-based portion 291 can contact the second central surface region 243. In aspects, as shown, the sixth major surface 295 of the polymer-based portion 291 can include a planar surface, e.g., coplanar with the second surface region 225 and the fourth surface region 235 (e.g., extending along the shared second plane 206 a). In aspects, polymer-based portion 291 comprises a polymer (e.g., an optically transparent polymer). In other aspects, the polymer-based portion 291 may include one or more of the following that are optically transparent: acrylic (e.g., polymethyl methacrylate (PMMA)), epoxy, silicone, and/or polyurethane. Examples of epoxides include bisphenol-based epoxy resins, phenolic-based epoxides, cycloaliphatic-based epoxides, and glycidoxylamine-based epoxides. In other aspects, the polymer-based portion 291 may include one or more of a polyolefin, a polyamide, a halogen-containing polymer (e.g., polyvinyl chloride or a fluoropolymer), an elastomer, a urethane, a phenolic resin, a parylene, a polyethylene terephthalate (PET), and/or a Polyetheretherketone (PEEK). Exemplary aspects of the polyolefin include low molecular weight polyethylene (LDPE), high molecular weight polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene (PP). Exemplary aspects of fluoropolymers include Polytetrafluoroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), perfluoroalkoxy (PFA), fluorinated Ethylene Propylene (FEP) polymers, and Ethylene Tetrafluoroethylene (ETFE) polymers. Exemplary aspects of the elastomer include rubber (e.g., polybutadiene, polyisoprene, chloroprene rubber, butyl rubber, nitrile rubber), polyurethane, and block copolymers (e.g., styrene-butadiene, impact-resistant polystyrene, dichlorophosphazene polymer) comprising one or more of polystyrene, dichlorophosphazene polymer and/or poly (5-ethylene-2-norcamphene). In aspects, polymer-based portion 291 may further include nanoparticles, such as carbon black, carbon nanotubes, silica nanoparticles, or nanoparticles comprising a polymer. In aspects, the polymer-based portion may further include fibers to form a polymer-fiber composite.

In aspects, as shown in fig. 2, the coated article 201 may further include an adhesive layer 261. Adhesive layer 261 can include an adhesive thickness 267 defined between seventh major surface 263 and eighth major surface 265. In aspects, bond thickness 267 can be about 5 μm or greater, about 10 μm or greater, about 25 μm or greater, about 40 μm or greater, about 60 μm or greater, about 80 μm or greater, about 100 μm or greater, about 400 μm or less, about 300 μm or less, about 250 μm or less, about 200 μm or less, about 180 μm or less, about 160 μm or less, or about 160 μm or less. In aspects, bond thickness 267 can be in a range of about 5 μm to about 400 μm, about 5 μm to about 300 μm, about 10 μm to about 200 μm, about 25 μm to about 180mm, about 40 μm to about 180 μm, about 40 μm to about 160 μm, about 60 μm to about 140 μm, about 80 μm to about 140 μm, about 100 μm to about 140 μm, or any range or subrange therebetween.

In other aspects, as shown, the seventh major surface 263 of the adhesive layer 261 can face and/or contact the second surface region 225 and the fourth surface region 235. In even other aspects, as shown, the seventh major surface 263 of the adhesive layer 261 can face and/or contact the sixth major surface 295 of the polymer-based portion 291. In even other aspects, the adhesive layer 261 may fill the second recess 241 instead of or in addition to the polymer-based portion 291. In aspects, the polymer-based portion 291 may be filled with the region as shown by the adhesive layer 261.

In aspects, the adhesive layer 261 can include one or more of a polyolefin, a polyamide, a halogen-containing polymer (e.g., polyvinyl chloride or a fluoropolymer), an elastomer, a urethane, a phenol resin, a poly-p-xylene, a polyethylene terephthalate (PET), and a Polyetheretherketone (PEEK). Exemplary aspects of the polyolefin include low molecular weight polyethylene (LDPE), high molecular weight polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene (PP). Exemplary aspects of fluoropolymers include Polytetrafluoroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), perfluoroalkoxy (PFA), fluorinated Ethylene Propylene (FEP) polymers, and Ethylene Tetrafluoroethylene (ETFE) polymers. Exemplary aspects of elastomers include rubbers (e.g., polybutadiene, polyisoprene, chloroprene rubber, butyl rubber, nitrile rubber) and block copolymers (e.g., styrene-butadiene, high impact polystyrene, dichlorophosphazene polymers). In other aspects, the adhesive layer 261 can include an optically clear adhesive. In even other aspects, the optically clear adhesive may comprise one or more of optically clear polymers: acrylic (e.g., polymethyl methacrylate (PMMA)), epoxy, silicone, and/or polyurethane. Examples of epoxides include bisphenol-based epoxy resins, phenolic-based epoxides, cycloaliphatic-based epoxides, and glycidoxylamine-based epoxides. In even other aspects, the optically clear adhesive may include, but is not limited to, an acrylic adhesive, such as a 3m 8212 adhesive, or an optically clear liquid adhesive, such as a LOCTITE optically clear liquid adhesive. Exemplary aspects of optically clear adhesives include transparent acrylic, epoxy, silicone, and polyurethane. For example, the optically clear liquid adhesive may include one or more of LOCTITE AD 8650, LOCTITE AA3922, LOCTITE EA E-05MR, LOCTITE UK U-09LV, all available from Henkel.

In aspects, as shown in fig. 2, the coated article 201 may further comprise a release liner 271. The release liner 271 can include a fifth major surface 273 and a sixth major surface 275 opposite the fifth major surface. In other aspects, as shown, the second major surface 207 of the substrate 203 may face the fifth major surface 273 of the release liner 271. In even other aspects, the eighth major surface 265 of the adhesive layer 261 can contact the fifth major surface 273 of the release liner 271. In other aspects, the release liner 271 can comprise paper and/or a polymer. Exemplary aspects of the paper include kraft paper, machine gloss paper, polymer coated paper (e.g., polymer coated glassine paper, silicon steel paper), or clay coated paper. Exemplary aspects of the polymer include polyesters (e.g., polyethylene terephthalate (PET)), fluoropolymers (e.g., polytetrafluoroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), perfluoroalkoxy (PFA), fluorinated Ethylene Propylene (FEP) polymers, and Ethylene Tetrafluoroethylene (ETFE) polymers), and polyolefins (e.g., low Density Polyethylene (LDPE), high Density Polyethylene (HDPE), polypropylene (PP)). In aspects, as shown in fig. 3, the coated article 301 may not include a release liner. Providing a release liner 271 can provide support for the layer and/or protect the first major surface of the layer from contamination so that a laminate that can incorporate the layer (e.g., film) has good adhesion.

In aspects, as shown in fig. 3, the coated article 301 can include a first portion 321 and a second portion 331. In other aspects, as shown, the first portion 321 can include a first surface region 323 opposite the second surface region 325. In other aspects, as shown, the second portion 331 may include a third surface region 333 opposite the fourth surface region 335. In other aspects, as shown, the first surface region 323 and/or the third surface region 333 may extend along the third plane 304, and/or the second surface region 325 and/or the fourth surface region 335 may extend along the fourth plane 306. In even other aspects, the partial thickness 329 may be defined between the third plane 304 and the fourth plane 306 and may be within one or more of the ranges discussed above for the substrate thickness 109.

In other aspects, as shown in fig. 3, the first portion 321 may include a first edge surface region 303 extending between the first surface region 323 and the second surface region 325, and/or the second portion 331 may include a second edge surface region 305 extending between the third surface region 333 and the fourth surface region 335. In even other aspects, as shown in fig. 3, the first edge surface region 303 and/or the second edge surface region 305 may include a first outwardly convex curved edge surface and/or a second outwardly convex curved edge surface, respectively. In still other aspects, the first edge surface region 303 and/or the second edge surface region 305 may include a cross-sectional profile perpendicular to the edge surface that is a circular arc shape, although other shapes (e.g., elliptical) are possible. In still other aspects, the first outwardly convex curved edge surface and/or the second outwardly convex curved edge surface may be characterized by a first radius of curvature 307 and/or a second radius of curvature 309, respectively. In still other aspects, the percentage of the first radius of curvature 307 and/or the second radius of curvature 309 to the partial thickness 329 may be about 30% or greater, about 40% or greater, about 45% or greater, about 49% or greater, about 70% or less, about 60% or less, about 55% or less, or about 51% or less. In even other aspects, the percentage of the first radius of curvature 307 and/or the second radius of curvature 309 to the portion of the thickness 329 may be in a range of about 30% to about 70%, about 30% to about 60%, about 30% to about 55%, about 30% to about 51%, about 40% to about 70%, about 40% to about 60%, about 40% to about 55%, about 40% to about 51%, about 45% to about 70%, about 45% to about 60%, about 45% to about 55%, about 45% to about 51%, about 49% to about 70%, about 49% to about 60%, about 49% to about 55%, about 49% to about 51%, or any range or sub-range therebetween. In other aspects, although not shown, the first and/or second edge surface regions may comprise linear (e.g., planar) edge surfaces, i.e., comprise first and/or second linear edge surfaces, respectively.

As shown in fig. 3, a minimum distance 343 between the first portion 321 and the second portion 331 may be defined between the first edge surface area 303 and the second edge surface area 305. When the coated article is in the configuration shown in fig. 3, the minimum distance 343 between the first portion 321 and the second portion 331 is equal to the minimum distance between the peripheral portion 345 of the first edge surface region 303 and the peripheral portion 347 of the second edge surface region 305. In aspects, as shown, the first portion 321 may be a different physical structure than the second portion 331, which is separated from the first portion 321 by a minimum distance 343. In aspects, the minimum distance 343 between the first portion 321 and the second portion 331 can be about 1 times or more, about 1.4 times or more, about 1.5 times or more, about 2 times or more, about 3 times or less, about 2.5 times or less, or about 2 times or less the minimum parallel plate distance of the coated article. In aspects, minimum distance 343 can be in a range of about 1.4 to about 3 times, about 1.4 to about 2.5 times, about 1.4 to about 2 times, about 1.5 to about 3 times, about 1.5 to about 2.5 times, about 1.5 to about 2 times, about 2 to about 3 times, about 2 to about 2.55 times, or any range or subrange therebetween relative to the minimum parallel plate distance value. Without wishing to be bound by theory, the length of the curved portion between the parallel plates in a circular configuration may be about 0.8 times the parallel plate distance 507. In aspects, the minimum distance 343 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, minimum distance 343 may be in the range of about 1mm to about 200mm, about 5mm 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, about 5mm to about 60mm, about 10mm to about 60mm, about 20mm to about 60mm, about 40mm to about 60mm, or any range or subrange therebetween. In aspects, minimum distance 343 may be in the range of about 1mm to about 100mm, about 1mm to about 60mm, about 1mm to about 40mm, about 1mm to about 30mm, about 2mm to about 20mm, about 5mm to about 20mm, about 10mm to about 20mm, or any range or subrange therebetween. In aspects, minimum distance 343 may be in the range of about 1mm to about 20mm, about 1mm to about 10mm, about 2mm to about 5mm, or any range or subrange therebetween. By providing a minimum distance between the first portion and the second portion, folding of the coated article without failure can be facilitated.

In aspects, as shown in fig. 3, the third major surface 115 of the coating 113 can contact the first surface region 323 and the third surface region 333. In other aspects, as shown, the coating 113 may extend across the third plane 304 to contact the first major surface 105 of the substrate 103 while filling the region 341 between the first portion 321 and the second portion 331. For example, as shown in fig. 3, the coating 113 can fill an area 341 between the first portion 321 and the second portion 331, the coating 113 can contact the first edge surface area 303 and/or the second edge surface area 305, and/or the coating 113 can extend to the fourth plane 306 (e.g., a portion of the third major surface 115 can extend along the fourth plane 306).

In aspects, the substrate 103 or 203, the first portion 321, and/or the second portion 331 may comprise a glass-based substrate and/or a ceramic-based substrate, wherein one or more portions of the substrate may comprise a compressive stress region. In aspects, the compressive stress region may be created by chemically strengthening the substrate. Chemical strengthening may include ion exchange processes in which ions in the surface layer are replaced by or exchanged with larger ions having the same valence or oxidation state. The method of chemical strengthening will be discussed later. Without wishing to be bound by theory, chemically strengthened substrates may achieve a smaller (e.g., less than about 10mm or less) bend radius because compressive stress from chemical strengthening may counteract bending-induced tensile stress on the outermost surface of the substrate (e.g., first major surface 105 in fig. 5 and 7, first major surface 205 in fig. 6). The compressive stress region may extend into a portion of the substrate to a depth, referred to as the compression depth. As used herein, compressive depth means the depth at which the stress in the chemically strengthened substrate described herein changes from compressive to tensile stress. The depth of compression can be measured by a surface stress meter or a scattered light polarizer (SCALP, where the values reported herein are measured by SCALP-5 manufactured by glastress co., estonia), depending on the ion exchange treatment and the thickness of the article being measured. In the case where stress in the substrate is generated by exchanging potassium ions into the substrate, a surface stress meter such as FSM-6000 (Orihara Industrial co., ltd. (Japan)) is used to measure the compression depth. Unless otherwise indicated, compressive stress (including surface CS) is measured by a surface stress meter (FSM) using commercially available instruments (e.g., FSM-6000 manufactured by Orihara). The surface stress measurement depends on an accurate measurement of the stress optical coefficient (stress optical coefficient; SOC), which is related to the birefringence of the glass. Unless otherwise indicated, SOC is measured according to procedure C (glass disk method) described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the contents of which are incorporated herein by reference in its entirety. In case the stress is generated by exchanging sodium ions into the substrate and the measured article is thicker than 75 μm, the compressive depth and the Central Tension (CT) are measured using the SCALP. In the case where the stress in the substrate is created by exchanging potassium and sodium ions into the glass and the measured article is thicker than 75 μm, the compression depth and CT are measured by SCALP. Without wishing to be bound by theory, the exchange depth of sodium ions may indicate the compression depth, while the exchange depth of potassium ions may indicate the magnitude of the compressive stress (but not the change in stress from compression to tension). The refractive near-field (RNF; RNF method is described in U.S. patent No. 8,854,623, entitled "Systems and methods for measuring a profile characteristic of a glass sample," which is incorporated herein by reference in its entirety), methods can also be used to derive a graphical representation of stress profiles. When the RNF method is used to derive a graphical representation of the stress profile, the maximum center tension value provided by the SCALP is used in the RNF method. The graphical representation of the stress profile derived by RNF is force balanced and calibrated to the maximum center tension value provided by the SCALP measurement. As used herein, "depth of layer" (DOL) means the depth to which ions (e.g., sodium, potassium) are exchanged to the substrate. Throughout this disclosure, when the central tension is not directly measurable by the SCALP (e.g., when the measured article is thinner than 75 μm), the maximum central tension may be approximately the product of the maximum compressive stress and the compressive depth divided by the difference between the substrate thickness and twice the compressive depth, where the compressive stress and the compressive depth are measured by the FSM.

In an aspect, the substrate 103 can be chemically strengthened to form a first compressive stress region extending from the first major surface 105 to a first compressive depth. In an aspect, the substrate 103 may be chemically strengthened to form a second compressive stress region extending from the second major surface 107 to a second compressive depth. In even other aspects, the percentage of 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) to the substrate thickness 109 may be 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 even other aspects, the percentage of the first compression depth and/or the second compression depth to the substrate thickness 109 may be in a range of about 1% to about 30%, about 1% to about 25%, about 5% to about 20%, about 10% to about 20%, or any range or subrange therebetween. In aspects, the first depth of compression and/or the second depth of compression 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 depth of compression and/or the second depth of compression may be in a range of about 1 μm to about 200 μm, about 1 μm to about 150 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 the same as the second compression depth. By providing a glass-based substrate and/or a ceramic-based substrate with a first compression depth and/or a second compression depth in the range of about 1% to about 30% of the first thickness, good impact and/or puncture resistance may be achieved.

In aspects, the substrate 103 may include a first depth of layer of one or more alkali metal ions associated with a first compressive stress region and a second depth of layer of one or more alkali metal ions associated with a second compressive stress region. In aspects, the percentage of the first layer depth and/or the second layer depth to the substrate thickness 109 may be 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 a range of 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, by percentage of the substrate thickness 109. 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 a range of about 1 μm to about 200 μm, about 1 μm to about 150 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 100 megapascals (MPa) or greater, about 300MPa 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 range of about 100MPa to about 1,500MPa, about 100MPa to about 1,200MPa, about 300MPa to about 1,000MPa, 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 100MPa to about 1,500MPa may achieve good impact and/or puncture resistance.

In an aspect, the substrate 103 may include a central tensile region positioned between the first compressive stress region and the second compressive stress region. In other aspects, the central tensile region may include a maximum central tensile stress. In aspects, the maximum central tensile stress may be about 50MPa or greater, about 100MPa or greater, about 200MPa or greater, about 250MPa or greater, 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 range of 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 other aspects, referring to fig. 2, the first surface region 223 of the first portion 221 and the third surface region 233 of the second portion 231 may include the first compressive stress region, the first compressive depth, the first depth of layer, and/or the maximum first compressive stress discussed above. In other aspects, referring to fig. 2, the second surface region 225 of the first portion 221 and the fourth surface region 235 of the second portion 231 may include the second compressive stress region, the second compressive depth, the second depth of layer, and/or the maximum second compressive stress discussed above. In other aspects, the central portion 281 may be chemically strengthened to form a first central compressive stress region extending from the first central surface region 213 to a first central compressive depth and/or a second central compressive stress region extending from the second central surface region 243 to a second central compressive depth. In even other aspects, the percentage of the first center compressed depth to the center thickness 289 and/or the percentage of the second center compressed depth to the center thickness 289 may be within one or more of the ranges discussed above for the percentage of the first compressed depth and/or the second compressed depth to the substrate thickness. In even 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 still other aspects, the percentage of the first center layer depth to the center thickness 289 and/or the percentage of the second center layer depth to the center thickness 289 may be within one or more of the ranges discussed above for the percentage of the first layer depth and/or the second layer depth to the substrate thickness. 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 for the first compressive stress and/or the maximum second compressive stress.

In other aspects, referring to fig. 3, the first portion 321 and/or the second portion 331 may comprise a glass-based substrate or a ceramic-based substrate. In aspects, the first portion 321 may be chemically strengthened to form a third compressive stress region extending from the first surface region 323 to a third compressive depth and/or a fourth compressive stress region extending from the second surface region 325 to a fourth compressive depth. In aspects, the second portion 331 may be chemically strengthened to form a fifth compressive stress region extending from the third surface region 333 to a fifth compressive depth and/or a sixth compressive stress region extending from the fourth surface region 335 to a sixth compressive depth. In even other aspects, the percentage of the third compression depth, the fourth compression depth, the fifth compression depth, and/or the sixth compression depth to the partial thickness 329 may be within one or more of the ranges discussed above for the percentage of the first compression depth and/or the second compression depth to the substrate thickness. In even other aspects, the third compressive stress region may include a third layer depth of the one or more alkali metal ions associated with the third compressive stress region, the fourth compressive stress region may include a fourth layer depth of the one or more alkali metal ions associated with the fourth compressive stress region, the fifth compressive stress region may include a fifth layer depth of the one or more alkali metal ions associated with the fifth compressive stress region, and/or the sixth compressive stress region may include a sixth layer depth of the one or more alkali metal ions associated with the sixth compressive depth. In still other aspects, the percentage of the third layer depth, the fourth layer depth, the fifth layer depth, and/or the sixth layer depth to the partial thickness 329 may be within one or more of the ranges discussed above for the percentage of the first layer depth and/or the second layer depth to the substrate thickness. In even other aspects, the third compressive stress region may comprise a maximum third compressive stress, the fourth compressive stress region may comprise a maximum fourth compressive stress, the fifth compressive stress region may comprise a maximum fifth compressive stress, and/or the sixth compressive stress region may comprise a maximum sixth compressive stress, which may be within one or more of the ranges discussed above for the maximum first compressive stress and/or the maximum second compressive stress.

In aspects, as shown in fig. 1-3 and 5-6, the coated articles 101, 201, 301, 401, and 601 can include a coating 113. As shown, the coating 113 can include a third major surface 115 and a fourth major surface 117 opposite the third major surface 115. The coating thickness 119 may be defined between the third major surface 115 and the fourth major surface 117 as a minimum distance between the third major surface 115 and the fourth major surface 117. In other aspects, the coating thickness 119 can be about 0.1 μm or greater, about 1 μm or greater, about 3 μm or greater, about 5 μm or greater, about 10 μm or greater, about 15 μm or greater, about 20 μm or greater, about 25 μm or greater, about 40 μm or greater, about 50 μm or greater, about 60 μm or greater, about 70 μm or greater, about 80 μm or greater, about 90 μm or greater, about 200 μm or less, about 150 μm or less, about 100 μm or less, about 80 μm or less, about 50 μm or less, about 30 μm or less, about 25 μm or less, about 20 μm or less, about 15 μm or less, or about 10 μm or less. In aspects, the coating thickness 119 can be in a range of about 0.1 μm to about 200 μm, about 1 μm to about 150 μm, about 5 μm to about 100 μm, about 10 μm to about 100 μm, about 20 μm to about 80 μm, about 30 μm to about 80 μm, about 40 μm to about 80 μm, about 50 μm to about 80 μm, about 60 μm to about 80 μm, or any range or subrange therebetween. In other aspects, the coating thickness 119 can be about 50 μm or less, such as about 0.1 μm to about 50 μm, about 1 μm to about 30 μm, about 3 μm to about 30 μm, about 5 μm to about 25 μm, about 10 μm to about 20 μm, about 15 μm to about 20 μm, or any range or subrange therebetween. In aspects, the coating thickness 119 can be about 50 μm or greater, such as about 50 μm to about 200 μm, about 60 μm to about 150 μm, about 70 μm to about 100 μm, about 80 μm to about 100 μm, or any range or subrange therebetween.

As shown in fig. 1-2, the coating 113 may be disposed over the substrate 103 or 203. In other aspects, as shown, the coating 113 can be disposed over the first major surface 105 or 205 of the substrate 103 or 203. In even other aspects, as shown, the fourth major surface 117 of the coating 113 can contact the first major surface 105 or 205 at the interface 111. In aspects, the interface 111 can include a silane coupling agent bonded to one or both of the first major surface 105 or 205 of the substrate 103 or 205 or the fourth major surface 117 of the coating 113.

Coating 113 may include a variety of functionalized oligomeric silsesquioxanes. In aspects, the functional groups of the first and/or second functionalized oligomeric silsesquioxanes that functionalize the plurality of functionalized oligomeric silsesquioxanes may include any of the functional groups discussed above as functionalized oligomeric silsesquioxanes. In other aspects, the functional groups of the first and/or second functionalized oligomeric silsesquioxanes that functionalize the plurality of functionalized oligomeric silsesquioxanes may include epoxypropyl functional groups (e.g., epoxypropyloxypropyl) and/or epoxyfunctional groups (e.g., epoxycyclohexyl). In aspects, wherein the plurality of functionalized oligomeric silsesquioxanes may comprise a plurality of functionalized polyhedral oligomeric silsesquioxanes (POSS). In even other aspects, the first functionalized POSS and/or the second functionalized POSS of the plurality of functionalized POSS can be functionalized with a glycidoxypropyl functional group (e.g., glycidoxypropyl) and/or an epoxyfunctional group (e.g., epoxycyclohexyl).

As discussed above with respect to the composition, the coating 113 can include a first functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes bound to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes by a linking group (e.g., a polymer) terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group. In aspects, the linking group may comprise a polymer comprising any of the polymers discussed above as attaching a first functionalized oligomeric silsesquioxane to a second functionalized oligomeric silsesquioxane. In aspects, the linking group may comprise any of the non-polymeric linking groups discussed above. In aspects, the linking group can include an oxygen atom in the backbone of the linking group. In other aspects, oxygen atoms may be present in a variety of monomers including the linking group of the polymer. In other aspects, the polymer may comprise poly (dimethylsiloxane) and/or poly (propylene oxide). In aspects, the linking group (e.g., polymer) may be substantially free of urethane acrylates and/or polycarbonates. In aspects, the linking group can include a linear polymer, a branched polymer, a star polymer, and/or a dendritic polymer. In aspects, the linking group may comprise a polymer comprising a glass transition temperature (Tg) within one or more of the ranges discussed above for the glass transition of the polymer. In other aspects, the number average molecular weight of the polymer may be within one or more of the ranges discussed above for the number average molecular weight of the polymer. In aspects, substantially all of the linking groups (e.g., polymers) can be attached to both functionalized oligomeric silsesquioxanes. In aspects, the first functional group and/or the second functional group may include one or more of the functional groups discussed above as functional groups at the ends (e.g., first end, second end) of the linking group (e.g., polymer). In other aspects, the first functional group and/or the second functional group may include an acid alcohol, an anhydride, an amide, an amine, an alcohol, a chloride, a cyanide, an epoxide, a thiol, and/or a magnesium halide. In even other aspects, the first functional group and/or the second functional group may comprise an amine (e.g., an aminopropyl group). In other aspects, the first functional group and/or the second functional group may be the same as the normal terminal functional group of the polymer. In other aspects, the first 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 can be different from the normal terminal functional group of the polymer and the second functional group can be different from the normal terminal group of the polymer. In aspects, the first functional group and/or the second functional group may include an alcohol, an acrylate, an epoxide, a ureido, or a combination thereof.

In aspects, the composition may include, in addition to the first functionalized oligomeric silsesquioxane, a third functionalized oligomeric silsesquioxane that is not bound to a linking group (e.g., polymer) and a second functionalized oligomeric silsesquioxane that is bound to a linking group (e.g., polymer). In other aspects, the coating 113 may include more functionalized oligomeric silsesquioxanes than the compositions discussed above. In aspects, the ratio of the number of linking groups (e.g., polymer) (e.g., on a molar basis) to the number of functionalized oligomeric silsesquioxanes (e.g., on a molar basis) can be within one or more of the ranges discussed above (e.g., about 0.001 to about 0.06). In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes to the total weight of the plurality of functionalized oligomeric silsesquioxanes and the linking group (e.g., polymer) can be within one or more of the ranges discussed above. In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes to the total weight of the plurality of functionalized oligomeric silsesquioxanes and the polymer can be about 20% or more, about 40% or more, about 60% or more, about 80% or more, about 90% or more, about 99% or less, about 97% or less, about 95% or less, or about 93% or less. In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes to the total weight of the plurality of functionalized oligomeric silsesquioxanes and the polymer may be in a range of about 30% to about 99%, about 40% to about 97%, about 50% to about 97%, about 60% to about 95%, about 70% to about 95%, about 80% to about 93%, about 90% to about 97%, about 90% to about 95%, or any range or subrange therebetween. In aspects, the weight percent (wt%) of the plurality of functionalized oligomeric silsesquioxanes may be within one or more of the wt% ranges previously discussed in this paragraph. Providing a low molar ratio of polymer to the plurality of functionalized oligomeric silsesquioxanes (e.g., about 0.06 or less) may result in a polymer that binds to both functionalized oligomeric silsesquioxanes, which may achieve the benefits described herein.

In aspects, the coating 113 can include a silane coupling agent. In other aspects, the silane coupling agent may include one or more of the silane coupling agents discussed above. In even other aspects, the silane coupling agent may include (3-triethoxysilyl) propyl succinic anhydride, (3-mercaptopropyl) trimethoxysilane and/or 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane. In aspects, the coating 113 may include a photoinitiator. In other aspects, the photoinitiator may comprise one or more of the photoinitiators discussed above. In even other aspects, the photoinitiator may comprise a UV sensitive photoinitiator. In even other aspects, the photoinitiator may be configured to initiate cationic polymerization. In even other aspects, the photoinitiator may be configured to initiate free radical polymerization. Without wishing to be bound by theory, the alcohol, acrylate, epoxide, and ureido functionalities readily react (e.g., polymerize) when the free radical photoinitiator is activated, and the acid alcohol, anhydride, amide, amine, alcohol, chloride, cyanide, epoxide, thiol, and magnesium halide functionalities readily react (e.g., polymerize) when the cationic photoinitiator is activated. In aspects, the coating 113 can include more of the silane coupling agent and/or photoinitiator than is present in the compositions discussed above, for example if the silane coupling agent and/or photoinitiator is added prior to forming the coating. In aspects, the coating 113 may be substantially free of fluorine-based compounds. As used herein, the coating may be substantially free of fluorine-based compounds, while containing trace amounts of fluorine in minor components of the composition (e.g., about 2wt% or less of the photoinitiator), corresponding to a total wt% of fluorine of about 0.5wt% or less. In other aspects, the coating 113 may be free of fluorine-based compounds. In aspects, the coating 113 may be free of photoinitiators. Providing a coating that does not contain a photoinitiator can avoid yellowing problems. In aspects, the coating 113 can be free of silane coupling agents, such as when the coating includes a high adhesion value in the absence of silane coupling agents.

In aspects, the coating may be substantially free of nanoparticles. In aspects, the coating may be substantially free of silica nanoparticles. In other aspects, the composition may be free of silica nanoparticles. Providing a coating and/or coated article that is substantially free and/or free of silica nanoparticles may improve the optical properties (e.g., maintain low haze and/or high transmittance even after aging at elevated temperature and/or humidity) and/or reduce mechanical properties (e.g., hardness, modulus, strain) of the resulting coating and/or coated article as compared to a corresponding coating and/or coated article comprising a plurality of functionalized oligomeric silsesquioxanes without silica nanoparticles. In aspects, the composition may comprise silica nanoparticles, alumina nanoparticles, zirconia nanoparticles, titania nanoparticles, carbon black, and/or combinations thereof. In aspects, the composition may comprise silica nanoparticles and/or alumina nanoparticles, which may be present in an amount within one or more of the ranges discussed above for wt% of the silica nanoparticles and/or alumina nanoparticles. In other aspects, the silica nanoparticles and/or alumina nanoparticles may include average effective diameters within one or more of the ranges discussed above for average effective diameters of the silica nanoparticles and/or alumina nanoparticles. In other aspects, the silica nanoparticles and/or alumina nanoparticles may not be bound to one of the plurality of functionalized oligomeric silsesquioxanes in the composition. In aspects, the effective diameter of the functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes, the average effective diameter of the plurality of functionalized oligomeric silsesquioxanes, and/or substantially all and/or all of the functionalized oligomeric silsesquioxanes may be within one or more of the ranges discussed above for the effective diameters of the functionalized oligomeric silsesquioxanes. In aspects, the functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes can be directly bound to only the linking group (e.g., polymer) or to only the linking group (e.g., polymer) and the silane coupling agent. In aspects, all of the plurality of functionalized oligomeric silsesquioxanes can be directly bound to only the linking group (e.g., polymer) or directly bound to only the linking group (e.g., polymer) and the silane coupling agent.

In aspects, the coating 113 may include pen hardness. In aspects, the pen hardness may be about 5H or greater, 6H or greater, 7H or greater, 8H or greater, 9H or greater, or 9H or less. In aspects, the coating 113 may include a pen hardness in the range of about 5H to about 9H, about 6H to about 9H, about 7H to about 9H, about 8H to about 9H, or any range or subrange therebetween. In aspects, the measured pen hardness after the coating 113 has been stored at 25 ℃ for 72 hours may be within one or more of the ranges discussed above for pen hardness (e.g., about 5H to about 9H, about 7H to about 9H).

Throughout this disclosure, the tensile strength, ultimate elongation (e.g., strain at failure), and yield point of the coating 113 are determined using ASTM D412A using a tensile testing machine such as Instron 3400 or Instron 6800 at 23 ℃ and 50% relative humidity with a type I dog bone sample. In aspects, the tensile strength of the coating 113 may 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 coating 113 may be in the range of 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 coating 113 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 coating 113 can be in the range of about 3% to about 20%, about 4% to about 20%, about 5% 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 final elongation of the coating 113 can be in the range of about 3% to about 8%, about 4% to about 8%, about 5% to about 8%, about 6% to about 8%, or any range or subrange therebetween.

Throughout the present disclosure, the modulus of elasticity (e.g., young's modulus) of the coating is measured using ISO 527-1:2019. In aspects, the modulus of elasticity of the coating 113 can be about 200MPa or greater, about 500MPa or greater, about 700MPa or greater, about 800MPa or greater, about 900MPa or greater, about 1,200MPa or greater, about 2,500MPa or less, about 2,000MPa or less, about 1,500MPa or less, about 1,400MPa or less, or about 1,300MPa or less. In aspects, the modulus of elasticity of the coating 113 can be in the range of about 200MPa to about 2,500MPa, about 200MPa to about 2,000MPa, about 500MPa to about 1,500MPa, about 700MPa to about 1,500MPa, about 800MPa to about 1,500MPa, about 900MPa to about 1,500MPa, about 1,200MPa to about 1,500MPa, about 1,300MPa to about 1,400MPa, or any range or subrange therebetween. In aspects, the modulus of elasticity of the coating 113 can be about 800MPa or greater, for example, in the range of about 800MPa to about 2,500MPa, about 800MPa to about 2,000MPa, about 800MPa to about 1,500MPa, about 800MPa to about 1,400MPa, about 900MPa to about 1,300MPa, or any range or subrange therebetween.

In aspects, the coating 113, the substrate 103 or 203, the first portion 321, the second portion 331, and/or the coated article 101, 201, 301, 401, 601, or 701 can be optically transparent. In aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, or 701 can include an average light transmittance of 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, measured in light wavelengths in the range of 400nm to 700 nm. In other aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, or 701 can include an average light transmittance in the range of about 90% to 100%, about 90% to about 96%, about 91% to about 95%, about 92% to about 94%, about 93% to about 94%, or any range or subrange therebetween, measured in light wavelengths in the range of 400nm to 700 nm. In aspects, the coating 113 may be substantially free of visible crystals and/or bubbles at 100-fold magnification.

In aspects, the coating 113, the substrate 103 or 203, the first portion 321, the second portion 331, and/or the coated article 101, 201, 301, 401, 601, or 701 can include haze. As used herein, haze refers to transmission haze measured according to ASTM E430. HAZE was measured using a HAZE meter under the trademark HAZE-GUARD PLUS supplied by BYK Gardner using an opening above the source port. The diameter of the opening was 8mm. CIE D65 illuminant is used as a light source for illuminating coatings and/or coated articles. Unless otherwise indicated, haze is measured in a direction perpendicular to the angle of incidence of light on the surface of the sample (e.g., the third major surface 115 of the coating 113, the first major surface 105 of the substrate 103, and/or the second major surface 107 of the substrate 203). The haze of the coating was measured with the coating mounted on a glass-based article having a thickness of 1.0 millimeter (mm). In other aspects, the haze of the coating 113 and/or the coated article 101, 201, 301, 401, 601, or 701 can be about 0.01% or greater, about 0.1% or greater, about 0.2% or greater, about 0.5% or less, about 0.4% or less, or about 0.3% or less. In other aspects, the haze of the coating 113, the substrate 103 or 203, the first portion 321, the second portion 331, and/or the coated article 101, 201, 301, 401, 601, or 701 may be in the range of about 0.01% to about 0.5%, about 0.01% 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 enable good visibility through the substrate.

Throughout this disclosure, coating 113 can include CIE (L, a, b) chromaticity coordinates measured using D65 illuminant using a colorimeter (e.g., a three-phase laser colorimeter) such as a CR-400Chroma Meter (Konica Minolta) or a TR 520 spectro-luminance Meter (Lazar Scientific) and/or a spectro-luminance Meter at an observer angle of 10 °. In aspects, the CIE b values may be about 1 or less, about 0.5 or less, about 0.4 or less, about 0 or more, about 0.2 or more, or about 0.3 or more. In aspects, the CIE b values may be in the range of about 0 to about 1, about 0.1 to about 0.5, about 0.2 to about 0.4, about 0.3 to about 0.4, or any range or subrange therebetween.

Throughout this disclosure, the refractive index may be 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 between the speed of light in vacuum and 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 a ratio of a sine of a first angle to a sine of a second angle, wherein light of a first wavelength is incident from air onto the surface of the material at the first angle and refracted at the surface of the material to propagate light in the material at the second angle. Both the first angle and the second angle are measured in a direction perpendicular 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 aspects, the refractive index of the 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 coating 113 may be in the range of 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 1.55, about 1.53 to about 1.55, about 1.49 to about 1.54, about 1.49 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 range of 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 1.55, about 1.53 to about 1.55, about 1.49 to about 1.54, about 1.49 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 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 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 coating 113 and the second refractive index of the substrate 103 or 203 may be in the range of about 0.001 to about 0.01, about 0.001 to about 0.008, about 0.002 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 the second refractive index.

In aspects, the first portion 321 may comprise a third refractive index, which may be within one or more of the ranges discussed above for the second refractive index. In other aspects, the first portion 321 and/or the second portion 231 may comprise substantially the same refractive index. In other aspects, the third refractive index of the first portion may be substantially equal to the second refractive index of the substrate 203. In other aspects, the absolute difference between the first refractive index of the coating 113 and the third refractive index of the first portion 321 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 coating 113 and the third refractive index of the first portion 321 may be in the range of about 0.001 to about 0.01, about 0.001 to about 0.008, about 0.002 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 the third refractive index.

In aspects, the coating 113 may include adhesion to the substrate 103. Throughout this disclosure, adhesion of the coating to the substrate can be measured according to ASTM D3359-09 method B using a cross-line adhesion test using a cross-bar paint adhesion test kit from Gardco. In aspects, the coating 113 (e.g., of the coated article 101, 201, 301, 401, 601, and/or 701) can include an adhesion of 1B or greater, 2B or greater, 3B or greater, 4B or greater, 5B or greater, 6B or greater, 1B to 6B, 1B to 5B, 1B to 4B, 1B to 3B, 1B to 2B, 3B to 6B, 3B to 5B, or 3B to 4B. In aspects, the coating 113 can include adhesion to the substrate that is any one of the values and/or ranges disclosed when formed by testing. In aspects, the coating 113 can include an adhesion to the substrate that is any of the values and/or ranges disclosed above after 10 days in a 50% relative humidity, 25 ℃ environment. In aspects, the coating 113 can include adhesion to the substrate that is any of the values and/or ranges disclosed above after 10 days in a 95% relative humidity, 25 ℃ environment. In aspects, the coating 113 can include an adhesion to the substrate that is any of the values and/or ranges disclosed above after 10 days in a 95% relative humidity, 65 ℃ environment.

In aspects, the coated article 101, 201, 301, 401, 601, and/or 701 can withstand 10 days without visible delamination or visible cracking in a 50% relative humidity, 25 ℃ environment. As used herein, "visible delamination" refers to separation (e.g., blistering, lifting, curling) of the macroscopic coating from the substrate. As used herein, "visible cracks" refers to cracks (e.g., breakage, crazing, separation into pieces) of a coating that are visible to the naked eye. In aspects, the coated article 101, 201, 301, 401, 601, and/or 701 can withstand 10 days without visible delamination or visible cracking in a 95% relative humidity, 25 ℃ environment. The coated articles 101, 201, 301, 401, 601 and/or 701 can withstand 10 days without visible delamination or visible cracking in a 95% relative humidity, 65 ℃ environment. The coated articles 101, 201, 301, 401, 601 and/or 701 can withstand 10 days without visible delamination or visible cracking in a 50% relative humidity, 65 ℃ environment.

In aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 can include a color shift, for example, as measured by a yellowing index. As used herein, the yellowing index is measured at a 10 ° observer angle according to ASTM D1925 using a D65 illuminant. In other aspects, the yellowness index of the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 can be about 0.2 or greater, about 0.3 or greater, about 0.4 or greater, about 0.45 or greater, about 0.48 or greater, about 0.8 or less, about 0.6 or less, about 0.55 or less, or about 0.5 or less. In other aspects, the yellowness index of the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 can be in the range of about 0.2 to about 0.8, about 0.2 to about 0.6, about 0.3 to about 0.6, about 0.4 to about 0.55, about 0.45 to about 0.55, about 0.48 to about 0.5, about 0.45 to about 0.5, or any range or subrange therebetween. In other aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 may include a yellowing index for one or more of the ranges of yellowing indexes after 10 days of retention in a 50% relative humidity, 25 ℃ environment. In other aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 may include a yellowing index for one or more of the ranges of yellowing indexes after 10 days of retention in a 95% relative humidity, 25 ℃ environment. In other aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 may include a yellowing index for one or more of the ranges of yellowing indexes after 10 days of retention in a 95% relative humidity, 65 ℃ environment.

In aspects, the coated article 101 can be folded about the folding axis 102 in the direction 108 (e.g., see fig. 1) to form the coated article 201 in a folded configuration (e.g., see fig. 4-5). As shown, the coated article may include a single folding axis to allow the coated article to include double folds, where, for example, the coated article may be doubled over. 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. 4-7 schematically illustrate example aspects of a coated article 401, 601, or 701 according to aspects of the present disclosure in a folded configuration. Although not shown, the coated article may be folded such that the coating 113 is on the inside of the folded coated article and the second major surface 107 or 207 of the substrate 103 or 203 is on the outside of the folded coated article. 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 coating 113 and the substrate 103, and will thus view from one side of the first major surface 105 of the substrate 103 (e.g., from one side of the third major surface 115 of the coating 113). Alternatively, as shown in fig. 5 and 7, the coated article may be folded such that the coating 113 is on the outside of the folded coated article and the second major surface 107 of the substrate 103 is on the inside of the folded coated article. If the display device is mounted on the second major surface 107 of the substrate, the user will view the device containing the coated article through the coating 113 and the substrate 103, and will thus view from one side of the first major surface 105 of the substrate 103 (e.g., from one side of the third major surface 115 of the coating 113). In this alternative configuration, the coated article may be curved in a direction such that the second major surface 107 faces itself (similar to the configuration in fig. 5 or 7) or in a direction such that the first major surface 105 faces itself (not shown). If the display device is mounted on the test adhesive layer 609 in the position of the PET sheet 607 shown in fig. 7 or on the eighth major surface 265 of the adhesive layer in the position of the release liner 271, the user will view the device containing the coated article through the coating 113 and the substrate 103 and will therefore view from one side of the first major surface 205 of the substrate 203.

As used herein, "foldable" includes fully folded, partially folded, bent, flexed, or multiple capabilities. As used herein, the term "fail" and similar terms refer to breakage, damage, delamination, or crack propagation. If a foldable substrate (e.g., substrate, coating, coated article) resists failure when held at a parallel plate distance "X" of about 60 ℃ and about 90% relative humidity for 24 hours, the substrate achieves a parallel plate distance "X" or a parallel plate distance having "X".

As used herein, the "parallel plate distance" of a foldable substrate (e.g., substrate 103 or 203, coating 113, coated article 101, 201, 301, 401, 601, and/or 701) is measured by the following test configuration and method of using a parallel plate apparatus 501 (see fig. 5-7) that includes a pair of parallel rigid stainless steel plates 503 and 505 that includes a first rigid stainless steel plate 503 and a second rigid stainless steel plate 505. When measuring the "parallel plate distance" of the coated article 401, as shown in fig. 5, the coated article 401 is placed between the pair of parallel rigid stainless steel plates 503 and 505 such that the coating 113 (e.g., the third major surface 115) is on the outside of the bend (e.g., facing and/or contacting the stainless steel plates 503 and 505) and the substrate 103 (e.g., the second major surface 107) is on the inside of the bend (facing itself). When measuring the "parallel plate distance" of a coated article (e.g., coated article 201) comprising an adhesive layer 261, the adhesive layer 261 and any article disposed on the adhesive layer (e.g., release liner) are removed and replaced with a test adhesive layer 609 having a thickness of 50 μm and an elastic modulus of 0.1MPa at the location of the adhesive layer such that the first major surface 611 of the test adhesive layer 609 contacts the surface contacted by the adhesive layer (e.g., second major surface 207 in fig. 2 and 6, second surface region 325 and fourth surface region 335 in fig. 3 and 7), and the second major surface 613 of the test adhesive layer 609 contacts a 100 μm thick poly (ethylene terephthalate) sheet 607. When measuring the "parallel plate distance" of the coating 113 independent of a particular substrate, the fourth major surface 117 of the coating 113 is attached to a test adhesive layer comprising a thickness of 50 μm and an elastic modulus of 0.1MPa, which is attached to a 100 μm thick poly (ethylene terephthalate) sheet, and the combined laminate is placed between a pair of parallel rigid stainless steel plates 503 and 505 such that the coating 113 (e.g., the third major surface 115) is on the outside of the bend (e.g., facing and/or contacting the stainless steel plates 503 and 505). The distance between the parallel plates decreases at a rate of 50 microns/second until the parallel plate distance 507 is equal to the "parallel plate distance" to be tested. Subsequently, the parallel plates were held at about 60 ℃ and about 90% relative humidity for 24 hours at the parallel plate distance to be tested. As used herein, a "minimum parallel plate distance" is the minimum parallel plate distance that a foldable substrate (e.g., substrate 103 or 203, coating 113, coated article 101, 201, 301, 401, 601, and/or 701) can withstand without failing under the conditions and configurations described above.

In aspects, the coated article 101, 201, 301, 401, 601, and/or 701 and/or the coating 113 can achieve a parallel plate distance of 100mm or less, 50mm or less, 20mm or less, or 10mm or less. In other aspects, the coated article 101, 201, 301, 401, 601, and/or 701 and/or the coating 113 can achieve a parallel plate distance of 10 millimeters (mm) or 7mm, or 5mm, 4mm, 3mm, 2mm, or 1 mm. In aspects, the coated article 101, 201, 301, 401, 601, and/or 701 and/or the coating 113 can include a parallel plate distance of 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, 201, 301, 401, 601, and/or 701 and/or the coating 113 can include a parallel plate distance in a range of 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 coating 113 can withstand cyclic bending testing. As used herein, cyclic bending testing includes placing a test apparatus including a material to be tested in a parallel plate apparatus 501 (see fig. 5) and bending a laminate including a coating 113, as described above for the parallel plate test of the coating 113, to achieve a predetermined parallel plate distance between the plates 503, 505, repeated a predetermined number of times at 23 ℃,50% relative humidity. The test apparatus included attaching a 100 μm material portion of the coating 113 to be tested to a 100 μm thick PET sheet having a 50 μm thick adhesive with an elastic modulus of 0.1MPa, with the coating facing the pair of rigid stainless steel plates 503 and 505. In an aspect, the coating 113 can withstand 2,000 bending cycles at a parallel plate distance of 3 millimeters. In other aspects, the coating 113 can withstand 20,000 bending cycles at a parallel plate distance of 3 millimeters. In even other aspects, the coating 113 can withstand 200,000 bending cycles at a parallel plate distance of 3 millimeters. In an aspect, the coating 113 can withstand 2,000 bending cycles at a parallel plate distance of 4 millimeters. In other aspects, the coating 113 can withstand 20,000 bending cycles at a parallel plate distance of 4 millimeters. In even other aspects, the coating 113 is subjected to 200,000 bending cycles at a parallel plate distance of 4 millimeters.

The coated article may have an impact resistance as defined by the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 to avoid failure at a certain pen-down height (e.g., 5 centimeters (cm) or more, 8cm or more, 10cm or more, 12cm or more, 15cm or more) when measured according to the "pen-down test". As used herein, a "pen drop test" is performed such that a sample of a coated article is tested by a load (i.e., from a pen dropped from a certain height) applied to the outer surface of the coated article and/or the coating configured as a parallel plate test (e.g., the third major surface 115 of the coating 113 in fig. 1-3, the second major surface 107 of the substrate 103 in fig. 1-3). During testing, the laminate comprising coating 113 and/or coated article 101, 201, 301, 401, 601 and/or 701 was placed on an aluminum plate (6063 aluminum alloy, polished to a surface roughness with 400 sandpaper). The side of the sample placed on the aluminum plate was not adhesive tape.

In the pen drop test, the pen used was a tungsten carbide ball-point pen comprising a diameter of 0.7mm (0.68 mm) and a BIC super-smooth pen comprising a cap weight of 5.73 grams (g) (without cap 4.68 g). The ballpoint pen is maintained at a predetermined height from an outer surface (e.g., the third major surface 115 of the coating 113 in fig. 1-3, the second major surface 107 of the substrate 103 in fig. 1-3) comprising the coating and/or the coated laminate. A tube was used for the pen drop test to guide the ballpoint pen to the outer surface of the coated article and the tube was placed in contact with the outer surface of the coated article such that the longitudinal axis of the tube was substantially perpendicular to the outer surface of the coated article. The tube had an outer diameter of 1 inch (2.54 cm), an inner diameter of sixteen nine inches (1.4 cm) and a length of 90cm. For each test, an acrylonitrile butadiene ("ABS") spacer was used to hold the ballpoint pen at a predetermined height. After each drop, the tube is repositioned relative to the outer surface of the sample to be tested to direct the ballpoint pen to a different impact location on the outer surface of the sample to be tested. It should be understood that the pen drop test may be used with any of the coatings and/or coated articles of aspects of the present disclosure.

For the pen drop test, the ballpoint pen is dropped with the cap attached to the tip (and the end opposite the tip) so that the ballpoint pen can interact with the outer surface of the coating (e.g., the third major surface 115 of the coating 113 in fig. 1-3, the second major surface 107 of the substrate 103 in fig. 1-3). In the falling sequence according to the pen drop test, one pen drop is performed at an initial height of 1cm, followed by continuous falling in 0.5cm increments up to 20cm, and then after 20cm, falling in 2cm increments until the sample to be tested fails. After each drop was made, any observable evidence of breakage, failure or other damage to the coated article was recorded, as well as the specific predetermined height of the pen drop. Using the pen drop test, multiple samples can be tested according to the same drop sequence to generate an ensemble of improved statistical accuracy. For the pen drop test, after every 5 drops and for each new coated article tested, the ballpoint pen was replaced with a new pen. In addition, unless otherwise indicated that no pens were falling near or on the edges of the coated article, all pens were falling at random locations on the coated article at or near the center of the coated article.

For the purposes of the pen drop test, "failure" means 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 the coating 113 and/or all or a portion of the coated article 101, 201, 301, 401, 601, and/or 701. The smallest dimension of the visible mechanical defect is 0.2 mm or more. In aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 can withstand a pen-drop height of 1cm or greater, 3cm or greater, 5cm or greater, 7cm or greater, 8cm or greater, 9cm or greater, 10cm or greater, 11cm or greater, 12cm or greater, 13cm or greater, 14cm or greater, 15cm or greater, 16cm or greater, 17cm or greater, 18cm or greater, 19cm or greater, and/or 20cm or greater above the third major surface 115 of the coating 113.

For a coated article comprising one or more recesses (e.g., first recess 234, second recess 241) and/or a minimum distance 343 between different portions (e.g., first portion 321 and second portion 331), for example, similar to fig. 2-3, for a coated article having a substrate thickness of 30 μm or greater, the coated article may withstand a pen-drop height of 5cm or greater, 8cm or greater, 10cm or greater, 12cm or greater, 13cm or greater, 14cm or greater, or 15cm or greater over a portion of third major surface 115 (corresponding to the minimum distance between the recesses and/or different portions). For a coated article comprising one or more recesses, e.g., similar to fig. 2, for a substrate having a thickness of 30 μm or greater, the coated article can withstand a pen-down height of about 10cm or greater, 15cm or greater, 17cm or greater, 18cm or greater, 19cm or greater, or about 20cm or greater on a portion (e.g., first portion 221, second portion 231) of the third major surface 115 or second major surface 107 that does not comprise recesses. For a coated article comprising a minimum distance between the different portions, for example, similar to fig. 3, for a substrate having a thickness of about 30 μm or greater and a portion having a thickness of about 30 μm or greater, the coated article may withstand a pen-drop height of about 10cm or greater, 15cm or greater, 17cm or greater, 18cm or greater, 19cm or greater, or about 20cm or greater on a portion of the second major surface 107, the second surface region 325, the fourth surface region 335 (corresponding to the first portion 321 or the second portion 331), or the third major surface 115 of the coating extending along the fourth plane 306.

In aspects, the coating 113 and/or the coated article 101, 201, 301, 401, 601, and/or 701 can include a contact angle of deionized water on the third major surface 115 of the coating 113. 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, 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 range of about 10 ° to about 140 °, about 10 ° to about 110 °, 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, including for example, contact angles in the range of 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.

In aspects, the coated article may further comprise an additional coating comprising one or more of an easy-to-clean coating, a low friction coating, an oleophobic coating, a diamond-like coating, a scratch-resistant coating, or a wear-resistant coating. In other aspects, an additional coating may be disposed over the third major surface of the coating. The scratch resistant coating may include an oxynitride, such as aluminum oxynitride or silicon oxynitride, wherein the thickness is about 500 microns or greater. In such aspects, the wear layer may comprise the same material as the scratch resistant layer. In aspects, the low friction coating may include a highly fluorinated silane coupling agent, such as an alkylfluorosilane having an oxymethyl group 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, e.g., a methylaminosilane with an oxymethyl group 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.

Throughout this disclosure, dynamic friction coefficients are measured according to ASTM D1894-14. In aspects, the third major surface 115 of the coating 113 can include a dynamic coefficient of friction of 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 major surface 115 of the coating 113 can include a dynamic coefficient of friction in the range of about 0.1 to about 0.8, about 0.3 to about 0.6, about 0.3 to about 0.5, about 0.4 to about 0.5, or any range or subrange therebetween.

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 further comprise an electronic component at least partially within the housing. The electronic components may include a controller, memory, and a display. The display may be located at 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 a portion of the housing or the cover substrate includes a coating and/or a coated article discussed throughout the present disclosure. The display may include a Liquid Crystal Display (LCD), an electrophoretic display (EPD), an organic light emitting diode display (OLED), or a Plasma Display (PDP). In aspects, the consumer electronic product may be a portable electronic device, such as a smart phone, tablet computer, wearable device, or laptop computer.

The coated articles and/or coatings disclosed herein can be incorporated into another article, such as an article (or display article) having a display (e.g., consumer electronics including cell phones, tablet computers, navigation systems, wearable devices (e.g., watches), and similar electronics), architectural articles, transportation articles (e.g., automobiles, trains, airplanes, sea-going vessels, etc.), electrical articles, or any article that can benefit from some transparency, scratch resistance, abrasion resistance, or a combination thereof. And an example article with any of the coated articles disclosed herein is shown in fig. 11 and 12. In particular, fig. 11 and 12 illustrate a consumer electronic device 1100 including a housing 1102 having a front surface 1104, a rear surface 1106, and side surfaces 1108. The consumer electronic device 1100 can include electronic components (not shown) that are located at least partially within or entirely within the housing and that include at least a controller, a memory, and a display 1110 located at or adjacent to a front surface of the housing. The consumer electronic device 1100 can include a cover substrate 1112 at or above the front surface of the housing such that the device is above the display. In aspects, at least one of the cover substrate 1112 or a portion of the housing 1102 can comprise any of the coated articles disclosed herein.

Aspects of a method of making a coated article 101, 201, 301, 401, 601, and/or 701 according to aspects of the present disclosure will be discussed with reference to the flowchart in fig. 13 and the example method steps shown in fig. 14-19. Referring to the flowchart in fig. 13, the method may begin at step 1301. In an aspect, step 1301 can include providing a substrate. In other aspects, the substrate may be similar to the substrate 103 of fig. 1 or 3 including the substrate thickness 109 or the substrate 203 of fig. 2 including the substrate thickness 209. In other aspects, the substrate 103 or 203 may be provided by purchasing or otherwise obtaining the substrate or by forming the substrate. In other aspects, the substrate may include a glass-based substrate and/or a ceramic-based substrate. In other aspects, the glass-based substrate may be provided by forming it using a variety of ribbon forming processes, such as slot draw, drop down, fusion drop down, pull up, roll up, heavy pull, 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 depth of layer (e.g., first depth of layer, second depth of layer) within one or more of the respective ranges discussed above.

After step 1301, the method may proceed to step 1303 of preparing the substrate 103 or 203. In an aspect, step 1303 can include treating at least the first major surface 105 or 205 of the substrate 103 or 203 with plasma and/or ozone. In other aspects, the first central surface region 213 may be treated with plasma and/or ozone. In an aspect, step 1303 can include disposing a silane coupling agent over the first major surface 105 or 205 of the substrate 103 or 203. In other aspects, the silane coupling agent may be disposed over the first central surface region 213. In other aspects, as shown in fig. 14, step 4603 can include disposing a silane coupling agent on the first major surface 105 of the substrate 103 via the solution 1405, for example, as layer 1401. In even other aspects, disposing a silane coupling agent may include dispensing a solution 1405 from a container 1403 (e.g., a catheter, hose, micropipette, or syringe). In other aspects, solution 1405 may be comprised of one or more silane coupling agents. In other aspects, disposing the silane coupling agent may further include heating the substrate 103 and the solution 1405 at a second temperature for a second period of time. In even other aspects, the second temperature may be about 80 ℃ or greater, about 100 ℃ or greater, about 110 ℃ or greater, about 120 ℃ or greater, about 160 ℃ or less, about 140 ℃ or less, or about 130 ℃. In even other aspects, the second temperature may be in a range of about 80 ℃ to about 160 ℃, about 80 ℃ to about 140 ℃, about 100 ℃ to about 130 ℃, about 110 ℃ to about 130 ℃, about 120 ℃ to about 130 ℃, or any range or subrange therebetween. In even other aspects, the second period of time may be about 15 minutes or more, about 30 minutes or more, about 45 minutes or more, about 6 hours or less, about 2 hours or less, about 90 minutes or less, about 75 minutes or less, or about 60 minutes or less. In even other aspects, the second period of time may be between about 15 minutes and about 6 minutes, between about 30 minutes and about 6 hours, between about 30 minutes and about 2 hours, between about 45 minutes and about 75 minutes, between about 45 minutes and about 60 minutes. In other aspects, the first major surface 105 or 205 of the substrate 103 or 203 can be treated with plasma and/or ozone prior to disposing the silane coupling agent on the first major surface 105 or 205 of the substrate 103 or 203. In other aspects, the silane coupling agent may include any one or more of the silane coupling agents discussed above with reference to the composition. In even other aspects, the silane coupling agent may comprise a thiol-functional silane coupling agent. In still other aspects, the silane coupling agent may include one or more of (3-triethoxysilyl) propyl succinic anhydride, (3-mercaptopropyl) trimethoxysilane, and/or 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane. In even other aspects, the silane coupling agent may comprise an epoxy-functional silane coupling agent. In even other aspects, the silane coupling agent may comprise an amine-functionalized silane coupling agent.

In aspects, after step 1301 or 1303, as shown in fig. 15-17, the method may proceed to step 1305 that includes depositing a layer 1401 comprising the composition over the first major surface 105 of the substrate 103. In other aspects, as shown, a layer 1401 comprising the composition may be deposited over the first major surface 105 of the substrate 103 by being disposed on a layer 1507 of a silane coupling agent, represented by the dashed line, which is in turn disposed on the first major surface 105 of the substrate 103. In other aspects, as shown, in the absence of layer 1507, layer 1401 comprising the composition may be deposited over the first major surface 105 of substrate 103 by deposition thereon, for example if no silane coupling agent is used or if a silane coupling agent is included in layer 1401 comprising the composition. In other aspects, as shown in fig. 17, the composition may be dispensed from a container 1403 (e.g., a catheter, hose, micropipette, or syringe) similar to how the silane coupling agent may be dispensed as described with reference to fig. 14. In other aspects, as shown in fig. 17, the layer 1401 may fill the first recess 234 and/or contact the first central surface region 213. In other aspects, as discussed above, the composition may include a linking group that includes a reactive diluent. In other aspects, the composition may be solvent-free, as discussed above with reference to the composition. In even other aspects, the composition can include particles that can be disposed over the first major surface 105 or 205 to form a particle layer over the first major surface 105 or 205. In even other aspects, the composition can comprise a liquid that can be dispersed over the first major surface 105 or 205. In still other aspects, depositing the composition can further include pulling an application bar through the first major surface 105 or 205 to achieve a layer of a predetermined thickness, for example, by controlling the amount of solvent in the composition and/or by controlling the height of the application bar. In still other aspects, depositing the composition can further include spin coating the first major surface 105 or 205 to achieve a layer of a predetermined thickness based on the viscosity of the composition. In other aspects, the composition may comprise a solvent, as discussed above with reference to the composition. In even other aspects, the composition can comprise a liquid that can be dispersed over the first major surface 105 or 205. In still other aspects, depositing the composition can further include pulling an application bar through the first major surface 105 or 205 to achieve a layer of a predetermined thickness. In still other aspects, depositing the composition can further include spin coating the first major surface 105 or 205 to achieve a layer of a predetermined thickness based on the viscosity of the composition. In other aspects, the predetermined thickness of the layer may be within one or more of the ranges discussed above with reference to coating thickness 119. In other aspects, although not shown, depositing the composition may include using a knife (e.g., a roll-coated doctor blade or knife) to achieve the predetermined thickness. In other aspects, although not shown, depositing the composition may include using a roller (e.g., roll coated gravure or knife). In other aspects, as described above, the composition can comprise a plurality of functionalized oligomeric silsesquioxanes and a linking group, wherein a first functionalized oligomeric silsesquioxane of the plurality of functionalized oligomeric silsesquioxanes is bound to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes through the linking group, the linking group being terminated with a first functional group at a first end of the linking group and a second functional group at a second end of the linking group opposite the first end of the linking group. In even other aspects, the first functionalized oligomeric silsesquioxane may be attached to the second functionalized oligomeric silsesquioxane by a linking group prior to depositing the composition in step 1305 and prior to curing the layer to form the coating in step 1307. In even other aspects, the linking group may comprise a polymer. In even other aspects, as discussed above with reference to the composition, the composition may comprise at least one functionalized oligomeric silsesquioxane that is not bound to a polymer of the plurality of polymers, for example, if the molar ratio of polymer to functionalized oligomeric silsesquioxane is low and/or if additional functionalized oligomeric silsesquioxane is added after the reaction, as discussed above with reference to the composition. In even other aspects, the composition may include a photoinitiator (e.g., a cationic photoinitiator, a free radical photoinitiator, or both a cationic photoinitiator and a free radical photoinitiator), as discussed above with reference to the composition. In even other aspects, the composition may comprise a silane coupling agent, as discussed above with reference to the composition. In still other aspects, the silane coupling agent may include one or more of (3-triethoxysilyl) propyl succinic anhydride, (3-mercaptopropyl) trimethoxysilane, and/or 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane. In still other aspects, the silane coupling agent may comprise an epoxy-functional silane coupling agent. In still other aspects, the silane coupling agent may comprise an amine-functionalized silane coupling agent.

In aspects, after step 1301 or 1305, as shown in fig. 15-16, the method may proceed to step 1307 which includes curing layer 1401 to form a coating. In other aspects, as shown in fig. 15, curing the layer 1401 to form the coating 113 (see fig. 1-3) in step 1307 may include affecting the material with radiation 1505 from the radiation source 1503. In even other aspects, radiation 1505 may include a wavelength to which the photoinitiator is sensitive. In even other aspects, the radiation may substantially (e.g., entirely) affect layer 1401. In even other aspects, radiation 1505 may include ultraviolet radiation and/or visible radiation. In even other aspects, radiation 1505 may include wavelengths of light in the range of 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 light wavelengths in the range of about 315nm to about 400nm, about 280nm to about 315nm, about 100nm to about 280nm, or 122nm to about 200 nm. In even other aspects, the wavelength of the light beam may be in the range of about 300nm to about 1,000nm, about 350nm to about 900nm, about 400 to about 800nm, about 500nm to about 700nm, or any range or subrange therebetween. In still other aspects, the wavelength of the radiation may be about 365nm, about 415nm, or about 590nm. In even other aspects, the radiation source 1503 may include a light-emitting diode (LED), an organic light-emitting diode (OLED), a laser, an incandescent bulb, and/or a fluorescent bulb (e.g., a cold cathode fluorescent lamp (cold cathode fluorescent lamp; CCFL)). In other aspects, the total energy density of the radiation (e.g., UV radiation) affecting layer 1401 comprising the composition may be about 1 joule per square centimeter (J/cm) ² ) Or greater, about 2J/cm ² Or greater, about 4J/cm ² Or greater, about 6J/cm ² Or greater, about 30J/cm ² Or less, about 15J/cm ² Or less, about 10J/cm ² Or less or about 8J/cm ² Or smaller. In other aspects, the total energy density of the radiation (e.g., UV radiation) affecting layer 1401 comprising the composition may be 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 Within a range, or within any range or subrange therebetween. As used herein, total energy density means the total energy of radiation from the entire curing process that affects (e.g., is incident on) the layer per surface area of the layer corresponding to the third major surface 115 of the coating 113 (see fig. 1-3). For example, the total energy density from the LED radiation source that continuously emits UV radiation at a predetermined power for a predetermined period of time during curing is equal to the predetermined power times the predetermined time divided by the surface area of the layer. In other aspects, the period of time for curing by irradiating the layer 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 curing by irradiating the layer 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. It should be appreciated that step 1307 discussed herein with reference to fig. 15-19 may be applied to aspects that include the substrate 203 or another substrate. During curing, the reactive diluent (if provided) may react with the one or more functionalized oligomeric silsesquioxanes during curing to form a bond between the one or more functionalized oligomeric silsesquioxanes and the reactive diluent. In aspects, the plurality of functionalized oligomeric silsesquioxanes may not be bound to the linking group prior to curing, but are bound to the linking group including the reactive diluent during curing. For example, during curing, the first functionalized oligomeric silsesquioxane may react with a third functional group of the reactive diluent and the second functionalized oligomeric silsesquioxane may react with a fourth functional group of the reactive diluent such that the first functionalized oligomeric silsesquioxane is bound to the second functionalized oligomeric silsesquioxane via the reactive diluent. However, more The seed functionalized oligomeric silsesquioxane may be bound to a linking group comprising a polymer prior to curing and further bound to a linking group comprising a reactive diluent after curing. Curing the photoinitiator-containing composition and curing the composition using radiation may reduce the overall processing time, processing equipment, and production costs.

In other aspects, as shown in fig. 16, curing layer 1401 to form coating 113 (see fig. 1-3) in step 1307 may include heating layer 1401. In even other aspects, as shown, the layer 1401 disposed over the first major surface 105 of the substrate 103 may be heated by placing the layer 1401 and the substrate 103 in an oven 1601 maintained at a third temperature for a third period of time. In still other aspects, the third temperature may be about 60 ℃ or greater, about 70 ℃ or greater, about 75 ℃ or greater, about 80 ℃ or greater, about 100 ℃ or greater, about 250 ℃ or less, about 200 ℃ or less, about 160 ℃ or less, about 150 ℃ or less, or about 130 ℃ or less. In still other aspects, the third temperature may be in a range of about 60 ℃ to about 250 ℃, about 70 ℃ to about 250 ℃, about 75 ℃ to about 250 ℃, about 80 ℃ to about 250 ℃, about 100 ℃ to about 200 ℃, about 100 ℃ to about 160 ℃, about 100 ℃ to about 150 ℃, about 100 ℃ to about 130 ℃, or any range or subrange therebetween. In still other aspects, the third period of time may be about 15 minutes or more, about 30 minutes or more, about 45 minutes or more, about 60 minutes or more, about 90 minutes or more, about 16 hours or less, about 8 hours or less, about 6 hours or less, about 4 hours or less, or about 2 hours or less. In still other aspects, the third period of time may be in the range of about 15 minutes to about 16 hours, about 15 minutes to about 8 hours, about 15 minutes to about 6 hours, about 15 minutes to about 4 hours, about 15 minutes to about 2 hours, about 30 minutes to about 2 hours, about 45 minutes to about 2 hours, about 60 minutes to about 2 hours, about 90 minutes to about 2 hours, or any range or subrange therebetween. In other aspects, step 1307 can comprise irradiating layer 1401 followed by heating layer 1401.

In aspects, as shown in fig. 18-19, after step 1307, the method can proceed to step 1309. In other aspects, step 1309 can comprise assembling the coated article. In other aspects, step 1309 can comprise including the coated article in an electronic device, such as a consumer electronic device as shown in fig. 11-12. In other aspects, as shown in fig. 18, a liquid 1801 may be disposed over the substrate 203, such as by dispensing from a container 1803 (e.g., a catheter, hose, micropipette, or syringe) to fill the second recess 241 and/or contact the second central surface region 243. The liquid 1801 may be cured (e.g., by heating the liquid, by exposing the liquid to radiation, and/or waiting a predetermined amount of time), which may result in the polymer-based portion 291 shown in fig. 2 and 19; however, the liquid may be cured to create an adhesive layer (e.g., adhesive layer 261). In an aspect, although not shown, the polymer-based portion 291 may be disposed above the substrate 203 by depositing a film including the polymer-based portion, for example, within the second recess 241. In other aspects, as shown in fig. 19, an adhesive layer 261 (e.g., an optically clear adhesive) may be disposed over the second major surface 207 of the substrate 203. For example, as shown, a film comprising an adhesive layer 261 can be disposed over the second major surface 207 such that it contacts the second surface region 225 and the fourth surface region 235. In even other aspects, a release liner may be disposed over the adhesive layer, wherein the release liner is removable, followed by attachment of the adhesive to another component of the display or electronic device. In even other aspects, the adhesive layer may be disposed over another component of the display or electronic device.

After step 1307 or 1309, the method can be completed at step 1311, and thus, the method of making the coated article 101, 201, 301, 401, 601, and/or 701 can be completed. In aspects, the coated article and/or coating may include pen hardness within one or more of the ranges discussed above for pen hardness. In aspects, the coated article may include adhesion within one or more of the ranges discussed above for adhesion discussed for one or more conditions. In aspects, the coating may include tensile strength, ultimate elongation, modulus of elasticity (e.g., young's modulus), and/or coating thickness within one or more of the ranges discussed above for the respective properties of the coating. In aspects, the coating and/or coated article may include refractive index, transmittance, haze, and/or yellowing index within one or more of the ranges discussed above for the respective properties. In aspects, the coating may be substantially free of visible crystals at 100-fold magnification. In aspects, the coating and/or coated article is a parallel plate distance within one or more of the ranges discussed above for parallel plate distances.

In aspects, as discussed above with reference to the flowchart in fig. 13, the method may begin at step 1301 and then proceed sequentially to steps 1303, 1305, 1307, 1309, and 1311. In aspects, arrow 1302 may omit step 1303 from step 1301 to step 1305, e.g., if no silane coupling agent is used to form the coated article, only a film is formed, other methods of preparation of the substrate are not necessary, or if the composition includes a silane coupling agent. In aspects, arrow 1304 may omit steps 1303 and 1305 from step 1301 to step 1307, e.g., if only a film is formed and/or the composition is in place at the end of step 1301. In aspects, arrow 1308 may omit step 1309 from step 1307 to step 1311, for example if the coating and/or coated article does not require further assembly after step 1307. Any of the above options may be combined to make a coated article according to aspects of the present disclosure.

Examples

Various aspects will be further elucidated by the following examples. Tables 2-10 present information regarding aspects of compositions that may be used to form coating 113 (e.g., of coated articles 101, 201, 301, 401, 601, and/or 701). Tables 11-20 present information regarding aspects of the coatings. The substrates used to measure the properties reported in tables 11-20 were glass-based substrates having a substrate thickness of 30 μm and similar to the substrate 103 shown in FIGS. 1 and 3 (nominally having a composition of 1 with the following: 69.1SiO in mol% ₂ ；10.2Al ₂ O ₃ ；15.1Na ₂ O；0.01K ₂ O；5.5MgO；0.09SnO ₂ )。

Examples a-G included the reactants in the amounts presented in table 2 in wt% that were used to form the compositions. In tables 2-10, GPOSS refers to EP0409 available from Hybrid Plastics, PDMS1 refers to DMS-A11 available from Gelest, PDMS2 refers to DMS-A21 available from Gelest, PDMS 3 refers to DMS-A214 available from Gelest and PPO refers to Jeffamine D2000 available from Huntsman. GPOSS is a functionalized oligomeric silsesquioxane comprising a functionalized polyhedral oligomeric silsesquioxane (POSS), wherein the functionalized POSS is functionalized by 3-epoxypropyloxypropyl and the GPOSS has a number average molecular weight (Mn) of about 1,338 daltons (e.g., g/mole (g/mol)). PDMS1, PDMS2 and PDMS 3 are polydimethylsiloxanes. The number average molecular weight (Mn) of PDMS1 was about 875 daltons. The number average molecular weight (Mn) of PDMS2 was about 5,000 Dalton. PDMS1 and PDMS2 were terminated by an aminopropyl function at each end of the polymer. The number average molecular weight (Mn) of PDMS 3 was about 900 daltons. PDMS 3 was terminated by ethylamino isobutyl functions at each end of the polymer. The number average molecular weight (Mn) of PPO is about 2,000 daltons. PPO is a poly (propylene oxide) having amine functionality at each end of the polymer. PDMS 4 comprises a mono- (aminopropyl) terminated poly (dimethylsiloxane) available as MCR-A11 from Gelest. The number average molecular weight (Mn) of PDMS 4 was about 2,000 Dalton. As used herein, a/B/C means that B connects a and C by binding B to a and B to C. For example, "GPOSS/PDMS1/GPOSS" indicates that PDMS1 is a linking group that links two GPOSS together due to PDMS1 binding to the two GPOSS.

Examples a-E included poly (dimethylsiloxane) polymers terminated with amine functionality, while examples F-G included poly (propylene oxide) polymers terminated with amine functionality, as shown in table 2. Examples a-F included solvents during the reaction, while example G was solvent-free. Examples a-G were all visually clear after the reaction. Examples a-G were also visually clear after removal of any solvent using a rotary evaporator at 3.8kPa and 60 ℃ for 1.5 hours and periodic cleaning of the solvent collectors. Examples A-B and D-F were reacted under reflux at 132℃for 16 hours under a nitrogen atmosphere. Example C was reacted at 120℃for 12 hours under reflux and nitrogen atmosphere. Example G was reacted at 100℃for 20 minutes under nitrogen atmosphere.

Examples a-G included 0.98wt% to 5.59wt% polymer reactant, as shown in table 2. Example a included less than 1wt% of polymer reactant. Examples B and G included greater than 5wt% polymer reactant. Examples a-G included 19.13wt% to 94.88wt% GPOSS reactant. Examples A-B and F-G included greater than 40wt% GPOSS reactant. For examples a-G, the mass ratio of polymer (e.g., PDMS1, PDMS2, PDMS3, PPO) to GPOSS was 0.0229 to 0.1375, with example B including the highest ratio and examples a and C-G including the mass ratio of reactants 0.0229 to 0.0688. For examples a-G, the molar ratio of polymer (e.g., PDMS1, PDMS2, PDMS3, PPO) to GPOSS was 0.018 to 0.037 of reactant.

Table 2: composition range (wt%) of the reactants

Examples	A	B	C	D	E	F	G
								GPOSS	42.63	40.64	30.42	19.13	19.02	42.07	94.88
PDMS1	0.98	0	0	0	0	0	0
								PDMS2	0	5.59	2.05	0	0	0	0
PDMS3	0	0	0	0.72	1.31	0	0
								PPO	0	0	0	0	0	2.27	5.12
Propyl acetate	0	0	67.53	0	0	0	0
								Butyl acetate	56.39	53.77	0	80.15	79.67	55.66	0

Table 3: final composition Range (wt%)

Table 3 presents the components of the compositions in wt% for examples A-G. TPSHFA means triphenylsulfonium hexafluoroantimonate, which is a UV sensitive cationic photoinitiator available as 654027 from Sigma Aldrich. For examples a-E and G, after the reaction of the corresponding components presented in table 2, a composition comprising additional GPOSS was added. For examples a-F, the solvent during the reaction was removed, and additional GPOSS was added after this solvent was removed, as discussed above. Examples a-B and D were solvent-free and the solvent from the photoinitiator solution was removed prior to depositing the composition onto the substrate. Examples C and E-G include solvents from photoinitiator solutions.

As used herein, a polymer composite means that a polymer is attached to one or more GPOSS. As used herein, "free GPOSS" refers to GPOSS not attached to a polymer. As used herein, a polymer complex refers to a polymer that links together GPOSS molecules. Examples a-F included polymer composites ranging from 2.57wt% to 10.76wt% of the composition, as shown in table 3. Examples A, C-E and G included less than 5% by weight of the composition of polymer. Examples B and F included more than 8% by weight of the composition of the polymer composite. Examples a-G included a weight ratio of polymer composite to free GPOSS of polymer composite of 0.0275 to 0.1298 of the composition. Examples A, D-E and G included a weight ratio of polymer composite to free GPOSS of less than 0.05 polymer of the composition. Examples B and F included polymer composites of compositions exceeding 0.1. Examples a-G included a weight ratio of polymer to all GPOSS of 0.0268 to about 0.115. Examples a-G included a molar ratio of polymer complex to free GPOSS of 0.009 to 0.0361 of the composition. Examples a-E and G included a molar ratio of polymer composite to free GPOSS of less than 0.02. Examples a-G included the molar ratio of polymer to all GPOSS of compositions from 0.0077 to 0.0169. Examples a and C-G included a molar ratio of polymer to all GPOSS of less than 0.01 of the composition. Examples a-G included TPSHFA as the cationic photoinitiator, which comprised 0.86wt% to 4.09wt% of the composition.

CAPA 3050 is a linking group comprising a polymer, as used in tables 4-6. CAPA 3050 refers to a polycaprolactone triol available from Perston as CAPA 3050, wherein the number average molecular weight (Mn) is 540 Dalton. M142 is a polymerization reactive diluent comprising a single acrylate functionality. M142 refers to a poly (ethylene glycol) phenylene ether acrylate comprising a number average molecular weight (Mn) of 324 daltons available as Miramer M142 from Miwon. S06E and TMPO include a non-polymeric linking group comprising a reactive diluent having two functional groups. S06E is 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate obtainable from Synasia as S-06E. TMPO refers to 3-ethyl-3-oxetane methanol available from Sigma Aldrich as 444197. Curalite OX and IBOA refer to reactive diluents that contain a single functional group. Curalite OX refers to 3-ethyl-3-oxetane methanol available from Perston as Curalite Ox. IBOA refers to isobornyl acrylate available from Miwon and Miramer M1140. PI6976 and TPO-L are photoinitiators. PI6976 refers to a triarylsulfonium hexafluoroantimonate salt mixture available from Synasia as Syna PI 6976. TPO-L refers to diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide obtainable from IGM as TPO-L. GOPTMS and ECHETMS refer to silane coupling agents. GOPTMS refers to (3-epoxypropyloxypropyl) trimethoxysilane available as 440167 from Sigma Aldrich, as Coatosil MP200 from Momentive, or as SIG5840.0 from Silquest. ECHETMS can be 2- (2, 4-epoxycyclohexyl) ethyl trimethoxysilane available as SIE4670.0 from Gelest or Silquest A186 from Momentive. Nanopox C620 refers to silica nanoparticles obtainable from Evonik as Nanopox C620, which comprise an average effective diameter of 20nm in a 40wt% solution of cycloaliphatic epoxy resin.

In tables 4-5, examples H-I and O-V included polymer complexes at 50wt% to 96wt% of the composition. Examples J-N and W include free GPOSS. Examples V-W included a 30wt% to 60wt% nanoparticle solution, nanopox C620, and a polymer composite or free GPOSS. Examples H, J and L include polymeric linking groups, namely CAPA 3050, to link GPOSS and/or polymer complexes and act as reactive diluents. Examples H-P and V-W include non-polymeric linking groups and reactive diluents, S06E, TMPO and/or Curalite OX, in a total amount of 20wt% to 48 wt%. Examples H-P and R-S include reactive diluents in an amount of 5wt% to 9.6wt% that are not linking groups, as M142 and IBOA contain only a single functional group. Examples H-W included PI6976 as a cationic photoinitiator in an amount of 2wt% to 4 wt%. Examples R-U further include TPO-L as a free radical photoinitiator. Examples M-N included silane coupling agents. Examples H-U were solvent-free, while examples V-W included solvents in Nanopox C620 solution. Examples H-I, O and P-V included a weight ratio of polymer to all GPOSS of about 0.65 and a molar ratio of polymer to all GPOSS of about 0.5. Example P included a weight ratio of polymer of about 0.428.

Table 4: final composition Range (wt%)

Table 5: final composition Range (wt%)

In Table 6, examples AA-CC include comparative examples. Examples AA-BB included GPOSS without a linking group. Example CC included silica nanoparticles and linking groups, but did not contain any functionalized oligomeric silsesquioxane.

As used in tables 7-10, DBU, TEA, pyridine, TMG and DMP were the curing agents. "DBU" refers to 1, 8-diazabicyclo [5.4.0] undec-7-ene available from Sigma Aldrich as 803282. "TEA" refers to triethylamine available as 808352 from Sigma Aldrich. Pyridine was available as 270970 from Sigma Aldrich, "TMG" refers to tetramethylguanidine available as 241768 from Sigma Aldrich. "DMP" means 2,4, 6-tris (dimethylaminomethyl) phenol available as T58203 from Sigma Aldrich. DBU, TEA, TMG and DMP comprise tertiary amines. As used in tables 7-10, HAD, TMD, IPDA, AEP, DMDC, MXDA, N and MHHPA are non-polymeric linking groups, "HAD" refers to 1, 6-hexamethylenediamine available as H11696 from Sigma Aldrich. "TMD" refers to trimethylhexamethylenediamine available as TCI-T0600 from Spectrum Chemical. "IPDA" refers to isophorone diamine available from Sigma Aldrich as 8.14123. "AEP" refers to n-aminoethylpiperazine available as A55209 from Sigma Aldrich. "DMDC" refers to 4,4' -methylene-bis (2-methylcyclohexylamine) available from Sigma Aldrich as 369500. "TTD" refers to 4,7, 10-trioxa-1, 13-tridecanediamine available from Sigma Aldrich as 369519. "MXDA" refers to a m-diamine available from Sigma Aldrich as X1202 and "N4" refers to N, N' -bis (3-aminopropyl) ethylenediamine available from Fischer Scientific as B195225 ML. "MHHPA" refers to methyl hexahydrophthalic anhydride available from Sigma Aldrich as 149934. TMD, IPDA, AEP, TTD, MXDA and N4 are amine-functionalized linking groups, while MHHPA is an anhydride-functionalized linking group. As used in tables 7-10, PPO, D400 and T403 are polymeric linking groups. "D400" refers to a diamine based poly (propylene glycol) available from Huntsman as Jeffamine D-400, including a number average molecular weight (Mn) of about 430 daltons. "T403" refers to trimethylolpropane parameter [ amine-terminated poly (propylene glycol) ] obtainable from Huntsman as Jeffamine T-403, including a number average molecular weight (Mn) of about 440 daltons. PPO, D400 and T403 are amine-functionalized polymeric linking groups. T403 is a trifunctional polymeric linking group.

Table 6: final composition Range (wt%)

Table 7: final composition Range (wt%)

Examples	AAA	BBB	CCC	DDD	EEE	FFF
							GPOSS	98	85	83	83	83	91
DBU	2	0	2	0	0	0
							TEA	0	0	0	0	0	0
Pyridine compound	0	0	0	2	0	0
							TMG	0	0	0	0	2	2
HAD	0	15	15	15	15	7

In tables 7-10, examples AAA-YYY and AAAA-FFFF include GPOSS (e.g., free GPOSS) of about 24wt% (example QQQ) to about 83wt% (example PPP), wherein examples AAA-PPP, RRR-YY and AAAA-FFFF include GPOSS of about 50wt% (example XXX) to about 83wt% (example PPP). Examples GGGG-HHHH include crosslinked GPOSS instead of free GPOSS. The example AAA includes a curing catalyst (i.e., DBU) without a linking group. Examples BBB, GGG, IIII and KKK include a linking group without a curing catalyst. Examples CCC-FFF, HHH, JJJ, LLL-YYY and AAAA-HHH include curing catalysts in combination with at least one linking group. Examples BBB-XXX, AAAA-DDDD and FFFF-HHH include amine-functional linking groups, while examples YYY and EEEEEEEEE include anhydride-functional linking groups. Examples BBB-EEE, GGG-XXX, AAAA-DDDD, and FFFF-HH include from about 15wt% to about 31wt% amine-functionalized linking groups. Examples TTT-XXX and CCCC-DDDD and FFFF-HHHH include TMPO. Examples RRR-XXX include mass ratios of polymer to all GPOSS ranging from about 0.288 (example RRR) to about 0.495 (example FFFF) and molar ratios of polymer to all GPOSS ranging from about 1.02 (example RRR) to about 1.54 (example XXX) (e.g., about 1 or greater). Examples AAAA-DDDD and FFFF include mass ratios of polymer to all GPOSS in the range of about 0.28 (example AAAA-BBBB) to about 0.33 (example CCCC-DDDD and FFFF) and molar ratios of polymer to all GPOSS in the range of about 0.89 (example AAAA) to about 1.01 (example CCCC-DDDD and FFFF). Example FFFF-GGGG includes a mass ratio of polymer to all GPOSS of about 1.335 and a molar ratio of about 1.65 to about 1.67. Example GGGG-HHHH comprises about 70wt% of the polymer composite.

Table 8: final composition Range (wt%)

Examples	GGG	HHH	III	JJJ	KKK	LLL	MMM	NNN	OOO
										GPOSS	81	80	80	79	79	78	73	84	74
DMP	0	1	0	1	0	1	1	1	1
										TMD	19	19	0	0	0	0	0	0	0
IPDA	0	0	20	20	0	0	0	0	0
										AEP	0	0	0	0	21	22	0	0	0
DMDC	0	0	0	0	0	0	26	0	0
										N4	0	0	0	0	0	0	0	15	0
TTD	0	0	0	0	0	0	0	0	25

Table 9: final composition Range (wt%)

Examples	PPP	QQQ	RRR	SSS	TTT	UUU	VVV	WWW	XXX
										GPOSS	82.4	24.9	77.0	69.0	69.4	63.3	58.0	53.7	49.9
DMP	0.8	0.3	0.8	0.7	0.7	0.6	0.6	0.5	0.5
										MXDA	16.8	0	0	0	0	0	0	0	0
PPO	0	74.8	0	0	0	0	0	0	0
										D400	0	0	22.2	0	22.9	23.5	24.0	24.4	24.7
T403	0	0	0	30.3	0	0	0	0	0
										TMPO	0	0	0	0	7.0	12.6	17.4	21.4	24.9

Table 10: final composition Range (wt%)

The properties reported in tables 11, 13-16 and 18 for examples A-G, M-N, AA-CC and JJ-RR were measured for coatings by irradiating the coatings with 365nm LEDs having a power density of 2.54J/cm2, these coatings being formed by curing the corresponding compositions of tables 3-6, irradiating the compositions for 5 minutes, followed by heating in an oven at 100℃for 30 minutes. The properties reported in tables 11 and 19 for examples H-K, O and Q-W were measured for coatings formed by curing the respective compositions of tables 3-6 by irradiating the compositions for 5 minutes without any subsequent heat treatment by irradiating the coatings with 365nm LEDs having a power density of 2.54J/cm 2. The properties reported in table 19 for examples P and L were measured for coatings formed by curing the corresponding compositions of tables 3-6 by irradiating the compositions for 5 minutes followed by heating in an oven at 65 ℃ or 85 ℃ for 30 minutes, respectively, by irradiating the coatings with 365nm LEDs having a power density of 2.54J/cm 2. The properties reported in tables 13-14 and 16-17 for examples AAA-YYY and AAAA-HHH were heated at the temperatures reported in tables 16-17 for 30 minutes without any irradiation. Unless otherwise indicated, the composition was deposited on the surface by pulling an applicator configured to produce a thickness of 25.4 μm on the substrate surface prior to curing the composition.

As shown in table 11, examples a-B and O included a tensile strength of about 26MPa or greater (e.g., in the range of about 26MPa to about 67.5 MPa), while examples a-B, E and O included a tensile strength of greater than 21 MPa. Examples a-B and O included a final elongation of 4% or greater (e.g., in the range of 4% to 8%), while examples a-B, E and O included a final elongation of greater than 3%. Example O included an elastic modulus of 1,255 MPa, example A included an elastic modulus of 1,270MPa, example E included an elastic modulus of 829MPa and example B included an elastic modulus of 680 MPa.

In table 12, the viscosity of the composition before curing is presented. Examples J-K include viscosities less than 1 Pa-s. Examples E-F and R-T include viscosities of about 7Pa-s to about 16 Pa-s. Example Q includes a viscosity of 41.8 Pa-s.

Table 11: properties of the coating

Examples	A	B	E	O	AA	BB
							Tensile strength (MPa)	36.9	26.5	21.9	67.4	55	--
Final elongation (%)	4.1	5.8	3.4	8.0	6.5	--
							Modulus of elasticity (MPa)	1,270	680	829	1,905	1,430	3,300

Table 12: viscosity of the composition

Examples	Viscosity (Pa-s)
		E	15.6
F	14.0
		J	0.3
K	0.2
		Q	41.8
R	18.4
		S	9.8
T	7.7

As shown in table 13, example AA included a contact angle of 62 °, while example BB included a contact angle of 99 °. Examples E-F, PPP-SSS, CCCC-DDDD and FFFF-HHHH include intermediate contact angles (e.g., 98, 68, 60, 98, 97, 60, 97 and 93, respectively). The PDMS polymer of example E increased the contact angle relative to examples F, AA, BBBB-DDDD and GGGG-HHH, while the poly (propylene oxide) polymers of examples F and FFFF increased the contact angle relative to example AA only slightly. Examples F and FFFF include rough surfaces relative to other examples, which illustrate lower contact angles than other examples with PDMS polymers (e.g., PDMS1-PDMS 4).

Table 13: contact angle of coating

Examples	Contact angle
		E	98°
F	68°
		AA	62°
BB	99°
		PPP	60°
SSS	60°
		BBBB	105°
CCCC	98°
		DDDD	97°
FFFF	60°
		GGGG	97°
HHHH	93°

In Table 14, the optical properties and dynamic coefficients of examples A-B, SSS and CCCC-HHH are reported. Examples SSS, CCCC-DDDD, and FFFF-HHH include dynamic coefficients of friction of about 0.38 to about 0.78 (e.g., less than 0.8). Examples CCCC-DDDD and GGGG-HHHH include dynamic coefficients of friction of less than about 0.5. As noted above, the roughened surface of the example FFFF results in a high dynamic coefficient of friction. Examples A-B, SSS, CCCC-DDDD and FFFF-HHH include an average light transmittance of about 90% or more averaged over a light wavelength of 400nm to 700 nm. Examples a-B and FFFF include an average transmittance of about 92% or more averaged over a light wavelength of 400nm to 700 nm. Examples a-B, CCCC and FFFF-GGGG include haze of about 0.15% to about 0.9% (e.g., less than about 1%). Examples A-B and FFFF-HHH include haze of about 0.15% to about 0.3% (e.g., less than about 0.5%, less than about 0.3%). Examples a-B included a yellowing index of about 0.6 or less and about 0.55 or less. Examples SSS, CCCC-DDDD, and FFFF-hh include CIE b x values of about 0.2 to about 0.4. Examples SSS and FFF-HHH include CIE b values of about 0.2 to about 0.3 (e.g., about 0.3 or less), while examples CCCC-DDDD include CIE b values of about 0.35 to about 0.4 (e.g., about 0.4 or more).

Table 14: properties of the coating (when formed)

Examples	Dynamic COF	Transmittance (%)	Haze (%)	CIE b*	Yellowing index
						A	--	92	0.27％	--	0.52
B	--	92	0.24％	--	0.49
						SSS	0.685	91	--	0.26	--
CCCC	0.382	91	0.9％	0.39	--
						DDDD	0.381	91	--	0.35	--
FFFF	0.775	92	0.16％	0.21	--
						GGGG	0.413	91	0.28％	0.22	--
HHHH	0.436	91	0.19％	0.23	--

Examples JJ-LL correspond to examples A-B and AA, respectively, but the cured composition comprises a cured composition having a J/cm of 2.54 ² The coating was irradiated by irradiating the composition for 5 minutes without subsequent heating of the composition. Examples MM-OO correspond to examples A-B and AA, but the cured composition comprises a composition having a J/cm of 13.44 ² The coating was irradiated by irradiating the composition for 5 minutes without subsequent heating of the composition. Examples PP-RR correspond to examples A-B and AA, respectively, but curing the composition includes curing the composition with a composition having a J/cm of 13.44 ² The coating was irradiated by 365nm LEDs of power density by irradiating the composition for 5 minutes followed by heating in an oven at 100 ℃ for 30 minutes. Examples AAA-YYY and AAAA-HHH were not irradiated; in contrast, AAA-YYY and AAAA-HHH were heated in an oven at 150℃for 30 minutes. Examples FFF-100 to KKK-100 correspond to the compositions of examples FFF-KKK, but examples FFF-100 to KKK-100 are heated in an oven at 100℃for 30 minutes instead of 150 ℃.

The adhesion values reported in table 15 were measured on samples formed without further processing examples using the cross-line adhesion test described above. Examples B, AA, KK-LL, NN-OO, RR, BBB-EEE, GGG-MMM, FFF-100-KKK-100, RRR, TTT-YYY, AAAA-DDDD, and FFFF-HHHH include an adhesion of 3B or more. Examples LL, OO, BBB-EEE, GGG-MMM, FFF-100-III-100, RRR, TTT-YYY, CCCC, and FFFF-HHHH include an adhesion of 4B or greater. Examples GGG-JJJ, FFF-100-JJ-100, TTT-YYY and FFFF-HHH include 5B adhesion. Examples A-B, AA-BB, JJ-RR, BBB, FFF, LLL-MMM, OOO-PPP and SSS include pen hardness of 5H or greater. Examples A-B, AA-BB, JJ-RR, FFF, LLL-MMM and OOO-PPP included pen hardness of 6H or greater. Examples A-B, BB, JJ-KK and MM-QQ included pen hardness of 7H or more. Examples B, BBB, JJ-KK and MM-RR included pen hardness of 8H or more. Examples B, BB, JJ-KK, MM-NN and PP-QQ included pen hardness of 9H or more. Examples B, KK-LL, NN, RR, BBB and LLL-MMM include pen hardness of 5H or greater and adhesion of 3B or greater. Examples B, KK, NN-OO and RR included a pen hardness of 8H or greater and an adhesion of 3B or greater. Examples LL, OO, BBB and LLL-MMM included pen hardness of 5H or greater and adhesion of 4B or greater. Examples LL, OO and LL-MMM include pen hardness of 6H or greater and adhesion of 4B or greater. The example BBB includes a pen hardness of 5H or greater and an adhesion of 4B or greater. Example NNN cracked during cure. The QQQ of example phase-separates so that a uniform coating cannot be formed.

Providing a linking group increases the pen hardness of the coating (compare example AAA with example BBB-FFF). The provision of a curing catalyst increases the pen hardness of the coating (compare examples BBB, III, III-100, KKK-100 with examples CCC, JJJ, JJJ-100, LLL). The polymeric linking group D400 (example RRR) provided the highest adhesion as compared to example QQQ-SSS. The addition of TMPO improved the adhesion and pen hardness of the coating (compare example RRR with examples TTT-XXX). Prior to curing, example ggggg-hhhhhh includes GPOSS connected by PDMS1, which provides a pen hardness of about 4H or greater and an adhesion of 5B or greater.

Table 15: hardness, adhesion and thickness of the coating (as formed)

The adhesion values reported in tables 16-17 were measured using the cross-line adhesion test described above after the coating (e.g., coated article) had been maintained at 95 relative humidity for 10 days in a 65 ℃ environment. The coatings of the examples reported in table 16 were deposited in the absence of surface treatments or silane coupling agents. Examples A-B, JJ-KK and MM-RR included pen hardness of 7H or greater. Examples B, JJ-KK, MM-NN and PP-QQ included 9H pen hardness. Examples B, JJ-LL, NN-OO and RR included adhesion of 1B or greater. Examples B, KK-LL, NN-OO and RR included adhesion forces of 3B or greater. Examples LL and OO include adhesion of 4B. Examples A, MM and PP-QQ included an adhesion of 0B. Comparing examples A-B, AA, JJ-LL with examples MM-RR, the total energy density of the irradiated composition did not significantly change the resultant adhesion, although the hardness may be slightly higher the total energy density. Unexpectedly, because it is expected to increase the total energy density to 10J/cm ² Or even 20J/cm ² Or higher will be apparentSignificantly improving adhesion and/or hardness. Thus, from the use of 2.54J/cm ² The pen hardness and adhesion of the composition cured by irradiation of the total energy density of (c) provides the unexpected benefits of reduced energy and time required, while yielding corresponding coating properties. Examples in table 16 based on example B (i.e., examples B, KK, NN, and QQ) included a hardness of 9H, while examples in table 16 based on example AA (i.e., examples AA, LL, OO, and RR) included a hardness of 8H or less.

Examples AA-CC are comparative examples. Unlike examples A-W, example AA does not contain any polymer. It is still possible to form the coating using the method described above, and the composition is visually transparent. However, the examples based on example AA (i.e., examples AA, LL, OO, and RR) included a hardness of 8H or less that was less than the 9H hardness achieved for the examples based on example B (i.e., examples B, KK, NN, and QQ). Unlike examples a-W, example BB includes a polymer having functional groups at only one end of the polymer chain, not at both ends. Thus, the polymer of example BB may not attach a first functionalized oligomeric silsesquioxane to another functionalized oligomeric silsesquioxane. Indeed, the composition of example BB was not visually clear when the solvent was removed. In contrast, when the solvent is removed, the composition of example BB is opaque white, which may be the result of the aggregation of the functionalized oligomeric silsesquioxane. Embodiment BB may not be applied to form a coating in the same manner as described for embodiments a-G, as irregular and/or segmented coatings will be formed. Thus, the coatings based on example BB required curing using a multi-step heating process to evaporate the solvent over 8 hours or more, which was significantly longer than the 5 minute UV radiation and even 30 minute heating experienced by some of examples A-W and JJ-RR. Example BB included an adhesion of 0B, which could not withstand 10 days without visible delamination or cracking in a 95% relative humidity, 65℃environment. Unlike examples A-W, example CC does not include any functionalized oligomeric silsesquioxane. In contrast, example CC includes silica nanoparticles and a linking group. Although example CC included an adhesion of 5B, example CC included a hardness of 0H, but was lower than the other examples. Therefore, example CC is not suitable as a hard coat layer.

Table 16: hardness, adhesion and thickness of the coating (10 days at 65 ℃ C., 95% relative humidity)

Examples	Hardness of pen	Adhesion force	Coating thickness (μm)
				A	7H	0B	48.6
B	9H	3B	24.9
				AA	6H	3B	24.8
BB	9H	0B	50.0
				JJ	9H	1B	32.6
KK	9H	3B	35.7
				LL	6H	4B	33.6
MM	9H	0B	30.0
				NN	9H	3B	34.3
OO	8H	4B	41.2
				PP	9H	0B	40.9
QQ	9H	0B	33.2
				RR	8H	3B	37.5

Table 17 presents the adhesion of examples A-B, AA-BB and SS-ZZ, as well as the treatment conditions based on the surface of the glass substrate prior to forming the coating. APTMS refers to (3-aminopropyl) trimethoxysilane available as 281778 from Sigma Aldrich. GOPTMS refers to (3-epoxypropyloxypropyl) trimethoxysilane available as 440167 from Sigma Aldrich, as Coatosil MP200 from Momentive, or as SIG5840.0 from Silquest. Ecletms refers to 2- (2, 4-epoxycyclohexyl) ethyl trimethoxysilane available as SIE4670.0 from Gelest or Silquest a186 from Momentive. TEPSA refers to (3-triethoxysilyl) propyl succinic anhydride available as SIT8192.6 from Gelest. MPTMS refers to (3-mercaptopropyl) trimethoxysilane available from Gelest as SIM 6476.0. Examples S-Z included coatings of example D attached to the substrate using the treatments indicated in table 17. The plasma treatments of examples TT, VV, XX and ZZ were performed prior to depositing any silane coupling agent and included exposing a surface (e.g., the first major surface) of the substrate to atmospheric plasma for 1 minute in a 25 ℃ environment.

Examples A, BB, SS, UU-WW and YY included an adhesion of 0B and were not subjected to plasma treatment prior to deposition of the silane coupling agent, as shown in table 17. Examples TT and ZZ include an adhesion of 1B or more and are plasma treated prior to the deposition of the silane coupling agent, while examples VV and XX include an adhesion of 0B even if plasma treatment is present prior to the deposition of the silane coupling agent. This demonstrates the unexpected benefit of APTMS and TEPSA that these silane coupling agents can improve the adhesion of the coating, while other silane coupling agents may not even be combined with plasma treatment. In addition, the results in Table 17 demonstrate that providing a surface treatment (e.g., a plasma treatment) prior to depositing the silane coupling agent can improve the adhesion of the coating.

Table 17: surface treatment, hardness and adhesion of the coating (10 days at 65 ℃ C., 95% relative humidity)

Examples	Plasma treatment	Silane coupling agent	Initiating substances	Hardness of	Adhesion force
						A	Whether or not	Whether or not	Whether or not	7H	0B
B	Whether or not	Whether or not	Whether or not	9H	3B
						AA	Whether or not	Whether or not	Whether or not	6H	3B
BB	Whether or not	Whether or not	Whether or not	9H	0B
						CC	Whether or not	Whether or not	Whether or not	0H	5B
SS	Whether or not	APTMS	Whether or not	--	0B
						TT	Is that	APTMS	Whether or not	--	1B
UU	Whether or not	GOPTMS	Whether or not	--	0B
						VV	Is that	GOPTMS	Whether or not	--	0B
WW	Whether or not	ECHETMS	Whether or not	--	0B
						XX	Is that	ECHETMS	Whether or not	--	0B
YY	Whether or not	TEPSA	Whether or not	--	0B
						ZZ	Is that	TEPSA	Whether or not	--	3B

Table 18: surface treatment, hardness and adhesion (as formed) of the coating

Unlike in table 17, the adhesion and hardness measurements reported in table 18 were measured on the coating of the coated article when formed. The substrates of examples M-N and P were treated with plasma prior to deposition of the composition. Examples H-I and O were coated with a 2wt% solution of the thiol-functionalized silane coupling agent MPTMS and heated at 100℃for 30 minutes. Examples M-N include compositions containing silane coupling agents, as shown in Table 4. Examples H-U include a hardness of 7H or greater. Examples H-I, K, M-P and R-U include hardness of 8H or more. Examples M-P and R-U included a hardness of 9H. Examples H-W include adhesion of 1B or greater. Examples H-K, M and O-W included adhesion of 2B or greater. Examples H-K, M, O, Q and S-W included adhesion of 3B or greater. Examples H, J-K, O, T and V-W include adhesion of 4B or greater. Examples J-K included 5B adhesion. Examples H-K, M and O, Q, S-U include a hardness of 7H or more and an adhesion of 3B or more. Examples H, K, O and T include an adhesion of 8H or greater and an adhesion of 4B or greater.

The adhesion values reported in table 19 were measured after the coating (e.g., coated article) had been held at 85% relative humidity in an environment of 85 ℃ for 30 minutes using the cross-line adhesion test described above. The coatings of the examples reported in table 19 were deposited without surface treatment or silane coupling agents. Examples GGG-RRR, GGG-100-JJJ-100, TTT-XXX, AAAA-DDDD, and FFFF-HHH include an adhesion of 3B or more. Examples GGG-JJJ, GGG-100-JJJ-100, UU-VVV, XXX, CCCC-DDDD, and FFFF-HHHH include an adhesion of 4B or more. Examples GGG-JJJ, GGG-100-JJJ-100, XXX, DDDD and GGGG-HHHH include an adhesion of 5B or more.

Table 19: hardness, adhesion and thickness of the coating (30 min at 85 ℃ C., 85% relative humidity)

In table 20, the pen-down heights of coated articles similar to the coated article 301 shown in fig. 3 are reported. The substrate 103 comprises composition 1 and the substrate thickness 109 is 30 μm. The first portion 321 and the second portion 331 comprise composition 1 and the partial thickness 329 is 30 μm. The coating 113 includes a coating thickness 119 of 30 μm. The coating was formed by curing the composition of example E. The median pen drop height was 17cm when the pen drop was performed on the second surface area 325 of the first portion 321. The median pen drop height was 16cm when the pen drop was performed on the third major surface 115 of the coating 113 extending along the fourth plane 306. The control was a 30 μm thick substrate containing composition 1, comprising a median pen drop height of 7.4 cm. Thus, providing a coating increases the median pen drop height of the two areas tested. Specifically, the median drop height above the coating (i.e., the third major surface 115 extending along the fourth plane 306) is only 1cm (6%) below the median drop height above the first portion.

Table 20: height of pen drop of coated article

Examples	Median pen drop height (cm)
		Control	7.4
Over the coating	16
		Above the first part	17

The parallel plate distance of a coated article similar to the coated article 201 shown in fig. 2 and 6 was measured. The substrate 203 comprises composition 1 and has a substrate thickness 209 of 100 μm and a center thickness 289 of 30 μm. The coating 113 includes a coating thickness 119 of 30 μm. The coating was formed by curing the composition of example E. After 10 days in a 25 ℃ environment at 50% relative humidity, the coated article achieved a parallel plate distance of 3 mm. In addition, the coated article as formed was able to withstand 200,000 cycles of bending to a parallel plate distance of 3 mm.

The above observations can be combined to provide compositions, coatings, and coated articles comprising a variety of functionalized oligomeric silsesquioxanes, as well as methods of making such compositions, coatings, and coated articles. A variety of functionalized oligomeric silsesquioxanes can provide good scratch resistance and/or high pen hardness (e.g., about 5H or greater, about 7H or greater, about 9H or greater). Providing a plurality of functionalized oligomeric silsesquioxanes can react with a first functional group and/or a second functional group of a linking group (e.g., a polymer). The degree of functionalization of the plurality of functionalized oligomeric silsesquioxanes may facilitate the binding of a linking group (e.g., a polymer) to two different ones of the plurality of functionalized oligomeric silsesquioxanes. Providing a coating on the substrate improves the durability of the coated article, for example by filling surface defects in the substrate and/or protecting the surface defects in the substrate from damage. In addition, the substrate may include a glass-based substrate and/or a ceramic-based substrate to enhance puncture resistance and/or impact resistance. In addition, the glass-based substrate and/or ceramic-based substrate may be chemically strengthened to further enhance the impact and/or puncture resistance of the coated article while promoting good bending properties.

The composition may comprise a linking group (e.g., a polymer) having a functional group at an opposite end of the linking group (e.g., a polymer), wherein the functional group reacts with the functionalized oligomeric silsesquioxane. The linking group may include a polymer that may reduce (e.g., prevent) aggregation of the various functionalized oligomeric silsesquioxanes, may provide good optical properties (e.g., high transmittance, low haze), and as a coating, may provide good durability and/or good adhesion to the substrate. Providing a linking group (e.g., a polymer) that includes oxygen atoms in the backbone of the linking group (e.g., a polymer) can increase the flexibility of the linking group, the resulting composition, and the resulting coating, which can increase the ultimate elongation, durability, and/or impact resistance (e.g., pen drop height). Providing a linking group comprising a polymer having a number average molecular weight (Mn) in the range of about 400 daltons to about 30,000 daltons can prevent aggregation of the functionalized oligomeric silsesquioxane attached thereto while reducing entanglement of the polymer, which can inhibit manufacturability of the resulting coating and/or coated article. Providing a low molar ratio of linking groups (e.g., polymer) to the various functionalized oligomeric silsesquioxanes (e.g., about 0.06 or less) can result in a polymer that binds to both functionalized oligomeric silsesquioxanes, which can achieve the benefits described above. Providing a polymer having a glass transition temperature outside the operating range of the coated article (e.g., outside the operating range of about-20 ℃ to about 60 ℃) may result in a coated article having consistent properties over the operating range. Providing a reactive diluent (e.g., a linking group that is not bonded to the functionalized oligomeric silsesquioxane prior to curing after the composition is disposed on a substrate) can be used to adjust the viscosity of the composition, which can facilitate uniform application and/or enable lower cost application techniques while reducing the overall cost of the composition and/or coating.

Providing a linking group comprising one or more amine and/or anhydride functional groups can provide a coating that has good adhesion to a substrate (e.g., about 4B or greater when formed, about 4B or greater after 10 days of holding at 50% relative humidity in a 25 ℃ environment, and/or about 4B or greater after 10 days of holding at 95% relative humidity in a 65 ℃ environment), whether or not a silane coupling agent is used. Providing a curing catalyst may increase the hardness of the resulting coating. Providing a composition comprising trimethylol propane oxetane can increase the hardness of the resulting coating. The coating may be hydrophobic, have a low dynamic coefficient of friction (i.e., about 0.8 or less, such as about 0.5 or less), good abrasion resistance, and/or function as an easy-to-clean (ETC) coating.

Forming the layer from a substantially solvent-free composition may increase its cure rate, which may reduce processing time. Furthermore, solvent-free compositions may reduce (e.g., reduce, eliminate) the use of rheology modifiers and increase composition uniformity, which may increase the optical clarity (e.g., transmittance) of the resulting coating. Furthermore, the solvent-free composition may reduce the incidence of visual defects (e.g., bubbles generated by volatile gases upon evaporation of any solvent) in the resulting coating. Providing a coating process that includes a solvent may enable a wide variety of compositions to be used to form a coating. In addition, the layer is cured by irradiating the layer for a short time to form a coating layer, which can improve the processing efficiency and reduce the manufacturing cost. Providing the composition with additional functionalized oligomeric silsesquioxane to form the layer may further increase the hardness of the resulting coating and/or coated article. Providing a composition that does not contain a photoinitiator (e.g., a thermosetting composition) may not present yellowing problems. Providing a silane coupling agent can increase the adhesion of the coating to a substrate (e.g., glass-based substrate, polymer-based substrate). In addition, the coating may include high light transmittance (e.g., about 90% or greater), low haze (e.g., about 0.5% or less), and/or low yellowing index (e.g., about 0.6 or less). Providing a composition that is substantially free and/or free of nanoparticles (e.g., silica nanoparticles, alumina nanoparticles) may reduce handling problems (e.g., agglomeration, aggregation, phase separation) of the composition, 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 resulting coating and/or coated article, and reduce mechanical properties (e.g., hardness, modulus, strain) of the resulting coating and/or coated article, as compared to a corresponding composition, coating and/or coated article that includes a plurality of functionalized oligomeric silsesquioxanes without nanoparticles (e.g., silica nanoparticles, alumina nanoparticles).

Directional terms used herein, such as up, down, right, left, front, rear, up, down, refer only to the drawing figures as drawn and are not intended to be meant to be absolute orientations.

It is to be understood that the various disclosed aspects may be directed to features, elements, or steps described in connection with the aspects. It should be understood that although described with respect to one aspect, features, elements or steps may be interchanged or combined with alternative aspects not shown.

It should also be understood that the terms "the", "a/an", as used herein, mean at least "one" and should not be limited to "only one" unless explicitly indicated to the contrary. For example, reference to "a component" includes aspects having two or more such components unless the context clearly indicates otherwise. Also, "plural" means "more than one" species.

As used herein, the term "about" means that the amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller (as desired), reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, aspects include from the one particular value and/or to the other 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 a range value or endpoint in the specification references an "about," the range value or endpoint is intended to include two aspects: one is modified by "about" and the other is not modified by "about". It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently at the other endpoint.

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

Any method set forth herein should not be construed as requiring that its steps be performed in a specific order, unless expressly stated otherwise. Thus, if a method claim does not actually recite an order to be followed by its steps or it is not otherwise explicitly stated in the claims or descriptions that the steps are limited to a particular order, it is in no way intended that any particular order be inferred.

While the use of the transitional phrase "comprising" may be used to disclose various features, elements, or steps of a particular aspect, it should be understood that inclusion of alternative aspects that may be described using the transitional phrase "consisting of" or "consisting essentially of … …" is implicit. Thus, for example, implicitly substituted aspects of a device that includes a+b+c include aspects in which the device consists of a+b+c and aspects in which the device consists essentially of a+b+c. As used herein, the terms "comprising" and "including" and variations thereof are to be interpreted as synonyms and openness unless otherwise indicated.

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 of the 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 spirit or scope of the disclosure. Accordingly, it is intended that the present disclosure cover modifications and variations of this provided they come within the scope of the appended claims and their equivalents.

Claims

1. A coated article comprising:

a substrate comprising a first major surface; and

Wherein the coating comprises a pen hardness of about 5H or greater.

2. The coated article of claim 1, further comprising a silane coupling agent that adheres the coating to the first major surface.

3. The coated article of claim 2, wherein the silane coupling agent is selected from the group consisting of: (3-triethoxysilyl) propylsuccinic anhydride, (3-mercaptopropyl) trimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

4. The coated article of any of claims 1-3, wherein the coating comprises an adhesion to the substrate of about 1B or greater after 10 days in a 95% relative humidity, 65 ℃ environment.

5. The coated article of any one of claims 1-4, wherein the first functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides, and the second functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides.

6. The coated article of any one of claims 1-4, wherein the first functional group is selected from the group consisting of: alcohol, acrylate, epoxide and urea groups, and the second functional group is selected from the group consisting of: alcohols, acrylates, and epoxides.

7. The coated article of any one of claims 1-6, wherein the backbone of the linking group comprises an oxygen atom.

8. The coated article of any of claims 1-7, wherein the plurality of functionalized oligomeric silsesquioxanes comprises a plurality of functionalized polyhedral oligomeric silsesquioxanes (POSS), the first functionalized oligomeric silsesquioxanes comprises a first functionalized POSS of the plurality of functionalized POSS, and the second functionalized oligomeric silsesquioxanes comprises a second functionalized POSS of the plurality of functionalized POSS.

9. The coated article of any of claims 1-8, wherein the first functionalized oligomeric silsesquioxane and/or the second functionalized oligomeric silsesquioxane is functionalized with a epoxypropyl functional group or an epoxycyclohexyl functional group.

10. The coated article of any one of claims 1-7, wherein the linking group comprises a polymer.

11. The coated article of any one of claims 1-10, wherein the coated article achieves a parallel plate distance in the range of about 3 millimeters to about 10 millimeters.

12. The coated article of any one of claims 1-11, wherein the coated article achieves a parallel plate distance of 4 millimeters.

13. A method of making a coated article comprising:

the layer is cured to form a coating.

14. The method of claim 13, wherein the first functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides, and the second functional group is selected from the group consisting of: acid alcohols, anhydrides, amides, amines, alcohols, chlorides, cyanides, epoxides, thiols, and magnesium halides.

15. The method of any one of claims 13-14, wherein the plurality of functionalized oligomeric silsesquioxanes comprises a third functionalized oligomeric silsesquioxanes of another functionalized oligomeric silsesquioxanes that is not bound to the polymer, the first major surface, or the plurality of functionalized oligomeric silsesquioxanes prior to the curing.

16. A method of making a coated article comprising

curing the layer to form a coating, wherein the linking group reacts with the plurality of functionalized oligomeric silsesquioxanes to bind a first functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes to a second functionalized oligomeric silsesquioxanes of the plurality of functionalized oligomeric silsesquioxanes, the linking group comprising a third functional group bound to the first functionalized oligomeric silsesquioxanes and a fourth functional group bound to the second functionalized oligomeric silsesquioxanes.

17. The method of claim 16, wherein the third functional group is selected from the group consisting of: acid alcohol, acrylate, anhydride, alcohol, epoxide, isocyanate, and urea groups, and the fourth functional group is selected from the group consisting of: acid alcohols, acrylic esters, anhydrides, alcohols, epoxides, isocyanates, and ureido groups.

18. The method of any one of claims 14 to 17, wherein the plurality of functionalized oligomeric silsesquioxanes comprises a plurality of functionalized polyhedral oligomeric silsesquioxanes (POSS), the first functionalized oligomeric silsesquioxanes comprises a first functionalized POSS of the plurality of functionalized POSS, and the second functionalized oligomeric silsesquioxanes comprises a second functionalized POSS of the plurality of functionalized POSS.

19. The method of any one of claims 14 to 18, wherein the first functionalized oligomeric silsesquioxane and/or the second functionalized oligomeric silsesquioxane is functionalized with a epoxypropyl functional group or an epoxycyclohexyl functional group.

20. The method of any one of claims 14 to 19, wherein the layer further comprises a silane coupling agent.