CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/235,430, filed on August 20, 2021 , which is incorporated herein by reference in its entirety.

BACKGROUND

[0002] As global temperatures rise, energy costs relating to heating and air conditioning in industrial buildings, hospitals, and other buildings increase. New building materials can address some of these issues for future construction, but it would be desirable to develop solar- and/or thermally-insulating coatings that could be used to reduce energy usage in both new and existing buildings, resulting in cost savings as well as a reduction in fossil fuel consumption, such as occurs when coal-fired power plants are used for energy generation.

[0003] Exterior and interior corrosion from acid rain, chemical exposure, and the like, can cause damage to building surfaces, resulting in an unsightly appearance and, potentially, damage to structural aspects of buildings, as well. Similarly, microbial growth (e.g., mildew, algae, fungi, and/or bacteria) can cause a decrease in interior air quality for building occupants and damage to surfaces as well as a decline in overall aesthetics. Additionally, it may be desirable under certain circumstances to modify additional properties of building surfaces such as fire resistance, electrical conductivity, and the like, while maintaining an aesthetically-pleasing appearance.

[0004] Existing coating compositions can be expensive to produce and may only include one or two beneficial properties in the same coating composition, thus requiring building owners to choose a reduced set of benefits or to apply multiple coatings, which may not be fully compatible with one another.

[0005] Despite advances in solar and thermally insulating coatings, there is still a scarcity of coating compositions that are inexpensive to produce, that have desirable viscosities for spray application and/or other application types, that are long-lasting, and that impart other beneficial properties such as, for example, anti-corrosive properties, antimicrobial properties, hydrophobicity, electrical insulation, and the like, to substrates to which they are applied. These needs and other needs are satisfied by the present disclosure. SUMMARY

[0006] In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to solar and thermally insulating coating compositions for building surfaces and other industrial surfaces. In one aspect, the coating compositions comprise a carrier, at least one pigment, at least one filler, and a microsphere composition, wherein the microsphere composition comprises one or more of aerogel microspheres, ceramic microspheres, glass microspheres, or any combination thereof. The coating compositions can also comprise additional components including, but not limited to, a biocide, and other wetting, curing, and defoaming aids as required by the identity of the carrier. Also disclosed are methods of making the compositions, coatings made from the compositions, and substrates incorporating the coatings. In one aspect, the coatings impart beneficial properties to the substrates to which they are applied including, but not limited to, high reflectivity, thermal insulation, hydrophobicity, antimicrobial properties, anti-corrosive properties, fire resistance, and combinations thereof.

[0007] Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features and modifications of the described embodiments are usable in all aspects of the disclosure taught herein. Furthermore, the individual features of the dependent claims, as well as all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with one another.

DETAILED DESCRIPTION

Coating Compositions

[0008] In one aspect, disclosed herein is a coating composition that includes a carrier, at least one pigment, at least one filler, and a microsphere composition.

[0009] In one aspect, the carrier is present in an amount of from about 30 to about 60 parts by weight, or at about 30, 35, 40, 45, 50, 55, or about 60 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. [0010] In a further aspect, the pigment can be selected from titanium dioxide, a fluorescent pigment, an infrared reflective pigment, or any combination thereof. Further in this aspect, the pigment imparts a color to the coating composition. In one aspect, the pigment is present in an amount of from about 5 parts by weight to about 15 parts by weight, or at about 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, or 15 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0011] In one aspect, the microsphere composition includes aerogel microspheres, ceramic microspheres, glass microspheres, or any combination thereof. In a further aspect, the microsphere composition is present in an amount of from about 1 to about 20 parts by weight, or at about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or about 20 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0012] In one aspect, the aerogel microspheres include trimethylated silica gel. In a further aspect, the aerogel microspheres can have an average diameter of from about 10 to about 60 pm, or of about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 pm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0013] In another aspect, the ceramic microspheres include an alkali aluminosilicate ceramic. In a further aspect, the ceramic microspheres can have an average diameter of from about 10 to about 60 pm, or of about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 pm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0014] In still another aspect, the glass microspheres include soda-lime-borosilicate glass microspheres. In a further aspect, the glass microspheres can have an average diameter of from about 10 to about 60 pm, or of about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 pm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0015] In one aspect, the carrier can be a water-based emulsion or a two-part epoxy resin. In another aspect, the water-based emulsion can be a polymeric emulsion, and can optionally be an acrylic emulsion. In any of these aspects, the water-based emulsion can be self-crosslinking.

[0016] In one aspect, when the carrier is a water-based emulsion, the coating composition can further include a coolant, a wetting agent, a defoamer, a coalescing aid, a rheology modifier, a solvent, or any combination thereof. [0017] In one aspect, the coolant can be ethylene glycol, propylene glycol, or any combination thereof. In a further aspect, the coolant can be present in an amount of from about 0.1 to about 2.5 parts by weight, or at about 0.1 , 0.5, 1 , 1.5, 2, or about 2.5 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0018] In another aspect, the wetting agent can be a surfactant, an alcohol, or any combination thereof. In a further aspect, the surfactant can be an anionic surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, or any combination thereof. In one aspect, the anionic surfactant can be an alcohol phosphate, an alcohol phosphonate, an alkyl alkoxy carboxylate, an alkyl aryl sulfate, an alkyl aryl sulfonate, an alkyl carboxylate, an alkyl ether carboxylate, an alkyl ether sulfate, an alkyl ether sulfonate, an alkyl phosphate, an alkyl polyethoxy carboxylate, an alkyl polyglucoside, an alkyl polyglucoside sulfate, an alkyl polyglucoside sulfonate, an alkyl succinamate, an alkyl sulfate, an alkyl sulfonate, an aryl sulfate, an aryl sulfonate, a fatty tauride, an isethionate, an N-acyl taurate, a nonoxynol phosphate, an octoxynol phosphate, a sarcosinate, a sulfated fatty acid ester, a taurate, or any combination thereof.

[0019] In another aspect, the cationic surfactant can be a quaternary ammonium salt. In still another aspect, the nonionic surfactant can be an ethoxylated alcohol, polysorbate 20, polysorbate 80, or any combination thereof. In yet another aspect, the zwitterionic surfactant can be a lecithin, a hydroxysultaine, a betaine, a sulfobetaine, or any combination thereof.

[0020] In one aspect, the alcohol can be butanediol, a hexane diol, propylene glycol, sorbitol, a hexane triol, glycerol, or any combination thereof.

[0021] In any of these aspects, the wetting agent can be present in an amount of from about 0.05 to about 1.5 parts by weight, or at about 0.05, 0.1 , 0.25, 0.5, 0.75, 1 , 1.25, or about 1.5 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0022] In one aspect, the defoamer can be nonyl phenol, ethoxylated nonyl phenol, tributyl phosphate, triisobutyl phosphate, polypropylene oxide, a hydrocarbon, a nonionic surfactant, or any combination thereof. In another aspect, the defoamer can be present in an amount of from about 0.05 to about 2 parts by weight, or about 0.05, 0.1 , 0.25, 0.5, 0.75, 1 , 1.25, 1.5, 1.75, or about 2 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. [0023] In still another aspect, the coalescing aid can be an ester alcohol, an ethylene glycol monoalkyl ether, or any combination thereof. In one aspect, the coalescing aid can be present in an amount of from about 0.5 to about 5 parts by weight, or about 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0024] In yet another aspect, the rheology modifier can be an acid-containing acrylic emulsion, an alkali-swellable polysaccharide, a poly(acrylate), a poly(alkene), a poly(alkyl oxide), a poly(amide), a poly(carbonate), a poly(diene), a poly(ester), a poly(methacrylate), a poly(saccharide), a poly(siloxane), a poly(styrene), a poly(urethane), a poly(vinyl ether), a derivative thereof, a copolymer thereof, or any combination thereof. In one aspect, the rheology modifier can be present in an amount of from about 0.1 to about 5 parts by weight, or about 0.1 , 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0025] In still another aspect, the solvent can be water and can be present in an amount of from about 1 to about 30 parts by weight, or at about 1 , 5, 10, 15, 20, 25, or about 30 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0026] In one aspect, the coating can be a two-part epoxy resin and further includes a solvent, a curing agent, an alcohol, an emulsifier, a coupling agent, or any combination thereof.

[0027] In one aspect, the solvent can be toluene, benzene, xylenes, diethyl ether, hexanes, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, or any combination thereof. In another aspect, the solvent can be present in an amount of from about 5 to about 20 parts by weight, or at about 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or about 20 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0028] In another aspect, the curing agent can be a monofunctional polyetheramine, a difunctional polyetheramine, a trifunctional polyetheramine, a cyclic aliphatic polyamine, a polyamidoamine, an imidazole or a salt thereof, a phenalkamine, a phenalkamide, or any combination thereof. In a further aspect, the difunctional polyetheramine can have the formula , wherein x has an average value of about 2.5. In still another aspect, the curing agent can be present in an amount of from about 30 to about 70 parts by weight, or at about 30, 35, 40, 45, 50, 55, 60, 65, or about 70 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0029] In one aspect, the alcohol can include benzyl alcohol, t-butyl alcohol, t-amyl alcohol, 1- heptanol, 1-octanol, 1-decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, cyclohexanol, or any combination thereof. In a further aspect, the alcohol can be present in an amount of from about 5 to about 10 parts by weight, or at about 5, 6, 7, 8, 9, or about 10 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0030] In one aspect, the emulsifier can be a nonylphenol, a polyethylene glycol (PEG), a PEG stearate, a glycol stearate, an ethoxylated fatty acid, a C12-C24 fatty acid, a rosin acid, polyacrylic acid, a polyacrylate, an alkyl sulfonate, an alkyl benzyl sulfonates, an alkyl sulfate, an alkyl phosphonates, an alkyl phosphate, a phenolic resin, an organic sulfate, an organic sulfonate, an organic phosphate, an organic phosphonate, or any combination thereof. In another aspect, the emulsifier can be present in an amount of from about 25 to about 50 parts by weight, or at about 25, 30, 35, 40, 45, or about 50 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0031] In one aspect, the coupling agent can be a silane-based coupling agent, a titanium-based coupling agent, a zirconium-based coupling agent, an aluminum-based coupling agent, or any combination thereof. In a further aspect, the silane-based coupling agent can be selected from N(P-aminoethyl) y-aminopropyltrimethoxy-silane, 3-aminopropyl silane, N-(2-aminoethyl)-3- aminopropyl silane, vinyl silane, methyl silane, N-phenylaminopropyl silane, (N- phenylamino)methyl silane, N-(2-vinylbenzylaminoethyl)-3-aminopropyl substituted alkoxy silane, 3-aminopropyltrimethoxy silane, 3-aminopropyldimethoxy silane, 3-aminopropyltriethoxy silane, 3 -aminopropyldi ethoxy silane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N- (2-aminoethyl)-3-aminopropyldiethoxysilane, a hydrolysate thereof, an oligomer thereof, or any combination thereof. In still another aspect, the titanium-based coupling agent can be selected from isopropyl(N-ethylaminoethylamino)titanate, isopropyl triisostearoyl titanate, titanium di(dioctylpyrophosphate)oxyacetate, tetra iso propyl di(dioctylphosphite)titanate, and neoalkoxy tri(p-N-(P-aminoethyl)aminophenyl)titanate, or any combination thereof. In still another aspect, the zirconium-based coupling agent can be Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxy tris(neodecanoyl) zirconate, neoalkoxy tris(dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris(ethylenediaminoethyl)zirconate, neoalkoxy tris(m- aminophenyl)zirconate, ammonium zirconium carbonate, or any combination thereof. In one aspect, the aluminum based coupling agent can be Al-acetylacetonate, Al-methacrylate, Al- propionate, or any combination thereof. In any of these aspects, the coupling agent can be present in an amount of 0.5 to about 5 parts by weight, or about 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0032] In another aspect, the coating composition includes at least one biocide. In a further aspect, the biocide can be selected from ammonia, a primary amine, a secondary amine, a tertiary amine, chlorhexidine, a biguanide, an acid amide, a peroxide, dibromopropamidine, tetrakis(hydroxymethyl)phosphonium, guanidine, ortho-phenyl phenol, dodecyl gallate, a salt thereof, or any combination thereof. Further in this aspect, the biocide can be present in an amount of from about 0.5 parts by weight to about 5 parts by weight, or at about 0.5, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or about 5 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0033] In another aspect, the coating composition further includes cellulose or a derivative thereof. In one aspect, the cellulose can be present in an amount of from about 1 to about 10 parts by weight, or in the amount of about 1 , 2, 3, 4, 5, 6, 7, 8, 9, or about 10 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0034] In one aspect, the coating composition can have a Zahn Cup #2 viscosity of from about 10 to about 70 seconds, or of about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or about 70 seconds, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In another aspect, the coating composition can have a pH of from about 8 to about 10, or of about 8, 8.5, 9, 9.5, or about 10, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0035] In one aspect, the filler can be selected from calcium carbonate, ammonium polyphosphate, pentaerythritol, aluminum hydroxide, melamine, or any combination thereof. In a further aspect, the filler can be present in an amount of from about 10 to about 40 parts by weight, or at about 10, 15, 20, 25, 30, 35, or about 40 parts by weight, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. Methods for Making the Coating Compositions

Water-Based Compositions

[0036] In one aspect, disclosed herein is a method for making a coating composition, the method including at least the steps of:

(a) admixing a microsphere composition and a pigment in water to form a first composition;

(b) admixing a water-based emulsion with the first composition to form the coating composition.

[0037] In a further aspect, the microsphere composition can include aerogel microspheres, ceramic microspheres, glass microspheres, or any combination thereof and the pigment can include titanium dioxide, a fluorescent pigment, an infrared reflective pigment, or any combination thereof. In one aspect, the method further includes admixing a coolant, a biocide, or any combination thereof, into the first composition in step (a). In another aspect, the method further includes admixing water, a wetting agent, a defoamer, a coalescing aid, a rheology modifier, a biocide, or any combination thereof with the first composition in step (b).

[0038] Epoxy-Based Compositions

[0039] In another aspect, disclosed herein is a method for making a coating composition, the method including at least the steps of:

(a) admixing one or more first epoxy resin components and a microsphere composition to form a first epoxy part, wherein the microsphere composition comprises aerogel microspheres, ceramic microspheres, and glass microspheres;

(b) providing a second epoxy part comprising one or more second epoxy resin components; and

(c) admixing the first epoxy part and the second epoxy part to form the coating composition.

[0040] In still another aspect, the method further includes admixing a solvent, an alcohol, a biocide, or any combination thereof into the first epoxy part in step (a). In still another aspect, the method further includes admixing a curing agent, an alcohol, an emulsifier, a coupling agent, a biocide, or any combination thereof into the second epoxy part in step (b). [0041] Also disclosed are coating compositions made by the disclosed methods.

Substrates and Application of the Coating Compositions

[0042] In one aspect, disclosed herein is a method for applying the disclosed coating compositions to a substrate, the method including spray coating, roll coating, dip coating, or flow coating the composition onto the substrate.

[0043] In another aspect, the substrate can be an exterior surface of a building, an interior surface of a building, a pipe, a boiler, a hospital surface, a kitchen surface, a marine surface, or a surface on industrial equipment. In one aspect, the exterior surface of the building can be an external wall, cladding, window frame, or roof. In a further aspect, the interior surface of the building can be a wall, ceiling, interior window frame, window attachment, flooring, or another surface. In one aspect, the roof can be a galvanized steel roof or an aluminum roof.

[0044] Also disclosed are coatings including the disclosed coating compositions. In one aspect, the coating can have a thickness of from about 0.05 mm to about 2 mm, or of about 0.05, 0.1 , 0.25, 0.5, 0.75, 1 , 1 .25, 1 .5, 1.75, or about 2 mm, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0045] In one aspect, the coatings can have one or more beneficial properties selected from high reflectivity, thermal insulation, low conductivity, hydrophobicity, antimicrobial properties, anticorrosive properties, fire resistance, low heat transfer coefficient, high elasticity, and combinations thereof.

[0046] Also disclosed are substrates including the disclosed coatings. In one aspect, the substrate can be an exterior surface of a building, an interior surface of a building, a pipe, a boiler, a hospital surface, a kitchen surface, a marine surface, or a surface on industrial equipment.

[0047] In an aspect, when the exterior surface of a building is a metal roof, the metal roof can have a gauge of from about 20 to about 29, or of about 20, 21 , 22, 23, 24, 25, 26, 27, 28, or about 29, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. Further in this aspect, the substrate can have a conductivity of at least 10% lower than a comparable roof without the coating, or can have a conductivity of from about 45 to about 60 W/m-K, or of about 45, 50, 55, or about 60 W/m-K, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values. In another aspect, the substrate can have an electrical resistance at least 25% lower than a comparable roof without the coating. In one aspect, the substrate can have an electrical resistance of from about 1.1 x 1O ^-4 to about 1.5 x w ⁴ m ² -K/W, or of about 1.1 x W ⁴ , 1.2 x 1O’ ⁴ , 1.3 x W ⁴ , 1.4 x W ⁴ , or about 1.5 x 10’ ⁴ m ² -K/W, or a combination of any of the foregoing values, or a range encompassing any of the foregoing values.

[0048] Many modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

[0049] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0050] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0051] Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0052] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation. [0053] While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present disclosure can be described and claimed in any statutory class.

[0054] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0055] Prior to describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure.

Definitions

[0056] As used herein, “comprising” is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms “by,” “comprising,” “comprises,” “comprised of,” “including,” “includes,” “included,” “involving,” “involves,” “involved,” and “such as” are used in their open, non-limiting sense and may be used interchangeably. Further, the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of” and “consisting of.” Similarly, the term “consisting essentially of’ is intended to include examples encompassed by the term “consisting of.

[0057] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a biocide,” “a coupling agent,” or “a defoamer,” includes, but is not limited to, mixtures or combinations of two or more such biocides, coupling agents, or defoamers, and the like.

[0058] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0059] When a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y.’ The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x,’ ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y’, and ‘less than z’. Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x,’ ‘about y,’ and ‘about z’ as well as the ranges of ‘greater than x,’ greater than y,’ and ‘greater than z.’ In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.

[0060] It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or subranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1 % to 5%” should be interpreted to include not only the explicitly recited values of about 0.1 % to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range.

[0061] As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that 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 such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, it is generally understood, as used herein, that “about” and “at or about” mean the nominal value indicated ±10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It is understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0062] As used herein, the term “effective amount” refers to an amount that is sufficient to achieve the desired modification of a physical property of the composition or material. For example, an “effective amount” of a biocide refers to an amount that is sufficient to achieve the desired improvement in the property modulated by the formulation component, e.g. achieving the desired level of control of microorganisms including, but not limited to, bacteria, fungi, algae, mildew, or the like. The specific level in terms of wt% in a composition required as an effective amount will depend upon a variety of factors including the amount and type of biocide, amount and type of epoxy resin or water-based emulsion used for the disclosed coatings, amount and type of pigment, microsphere composition, local climate conditions for application of the coating that includes the biocide and intended substrate of the coating that includes the biocide.

[0063] As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0064] Unless otherwise specified, pressures referred to herein are based on atmospheric pressure (i.e. one atmosphere).

[0065] Now having described the aspects of the present disclosure, in general, the following Examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure. ASPECTS

[0066] The following list of exemplary aspects supports and is supported by the disclosure provided herein.

[0067] Aspect 1. A coating composition comprising a carrier, at least one pigment, at least one filler, and a microsphere composition.

[0068] Aspect 2. The coating composition of aspect 1 , wherein the pigment comprises titanium dioxide, a fluorescent pigment, an infrared reflective pigment, or any combination thereof, and wherein the pigment imparts a color to the coating composition.

[0069] Aspect 3. The coating composition of aspect 1 or 2, further comprising at least one biocide.

[0070] Aspect 4. The coating composition of any one of the preceding aspects, further comprising cellulose.

[0071] Aspect 5. The coating composition of aspect 4, wherein the cellulose is present in an amount of from about 1 to about 10 parts by weight.

[0072] Aspect 6. The coating composition of any one of the preceding aspects, wherein the carrier is present in an amount of from about 30 to about 60 parts by weight.

[0073] Aspect 7. The coating composition of any one of the preceding aspects, wherein the pigment is present in an amount of from about 5 to about 15 parts by weight.

[0074] Aspect 8. The coating composition of any one of the preceding aspects, wherein the microsphere composition comprises aerogel microspheres, ceramic microspheres, glass microspheres, or any combination thereof.

[0075] Aspect 9. The coating composition of any one of the preceding aspects, wherein the microsphere composition is present in an amount of from about 1 to about 20 parts by weight.

[0076] Aspect 10. The coating composition of any one of the preceding aspects, wherein the aerogel microspheres comprise trimethylated silica gel.

[0077] Aspect 11. The coating composition of any one of the preceding aspects wherein the aerogel microspheres have an average diameter of about 10 to about 60 pm.

[0078] Aspect 12. The coating composition of any one of the preceding aspects, wherein the ceramic microspheres comprise an alkali aluminosilicate ceramic. [0079] Aspect 13. The coating composition of any one of the preceding aspects wherein the ceramic microspheres have an average diameter of from about 10 to about 60 pm.

[0080] Aspect 14. The coating composition of any one of the preceding aspects, wherein the glass microspheres comprise soda-lime-borosilicate glass microspheres.

[0081] Aspect 15. The coating composition of any one of the preceding aspects wherein the glass microspheres have an average diameter of from about 10 to about 60 pm.

[0082] Aspect 16. The coating composition of any one of the preceding aspects, wherein the carrier comprises a water-based emulsion or a two-part epoxy resin.

[0083] Aspect 17. The coating composition of aspect 16, wherein the water-based emulsion comprises a polymeric emulsion, optionally wherein the polymeric emulsion is an acrylic emulsion

[0084] Aspect 18. The coating composition of aspect 16 or 17, wherein the water-based emulsion is self-crosslinking.

[0085] Aspect 19. The coating composition of any one of aspects 16-18, wherein the coating composition comprises a water-based emulsion and further comprises a coolant, a wetting agent, a defoamer, a coalescing aid, a rheology modifier, a solvent, or any combination thereof.

[0086] Aspect 20. The coating composition of aspect 19, wherein the coolant comprises ethylene glycol, propylene glycol, or any combination thereof.

[0087] Aspect 21. The coating composition of aspect 19 or 20, wherein the coolant is present in an amount of from about 0.1 to about 2.5 parts by weight.

[0088] Aspect 22. The coating composition of any one of aspects 19-21 , wherein the wetting agent comprises a surfactant, an alcohol, or any combination thereof.

[0089] Aspect 23. The coating composition of aspect 22 wherein the surfactant comprises an anionic surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, or any combination thereof.

[0090] Aspect 24. The coating composition of aspect 23, wherein the anionic surfactant comprises an alcohol phosphate, an alcohol phosphonate, an alkyl alkoxy carboxylate, an alkyl aryl sulfate, an alkyl aryl sulfonate, an alkyl carboxylate, an alkyl ether carboxylate, an alkyl ether sulfate, an alkyl ether sulfonate, an alkyl phosphate, an alkyl polyethoxy carboxylate, an alkyl polyglucoside, an alkyl polyglucoside sulfate, an alkyl polyglucoside sulfonate, an alkyl succinamate, an alkyl sulfate, an alkyl sulfonate, an aryl sulfate, an aryl sulfonate, a fatty tauride, an isethionate, an N-acyl taurate, a nonoxynol phosphate, an octoxynol phosphate, a sarcosinate, a sulfated fatty acid ester, a taurate, or any combination thereof.

[0091] Aspect 25. The coating composition of aspect 23, wherein the cationic surfactant comprises a quaternary ammonium salt.

[0092] Aspect 26. The coating composition of aspect 23, wherein the nonionic surfactant comprises an ethoxylated alcohol, polysorbate 20, polysorbate 80, or any combination thereof.

[0093] Aspect 27. The coating composition of aspect 23, wherein the zwitterionic surfactant comprises a lecithin, a hydroxysultaine, a betaine, a sulfobetaine, or any combination thereof.

[0094] Aspect 28. The coating composition of aspect 22, wherein the alcohol comprises butanediol, a hexane diol, propylene glycol, sorbitol, a hexane triol, glycerol, or any combination thereof.

[0095] Aspect 29. The coating composition of any one of aspects 22-28, wherein the wetting agent is present in an amount of from about 0.05 to about 1.5 parts by weight.

[0096] Aspect 30. The coating composition of any one of aspects 19-29, wherein the defoamer comprises nonyl phenol, ethoxylated nonyl phenol, tributyl phosphate, triisobutyl phosphate, polypropylene oxide, a hydrocarbon, a nonionic surfactant, or any combination thereof.

[0097] Aspect 31. The coating composition of any one of aspects 19-30, wherein the defoamer is present in an amount of from about 0.05 to about 2.0 parts by weight.

[0098] Aspect 32. The coating composition of any one of aspects 19-31 , wherein the coalescing aid comprises an ester alcohol, an ethylene glycol monoalkyl ether, or any combination thereof.

[0099] Aspect 33. The coating composition of any one of aspects 19-32, wherein the coalescing aid is present in an amount of from about 0.5 to about 5 parts by weight.

[0100] Aspect 34. The coating composition of any one of aspects 19-33, wherein the rheology modifier comprises an acid-containing acrylic emulsion, an alkali-swellable polysaccharide, a poly(acrylate), a poly(alkene), a poly(alkyl oxide), a poly(amide), a poly(carbonate), a poly(diene), a poly(ester), a poly(methacrylate), a poly(saccharide), a poly(siloxane), a poly(styrene), a poly(urethane), a poly(vinyl ether), a derivative thereof, a copolymer thereof, or any combination thereof.

[0101] Aspect 35. The coating composition of any one of aspects 19-34, wherein the rheology modifier is present in an amount of from about 0.1 to about 5 parts by weight. [0102] Aspect 36. The coating composition of any one of aspects 19-35, wherein the solvent comprises water.

[0103] Aspect 37. The coating composition of any one of aspects 19-36, wherein the solvent is present in an amount of from about 1 to about 30 parts by weight.

[0104] Aspect 38. The coating composition of any one of aspects 19-37, wherein the coating composition comprises a Zahn Cup #2 viscosity of from about 10 to about 70 seconds.

[0105] Aspect 39. The coating composition of any one of aspects 19-38, wherein the coating composition comprises a pH of from about 8 to about 10.

[0106] Aspect 40. The coating composition of aspect 16, wherein the coating composition comprises a two-part epoxy resin and further comprises a solvent, a curing agent, an alcohol, an emulsifier, a coupling agent, or any combination thereof.

[0107] Aspect 41. The coating composition of aspect 40, wherein the solvent comprises toluene, benzene, xylenes, diethyl ether, hexanes, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, or any combination thereof.

[0108] Aspect 42. The coating composition of aspect 40 or 41 , wherein the solvent is present in an amount of from about 5 to about 20 parts by weight.

[0109] Aspect 43. The coating composition of any one of aspects 40-42, wherein the curing agent comprises a monofunctional polyetheramine, a difunctional polyetheramine, a trifunctional polyetheramine, a cyclic aliphatic polyamine, a polyamidoamine, an imidazole or a salt thereof, a phenalkamine, a phenalkamide, or any combination thereof.

[0110] Aspect 44. The coating composition of aspect 43, wherein the difunctional polyetheramine has the formula , wherein x has an average value of about 2.5.

[0111] Aspect 45. The coating composition of any one of aspects 40-44, wherein the curing agent is present in an amount of from about 30 to about 70 parts by weight.

[0112] Aspect 46. The coating composition of any one of aspects 40-45, wherein the alcohol comprises benzyl alcohol, t-butyl alcohol, t-amyl alcohol, 1-heptanol, 1-octanol, 1-decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, cyclohexanol, or any combination thereof.

[0113] Aspect 47. The coating composition of any one of aspects 40-46, wherein the alcohol is present in an amount of from about 5 to about 10 parts by weight. [0114] Aspect 48. The coating composition of any one of aspects 40-47, wherein the emulsifier comprises a nonylphenol, a polyethylene glycol (PEG), a PEG stearate, a glycol stearate, an ethoxylated fatty acid, a C12-C24 fatty acid, a rosin acid, polyacrylic acid, a polyacrylate, an alkyl sulfonate, an alkyl benzyl sulfonates, an alkyl sulfate, an alkyl phosphonates, an alkyl phosphate, a phenolic resin, an organic sulfate, an organic sulfonate, an organic phosphate, an organic phosphonate, or any combination thereof.

[0115] Aspect 49. The coating composition of any one of aspects 40-48, wherein the emulsifier is present in an amount of from about 25 to about 50 parts by weight.

[0116] Aspect 50. The coating composition of any one of aspects 40-49, wherein the coupling agent comprises a silane-based coupling agent, a titanium-based coupling agent, a zirconium- based coupling agent, an aluminum-based coupling agent, or any combination thereof.

[0117] Aspect 51 . The coating composition of aspect 50, wherein the silane-based coupling agent comprises N(P-aminoethyl) y-aminopropyltrimethoxy-silane, 3-aminopropyl silane, N-(2- aminoethyl)-3-aminopropyl silane, vinyl silane, methyl silane, N-phenylaminopropyl silane, (N- phenylamino)methyl silane, N-(2-vinylbenzylaminoethyl)-3-aminopropyl substituted alkoxy silane, 3-aminopropyltrimethoxy silane, 3-aminopropyldimethoxy silane, 3-aminopropyltriethoxy silane, 3 -aminopropyldi ethoxy silane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N- (2-aminoethyl)-3-aminopropyldiethoxysilane, a hydrolysate thereof, an oligomer thereof, or any combination thereof.

[0118] Aspect 52. The coating composition of aspect 50, wherein the titanium-based coupling agent comprises isopropyl(N-ethylaminoethylamino)titanate, isopropyl triisostearoyl titanate, titanium di(dioctylpyrophosphate)oxyacetate, tetraisopropyl di(dioctylphosphite)titanate, and neoalkoxy tri(p-N-(P-aminoethyl)aminophenyl)titanate, or any combination thereof.

[0119] Aspect 53. The coating composition of aspect 50, wherein the zirconium-based coupling agent comprises Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxy tris(neodecanoyl) zirconate, neoalkoxy tris(dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris(ethylenediaminoethyl)zirconate, neoalkoxy tris(m-aminophenyl)zirconate, ammonium zirconium carbonate, or any combination thereof.

[0120] Aspect 54. The coating composition of aspect 50, wherein the aluminum-based coupling agent comprises Al-acetylacetonate, Al-methacrylate, Al-propionate, or any combination thereof. [0121] Aspect 55. The coating composition of any one of aspects 40-54, wherein the coupling agent is present in an amount of from about 0.5 to about 5 parts by weight.

[0122] Aspect 56. The coating composition of any one of the preceding aspects, wherein the biocide comprises ammonia, a primary amine, a secondary amine, a tertiary amine, chlorhexidine, a biguanide, an acid amide, a peroxide, dibromopropamidine, tetrakis(hydroxymethyl)phosphonium, guanidine, ortho-phenyl phenol, dodecyl gallate, a salt thereof, or any combination thereof.

[0123] Aspect 57. The coating composition of any one of the preceding aspects, wherein the biocide is present in an amount of from about 0.5 parts by weight to about 5 parts by weight.

[0124] Aspect 58. The coating composition of any one of the preceding aspects, wherein the filler comprises calcium carbonate, ammonium polyphosphate, pentaerythritol, aluminum hydroxide, melamine, or any combination thereof.

[0125] Aspect 59. The coating composition of any one of the preceding aspects, wherein the filler is present in an amount of from about 10 to about 40 parts by weight.

[0126] Aspect 60. A method for making a coating composition, the method comprising:

(a) admixing a microsphere composition and a pigment in water to form a first composition;

(b) admixing a water-based emulsion with the first composition to form the coating composition.

[0127] Aspect 61. The method of aspect 60, wherein the microsphere composition comprises aerogel microspheres, ceramic microspheres, glass microspheres, or any combination thereof.

[0128] Aspect 62. The method of aspect 60 or 61 , wherein the pigment comprises titanium dioxide, a fluorescent pigment, an infrared reflective pigment, or any combination thereof.

[0129] Aspect 63. The method of any one of aspects 60-62, further comprising admixing a coolant, a biocide, or any combination thereof, into the first composition in step (a).

[0130] Aspect 64. The method of any one of aspects 60-63, further comprising admixing water, a wetting agent, a defoamer, a coalescing aid, a rheology modifier, a biocide, or any combination thereof with the first composition in step (b).

[0131] Aspect 65. A method for making a coating composition, the method comprising: (a) admixing one or more first epoxy resin components and a microsphere composition to form a first epoxy part, wherein the microsphere composition comprises aerogel microspheres, ceramic microspheres, and glass microspheres;

(b) providing a second epoxy part comprising one or more second epoxy resin components; and

(c) admixing the first epoxy part and the second epoxy part to form the coating composition.

[0132] Aspect 66. The method of aspect 65, further comprising admixing a solvent, an alcohol, a biocide, or any combination thereof into the first epoxy part in step (a).

[0133] Aspect 67. The method of aspect 65 or 66, further comprising admixing a curing agent, an alcohol, an emulsifier, a coupling agent, a biocide, or any combination thereof into the second epoxy part in step (b).

[0134] Aspect 68. A coating composition made by the method of any one of aspects 60-67.

[0135] Aspect 69. A method for applying the coating composition of any one of aspects 1-59 or 68 to a substrate, the method comprising spray coating, roll coating, dip coating, or flow coating the composition onto the substrate.

[0136] Aspect 70. The method of aspect 69, wherein the substrate comprises an exterior surface of a building, an interior surface of a building, a pipe, a boiler, a hospital surface, a kitchen surface, a marine surface, or a surface on industrial equipment.

[0137] Aspect 71. The method of aspect 70, wherein the exterior surface of the building comprises an external wall, cladding, window frame, or roof.

[0138] Aspect 72. The method of aspect 70, wherein the interior surface of the building comprises a wall, ceiling, interior window frame, window attachment, flooring, or another surface.

[0139] Aspect 73. The method of aspect 72, wherein the roof comprises a galvanized steel roof or an aluminum roof.

[0140] Aspect 74. A coating comprising the coating composition of any one of the aspects 1-59 or 68.

[0141] Aspect 75. The coating of aspect 74, wherein the coating has a thickness of from about 0.05 mm to about 2 mm. [0142] Aspect 76. The coating of aspect 74 or 75, wherein the coating has one or more beneficial properties selected from high reflectivity, thermal insulation, low conductivity, hydrophobicity, antimicrobial properties, anti-corrosive properties, fire resistance, low heat transfer coefficient, high elasticity, and combinations thereof.

[0143] Aspect 77. A substrate comprising the coating of any one of aspects 74-76.

[0144] Aspect 78. The substrate of aspect 77, wherein the substrate comprises an exterior surface of a building, an interior surface of a building, a pipe, a boiler, a hospital surface, a kitchen surface, a marine surface, or a surface on industrial equipment.

[0145] Aspect 79. The substrate of aspect 78, wherein the exterior surface of a building comprises a metal roof.

[0146] Aspect 80. The substrate of aspect 79, wherein the metal roof has a gauge of from about 20 to about 29.

[0147] Aspect 81. The substrate of any one of aspects 77-80, wherein the substrate has a conductivity at least 10% lower than a comparable roof without the coating.

[0148] Aspect 82. The substrate of any one of aspects 77-81 , wherein the substrate has a conductivity of from about 45 to about 60 W/m-K.

[0149] Aspect 83. The substrate of any one of aspects 77-82, wherein the substrate has an electrical resistance at least 25% lower than a comparable roof without the coating.

[0150] Aspect 84. The substrate of any one of aspects 77-83, wherein the substrate has an electrical resistance of from about 1.1 x 10-4 to about 1.5 x 10-4 m2-K/W.

EXAMPLES

[0151] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. Example 1: Water-Based Coating and Method of Making

[0152] A water-based coating composition was prepared as follows. The components in Table 1 were mixed in the order listed and mixed at slow speed until homogeneous.

[0153] The components in Table 2 were slowly added to the mixture on top of the aqueous solution while mixing.

[0154] The components in Table 3 were pre-mixed and slowly added to the composition from Table 2 to adjust viscosity.

[0155] The final product had a Zahn Cup #2 viscosity of 12-18 seconds and a pH of between 8.5 and 9.5.

Example 2: Epoxy-Based Coating and Method of Making

[0156] Part A of the epoxy-based coating was prepared from the components in Table 4. Components were mixed for 30 minutes at low speed and then the microsphere composition was added slowly while mixing for another 30-45 minutes.

[0157] Part B of the epoxy-based coating was prepared from the components in Table 5.

Components were mixed at slow speed for 60 minutes.

[0158] Part A and Part B were mixed in a 1 :1 ratio to prepare a two-part epoxy-based coating according to the present disclosure.

Example 3: Predicted Properties of Exemplary Coatings

[0159] An exemplary paint according to the present disclosure is expected to impart the properties shown in Table 6 to a 24 gauge galvanized steel roof:

[0160] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the abovedescribed embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.