Method of making a trashcan with an antimicrobial coating

Information

  • Patent Grant
  • 12145795
  • Patent Number
    12,145,795
  • Date Filed
    Tuesday, August 1, 2023
    a year ago
  • Date Issued
    Tuesday, November 19, 2024
    3 days ago
Abstract
Various trashcans, their coatings, and coatings for other household goods are disclosed. In certain implementations, the disclosed coatings are antimicrobial. Various methods for forming antimicrobial coatings for household goods are also disclosed. In some embodiments, the antimicrobial coating comprises a substrate and an antimicrobial agent. In certain implementations the coating can be applied to a household good where the coating leaves a substantially streak-free finish. Some embodiments pertain to protective films that can be removed from a coated household good without leaving residue.
Description
BACKGROUND
Field

The disclosure relates generally to the field of household goods with antimicrobial coatings and methods of making the same.


Description of the Related Art

Household goods and/or their components comprise surfaces that can be exposed to contaminants during use. For example, trashcans are often exposed to raw meat, food stuffs, and other forms of garbage. Soap dispensers are exposed to users' soiled hands. This exposure to contaminants can lead to bacterial and other microbial build-up and growth.


SUMMARY

Certain embodiments disclosed herein pertain to a coating for a household good. In some embodiments, the coating comprises a polymeric substrate configured to adhere to a surface of the household good. In some embodiments, the coating comprises an antimicrobial agent dispersed on or within the substrate.


Any of the embodiments described above, or described elsewhere herein, can include one or more of the following features.


In some embodiments, the antimicrobial agent comprises a zeolite. In some embodiments, the antimicrobial agent comprises ionic silver. In some embodiments, the antimicrobial agent comprises ionic copper. In some embodiments, the antimicrobial agent comprises ammonium.


In some embodiments, the antimicrobial agent comprises at least about 2% and/or less than or equal to about 5% weight percent of the substrate. In some embodiments, the antimicrobial agent comprises equal to or at least about 2% and/or less than or equal to about 5% ionic silver by weight. In some embodiments, antimicrobial agent comprises equal to or at least about 4.0% and/or less than or equal to about 7.0% ionic copper by weight. In some embodiments, the antimicrobial agent comprises equal to or at least about 0.1% and/or less than or equal to about 2.0% ammonium by weight. In some embodiments, the antimicrobial agent comprises a zeolite having antimicrobial ions adhered to, deposited on, or diffused therein. In some embodiments, the antimicrobial agent comprises AGION®. In some embodiments, the antimicrobial agent is present in an amount of about 1.25 wt % relative to the substrate.


In some embodiments, the polymeric substrate comprises polyethylene. In some embodiments, the polymeric substrate comprises a material that resists or makes it easier to wipe away fingerprints and smudges.


In some embodiments, the coating is sufficiently durable so that it can withstand repeated cleanings or washings without losing its antimicrobial properties.


Some embodiments pertain to a coating for a household good comprising a polymeric substrate configured to adhere to a surface of the household good and an antimicrobial agent or a combination of antimicrobial agents dispersed on or within the substrate, such as wherein the one or more antimicrobial agents comprise one or more of a zeolite, ionic silver, ionic copper, or ammonium. In some embodiments, the coating is the antimicrobial agent.


In some embodiments, the polymeric substrate comprises polyethylene.


In some embodiments, the coating comprises equal to or greater than about 0.1% and/or less than or equal to about 1.5% antimicrobial agent by weight.


In some embodiments, the antimicrobial agent comprises equal to or greater than about 68% and/or less than or equal to about 94% zeolite by weight. In some embodiments, the antimicrobial agent comprises equal to or greater than about 2% and/or less than or equal to about 5% ionic silver by weight. In some embodiments, the antimicrobial agent comprises equal to or greater than about 4.0% and/or less than or equal to about 7.0% ionic copper by weight. In some embodiments, the antimicrobial agent comprises equal to or greater than about 0.1% and/or less than or equal to about 2.0% an ammonium ion (or ammonium salt) by weight. In some embodiments, the antimicrobial agent comprises AGION®. In some embodiments, the antimicrobial agent is present in an amount of about 1.25 wt % relative to the substrate.


In some embodiments, the polymeric substrate comprises a material that resists or makes it easier to wipe away fingerprints and smudges. In some embodiments, the coating is sufficiently durable so that it can withstand repeated cleanings or washings without losing its antimicrobial properties.


Some embodiments pertain to a metal sheet comprising a coating that includes any one or more of the features described above.


Some embodiments pertain to a household product, such as a trashcan comprising a coating that includes any one or more of the features described in this specification. In some embodiments, the coating is located to the outside surface of the trashcan. In some embodiments, the trashcan comprises a metal body, the coating being located on the metal body.


Some embodiments pertain to a trashcan comprising a metal body, a lid coupled to the body and configured to move between open and closed positions, and a base on which the metal body is configured to rest. In some embodiments, an outside surface of the metal body comprises a coating, the coating comprising a substrate with an antimicrobial agent dispersed on or within the substrate, the antimicrobial agent comprising silver ions. In some embodiments, the coating is substantially even or homogeneous in thickness and/or composition and/or reflectivity across the surface of the substrate. For example, the coating can be substantially streak-free.


In some embodiments, the antimicrobial agent comprises a zeolite. In some embodiments, the substrate comprises polyethylene. In some embodiments, the antimicrobial agent comprises ionic copper. In some embodiments, the antimicrobial agent comprises ammonium. In some embodiments, the coating reduces an amount of bacteria of about 9.5×106 colony forming units (CFU)/carrier on the coating to less than about 5 CFU/carrier on the coating over a period of about 24 hours. In some embodiments, the coating reduces an amount of E. coli from about 2.3×105 CFU/carrier to less than about 5 CFU/carrier on the coating over a period of about 24 hours.


Some embodiments pertain to a trashcan comprising a metal body forming at least a portion of a container configured to receive refuse. In some embodiments, an outside surface of the metal body comprises a coating. In some embodiments, the coating comprises a substrate with an antimicrobial agent dispersed on or within the substrate. In some embodiments, the coating is substantially even or homogeneous in thickness and/or composition and/or reflectivity across the surface of the substrate. For example, the coating can be substantially streak-free.


In some embodiments, the antimicrobial agent comprises one or more of a zeolite, ionic silver, ionic copper, or ammonium. In some embodiments, the antimicrobial agent comprises a zeolite having antimicrobial ions adhered to, deposited on, or diffused therein. In some embodiments, the antimicrobial agent comprises AGION®.


In some embodiments, the substrate comprises polyethylene.


In some embodiments, the coating is applied to a metal sheet used to prepare the metal body by applying a slurry comprising a solvent, a substrate material, and the antimicrobial agent to the metal sheet using a reverse-rolling device.


In some embodiments, the coating comprises a fingerprint resistant material or a material that allows fingerprints to be easily removed, such as by wiping without requiring a solution or excessive or forceful rubbing of the surface where the fingerprint is made.


In some embodiments, about 24 hours after bacterial exposure on the coating, an amount of bacteria remaining on the coating is at least about 95% less than upon initial exposure. In some embodiments, about 24 hours after bacterial exposure on the coating, an amount of bacteria remaining on the coating is at least about 99.99% less than upon initial exposure. In some embodiments, about 24 hours after bacterial exposure on the coating, an amount of bacteria remaining on the coating is reduced by about 95% to about 100%. In some embodiments, the coating reduces an amount of E. coli from about 2.3×105 CFU/50 mm×mm carrier to less than or equal to about 5 CFU/carrier over a period of about 24 hours. In some embodiments, the coating reduces an amount of S. aureus from about 3.85×105 CFU/mm×50 mm carrier to less than or equal to about 5 CFU/carrier over a period of about 24 hours.


Some embodiments pertain to methods of coating a metal surface. In some embodiments, the method of coating a metal surface comprises obtaining a solution of a polymer substrate in solvent. In some embodiments, the method comprises dispersing an antimicrobial agent on or within the solution forming a mixture. In some embodiments, the method comprises agitating the mixture to form a substantially uniform slurry. In some embodiments, the method comprises obtaining a sheet of material. In some embodiments, the method comprises applying the slurry onto the sheet of material as a layer. In some embodiments, the method comprises curing the slurry on the sheet to provide a coated sheet. In some embodiments, the resultant coated metal sheet is substantially streak-free. Some embodiments pertain to a method of manufacturing a metallic sheet having an antimicrobial coating. In some embodiments, the method comprises providing a metallic sheet. In some embodiments, the method comprises applying a slurry comprising an antimicrobial agent and a solvent onto the metallic sheet. In some embodiments, the method comprises drying the slurry on the metallic sheet to provide the antimicrobial coating. In some embodiments, the metallic sheet is shaped to provide a portion of a surface of a household good. In some embodiments, the slurry is applied to the metallic sheet using a reverse-rolling device.


In some embodiments, the method comprises applying an acrylic and/or silicone and/or silicone rubber adhesive over the coated portion of the coated metal sheet and thereafter applying a protective film over such adhesive on the coated metal sheet.


In some embodiments, the antibacterial agent used in the method comprises a zeolite (and/or any one of ionic silver, ionic copper, or ammonium).


Some embodiments pertain to a metal sheet comprising a coating, layer, and/or sheet. In some embodiments, the coating comprises a polymeric substrate configured to adhere to a surface of the household good. In some embodiments, the coating comprises an antimicrobial agent dispersed on or within the substrate. In some embodiments, the coating is an antimicrobial agent. In some embodiments, the coating comprises a protective film that protects the coating from abrasions during shipment of the metal sheet. In some embodiments, the coating comprises an acrylic and/or silicone and/or silicone rubber adhesive that adheres the protective film to the coating. In some embodiments, the adhesive leaves substantially no residue on the coating after removal of the protective film.


Some embodiments pertain to a coating for a household good comprising a coating comprising an antimicrobial agent. In some embodiments, the coating further comprises a fingerprint resistant agent, such as an agent that resists the formation of visible fingerprints and/or that an agent that allows fingerprints to be easily removed. In some embodiments, the coating is applied to a surface of a household good. Any feature, structure, component, or step that is described and/or illustrated in any embodiment in this specification can be used with or instead of any feature, structure, component, or step that is described and/or illustrated in any other embodiment in this specification. Everything disclosed and/or illustrated in this specification is intended to be interchangeable and combinable.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 illustrates a trashcan having an antimicrobial coating.



FIG. 2 is front view of the trashcan of the FIG. 1 and a close-up, cross-sectional view of a portion of the trashcan.



FIGS. 3A-B are photographs of sheets of material comprising one or more coatings containing an antimicrobial agent.



FIGS. 4A-B are close-up views of portions of the photographs of FIGS. 3A-B.



FIG. 5 is a graph showing Escherichia coli growth on uncoated versus coated metal sheets.



FIG. 6 is a graph showing Staphylococcus aureus growth on uncoated versus coated metal sheets.



FIG. 7 is a flow chart showing a process of preparing an antimicrobial coating on a metal sheet.



FIG. 8 illustrates diagram of a sheet being coated using a reverse-rolling process.



FIG. 9 is a flow chart showing a process of protecting an antimicrobial coating on a metal sheet.



FIGS. 10A-B are photographs of partially removed protective films applied to sheets of material comprising coatings containing an antimicrobial agent.





DETAILED DESCRIPTION OF SOME EMBODIMENTS

A variety of antimicrobial coatings and methods of forming and using the same are described below to illustrate various examples that may be employed to achieve one or more desired improvements. These examples are only illustrative and not intended in any way to restrict the general inventions presented and the various aspects and features of these inventions. Furthermore, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. No features, structure, or step disclosed herein is essential or indispensable.


Overview

Some embodiments disclosed herein pertain to a coating for a household good. In certain implementations, the coating is antimicrobial. As used herein, the term “antimicrobial,” and its derivatives, describes the property of killing microbes and/or preventing or slowing microbial growth. As used herein, the term “microbe,” and its derivatives, means an organism that is too small to be seen by the unaided eye, such as various bacteria, archaea, fungi, and protists.


As will be described in more detail below, in some embodiments, the coating comprises a substrate and an antimicrobial agent distributed in that substrate. In certain embodiments, the coating is applied to a metal (e.g., stainless steel or aluminum), which is formed into a portion of a household product (e.g., a trashcan). In some variants, the coating comprises the antimicrobial agent, substrate, and a compound that facilitates avoiding or wiping-off fingerprints. Such a combined coating can be applied to a surface (e.g., a metal sheet), which can be formed into a portion of a household product.


As shown in FIGS. 1 and 2, certain embodiments are disclosed herein in the context of a coating 120 for a trashcan 100 comprising sheet metal 110, as the coating may have particular utility in this context. However, the various aspects of the present disclosure can be used on sheet goods generally and for other household goods having metal or non-metal components. For example, some illustrative household goods are: soap dispensers, minors (e.g. metal trim on minors, stands, etc.), soap dishes, grocery bag dispensers, shower/sink caddies, utensil holders, organizers (e.g., for drawers or countertops), paper towel holders, dishracks, wall mount liquid pumps (e.g., for soap, shampoo, etc.), toilet plunger handles, appliance handles (e.g., for microwaves, refrigerators, dishwashers, ovens, coffee makers, etc.), appliances (e.g., refrigerators, microwaves, dishwashers, ovens, blenders, coffee makers, trash compactors, BBQ grills, etc.), sink accessories (e.g., handles, faucets, etc.), liquid dispensers (e.g., for drinkables), washers, driers, components for the same, and the like. In some variants, the coating is applied to the handles, trim, or removable inner buckets of trashcans (e.g., removable inserts that fit within a larger trashcan body). In some embodiments, the coatings described herein can be applied to handheld devices or touchscreens.


In some embodiments, the household good is broadly a metal good. In some variants, the household good comprises stainless steel. In some embodiments, the metal of the household good comprises one or more of stainless steel, brass, copper, steel, aluminum, iron, platinum, gold, silver, zinc, other metals, metal alloys of the same, and the like. In certain embodiments, the household good is made of a nonmetal material (e.g., plastic, glass, etc.) and/or a composite material.


In certain variants, the coating is configured to adhere to one or more surfaces of the household good. In some implementations, the coating is applied to a material sheet surface used to make a household good. For example, as discussed in more detail below, the coating can be applied to a sheet of metal that is subsequently formed into a portion of the household good, such as the body and/or lid of a trashcan. In some variants, for example, the coating can be applied to the inside and outside surfaces of the household good (e.g., both sides of a stainless steel sheet used to prepare a trashcan). In certain variants, the coating is applied to only select surfaces of the household good. For example, in some implementations, the coating is applied only to the outside of the household good, (e.g., trashcan, etc.). In other variants, the coating is applied only to the inside of the household good (e.g., trashcan, etc.). In some embodiments, the coating is applied to one or more of the inside, outside, lid, handle, or pedal of the household good (e.g., trashcan, etc.).


In some variants, the coatings and methods of coating materials described herein increase and/or maximize antimicrobial effects of an antimicrobial agent in the coating without substantially affecting the appearance of the household good. For example, in some embodiments, the antimicrobial coating is smooth and uniform without visible streaking and/or is clear (or substantially clear). In some embodiments, the antimicrobial coating is substantially smooth and/or substantially uniform and/or substantially even or consistent in reflectivity across a particular surface of the coating or a particular portion of a surface of the coating, without substantial visible streaking and/or is clear (or substantially clear). FIGS. 3A-B and 4A-B shows side-by-side examples of an antimicrobial coating that are streaked or smooth and uniform without visible streaking. For instance, the coatings of FIGS. 3B and 4B are substantially streak-free, while those of FIGS. 3A and 4A are not. In certain implementations, the antimicrobial coating shows unobstructed views of the surfaces underneath the coating, such as the top of the surface to which the coating is applied. In certain implementations, the coating is colorless or substantially colorless. In some implementations, the coating has a blue tint.


In certain implementations, the coating is generally planar and/or substantially flat. In some embodiments, the coating is substantially uniform and/or smooth. In some variants, the coating is generally contiguous. In some embodiments, the aforementioned properties of the coating make it appear substantially streak-free where streaks are not generally visible upon casual visual observation.


Certain Substrates

In certain implementations, as disclosed above, the coating comprises a substrate and one or more antimicrobial agents. In certain implementations, the antimicrobial is dispersed under, within (e.g., homogenously throughout the substrate or as a gradient), or on the substrate (e.g., adhered and/or functionalized to the substrate surface). In some embodiments, the substrate is any material that provides a support for the antimicrobial agent while allowing access to the antimicrobial agent by bacteria or other microbes that come into contact with the coating. In some implementations, the substrate is substantially clear (e.g., selected to be substantially optically transparent to the naked eye).


In certain implementations, the substrate comprises a polymeric material. For example, the substrate can comprises polyethylene. In some variants, the substrate comprises a mixture of more than one polymeric material.


While polymeric substrates are described here, any other matrices could be used, keeping in mind that the goal of the substrate (i.e., the matrix, the support, etc.) is, in some embodiments, to provide a material that is capable of supporting an antimicrobial agent while adhering to a household good in a manner that does not substantially distort the appearance of that good. For example, in some embodiments, the substrate comprises a crosslinkable polymer matrix or copolymer matrix.


In some embodiments, the substrate itself is formulated using one or more polymers that themselves have antimicrobial effects. For example, in certain implementations, the substrate comprises a polymeric material comprising one or more polymeric antimicrobial materials, such as polyethyleneimine, NIPAM, or other cationic or polycationic polymers.


Certain Antimicrobial Agents

Some embodiments pertain to an antimicrobial agent bound to a surface (e.g., a metal portion) of a household good. In some embodiments, the antimicrobial is adhered to the surface of a household good via a substrate as described elsewhere herein. In some embodiments, the substrate and antimicrobial agent form a coating. In certain embodiments, the antimicrobial agent itself provides a coating and/or is the coating on the household good. In certain implementations, as described above and as shown in FIG. 2, the coating comprises an antimicrobial agent 220 dispersed within a substrate 210. In certain implementations, as shown in the expanded cross-sectional view of FIG. 2, at least a portion of the antimicrobial agent 220 is exposed on the outside surface of the coating 120. In some variants, the antimicrobial agent 220 is able to directly contact microbes that are on the surface of the coating 120 because the antimicrobial agent 220 escapes and/or protrudes from (e.g., is sticking out of) the substrate 210. In some embodiments, the antimicrobial agent can diffuse over time to the surface of the coating to interact directly with microbes on the surface of the household good.


In some embodiments, the antimicrobial agent comprises an antimicrobial zeolite. In some embodiments, the antimicrobial zeolite comprises one or more antimicrobial metal ions, antimicrobial metals, or antimicrobial organic ions. In some embodiments, the antimicrobial agent and/or antimicrobial zeolite comprises water. For instance, in some embodiments, where the antimicrobial agent comprises a zeolite, some portion of water can be trapped in or adhered to the zeolite. In some embodiments, the antimicrobial zeolite or antimicrobial agent comprises one or more of ionic silver, ionic copper or copper metal, or ammonium. In some embodiments, the antimicrobial zeolite and/or the antimicrobial agent comprises each of silver ions, copper (ionic or metallic), and ammonium. In some embodiments, the antimicrobial agent comprises AGION®, available from Sciessent LLC of Wakefield, Massachusetts. In some embodiments, the weight percent of zeolite (e.g., an aluminosilicate portion of the zeolite without water, antimicrobial anions, or antimicrobial organic cations) in the antimicrobial zeolite and/or the antimicrobial agent is equal to or greater than about 68% and/or less than or equal to about 94%. In some embodiments, the weight percent of zeolite in the antimicrobial agent and/or antimicrobial zeolite is equal to or at least: about 60%, about 65%, about 70%, about 80%, about 90%, about 95%, about 99%, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, the weight percent of zeolite in the antimicrobial agent and/or antimicrobial zeolite is less than or equal to: about 99%, about 95%, about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, the antimicrobial agent comprises one or more antimicrobial zeolites and/or other antimicrobial entities (e.g., silver ions, ionic copper, ammonium, etc.).


In some embodiments, ionic silver can be present in an amount equal to or greater than about 2% and/or less than or equal to about 5% by weight of the antimicrobial zeolite and/or by weight of the antimicrobial agent. In some embodiments, the weight percent of ionic silver in the antimicrobial zeolite (and/or in the antimicrobial agent) is equal to or greater than at least: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, the weight percent of ionic silver in the antimicrobial zeolite (and/or in the antimicrobial agent) is less than or equal to: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, values between the aforementioned values, ranges spanning those values, or otherwise.


In some variants, ionic copper or copper metal can be present in an amount equal to or greater than about 4% and/or less than or equal to about 7% by weight of the antimicrobial zeolite (and/or by weight of the antimicrobial agent). In some embodiments, the weight percent of ionic copper or copper metal in the antimicrobial zeolite (and/or in the antimicrobial agent) is equal to or at least: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, the weight percent of ionic copper or copper metal in the antimicrobial zeolite (and/or in the antimicrobial agent) is less than or equal to: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, values between the aforementioned values, ranges spanning those values, or otherwise.


In various embodiments, ammonium can be present in an amount equal to or greater than about 0% and/or less than or equal to about 2% by weight of the antimicrobial zeolite (and/or in the antimicrobial agent). In some embodiments, the weight percent of ammonium in the antimicrobial zeolite (and/or in the antimicrobial agent) is equal to or at least: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, weight percent of ammonium in the antimicrobial zeolite (and/or in the antimicrobial agent) is less than or equal to: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, values between the aforementioned values, ranges spanning those values, or otherwise.


In some embodiments, the antimicrobial agent comprises water. For instance, zeolites can also be hygroscopic and can naturally absorb water from the environment. In some embodiments, water can be present in an amount equal to or greater than about 0% to less than or equal to about 18% by weight of the antimicrobial zeolite (and/or of the antimicrobial agent). In some embodiments, the weight percent of water in the antimicrobial zeolite (and/or the antimicrobial agent) is equal to or at least: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, about 15.0%, about 20.0%, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, the weight percent of water in the antimicrobial zeolite (and/or in the antimicrobial agent) is less than or equal to: about 0.5%, about 1.0%, about 2.0%, about 3.0%, about 4.0%, about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, about 15.0%, about 20.0%, values between the aforementioned values, ranges spanning those values, or otherwise. In certain implementations, the antimicrobial zeolite comprises about 18% water by weight (“AC10N”), about 5% water by weight (“AC10D”), or about 2% water by weight (“AC10H”).


In some embodiments, one or more antimicrobial agents are supported by a sub-support structure that, by itself, may or may not be antimicrobial. For instance, in some embodiments, one or more antimicrobial agents are supported on a nanoparticle (e.g., a particle with an average particle sizes ranging from equal to or greater than about 10 nm to less than or equal to about 1000 nm) or microparticle (e.g., a particle with an average particle sizes ranging from equal to or greater than about 1 μm to less than or equal to about 1000 μm). In some embodiments, the sub-support comprises a zeolite. In some embodiments, the sub-support structure can comprise any one of ionic silver, ionic copper, ammonium, and/or water in any of the weight percentages described elsewhere herein. In some embodiments, as described above, the antimicrobial agent comprises a zeolite sub-support with one or more antimicrobial ions adhered to it (or diffused within it). In some embodiments, the average particle size of the zeolite (or other sub-support structure) is equal to or less than: about 100 μm, about 10 μm, about 1 μm, values ranging between the aforementioned values, values between the aforementioned values or otherwise. In some embodiments, the average particle size of the zeolites (and/or other sub-support structure) is less than about 6 μm.


In some variants, the antimicrobial agent lacks a zeolite (e.g., a zeolite sub-support structure) or other sub-support structure and instead comprises one or more of free silver (e.g., silver ions, a silver salt, metallic, etc.), copper (copper ions, a copper salt, or metallic copper, etc.), organosilanes, ammonium, or cationic materials (e.g., 3-(trimethoxy silyl)-propyldimethyloctadecyl ammonium chloride, etc.) that provide antimicrobial effect. For instance, in some embodiments, the coating comprises silver ions.


In some embodiments, the substrate that supports the antimicrobial agent comprises the bulk dry weight of the coating. In some embodiments, the antimicrobial agent makes up equal to or less than about 1.25 wt % (i.e., weight percent) of the total coating weight. In some embodiments, the coating comprises equal to or greater than about 0.1% and/or less than or equal to about 1.5% antimicrobial agent by weight. In some embodiments, the coating comprises equal to or greater than about 1.1% and/or less than or equal to about 1.3% antimicrobial agent by weight. In some embodiments, the coating comprises equal to or greater than about 1.1% and/or less than or equal to about 1.2% antimicrobial agent by weight. In some embodiments, the weight percent of antimicrobial agent in the coating is at least: about 0.0001%, about 0.001%, about 0.01%, about 0.1%, about 0.5%, about 1.0%, about 1.25, about 1.5%, about 2.0%, values between the aforementioned values, values greater than the aforementioned values, values less than the aforementioned, or otherwise. In some embodiments, the weight percent of the antimicrobial agent in the sub-support is less than or equal to: about 0.0001%, about 0.001%, about 0.01%, about 0.1%, about 0.5%, about 1.0%, about 1.25, about 1.5%, about 2.0%, values between the aforementioned values, ranges spanning those values, or otherwise.


As described below in Examples 2 and 3, and as shown in FIGS. 5 and 6, the antimicrobial coating kills substantially all of the bacteria present on the coating after a period of about 24 hours of exposure to the coating. As shown in the Escherichia coli (E. coli) results from Example 2 (and FIG. 5), both coatings comprising about 1.25 wt % AGION® or about 1.5 wt % AGION® kill substantially all of the E. coli present on the coating after a period of about 24 hours of exposure to the coating. As shown in the Staphylococcus aureus (“S. aureus”) results from Example 2 (and as shown in FIG. 6), the coating comprising about 1.25 wt % AGION® kills this form of bacteria slightly more effectively than the about 1.5 wt % AGION® coating after a period of about 24 hours of exposure to the coating. This result surprisingly shows that a lower amount of AGION® can be used to achieve a nearly 100% kill rate relatively to larger doses. Without being bound to any particular mechanism, it is thought that the lower dose of AGION® (e.g., 1.25 wt % or less) allows it to be better distributed within the coating layer (e.g., by preventing aggregation) giving it a more efficient and effective antibacterial effect.


In embodiments, where the antimicrobial agent is provided without a sub-support structure (e.g., free of the zeolite), the weight % of antimicrobial agent in the coating can be reduced to account for the lack of this sub-support.


In some embodiments, about 24 hours after bacterial exposure on the coating, an amount of bacteria remaining on the coating is reduced by equal to or at least about 95% to about 100%. In some embodiments, 24 hours after bacterial exposure on the antibacterial coating, the amount of bacteria present is reduced by equal to or at least: about 75%, about 85%, about 95%, about 98%, about 99%, about 99.9%, about 99.99%, about 99.999%, about 99.9999%, or about 99.99999%. In some embodiments, the coating reduces the amount of E. coli from about 2.3×105 CFU/carrier to about 0 CFU/carrier and/or less than or equal to about 5 CFU/carrier (with a limit of detection of about 5 CFU/carrier) over a period of about 24 hours. In some embodiments, as shown in Table 1, relative to a control, the coating reduces the amount of bacteria from about 2.35×107 colony forming units (CFU)/carrier (on a control surface) to about 0 CFU/carrier and/or less than or equal to about 5 CFU/carrier (with a limit of detection of about 5 CFU/carrier) over a period of about 24 hours. In some embodiments, the coating reduces the amount of S. aureus from about 3.85×105 CFU/carrier to about 0 CFU/carrier and/or less than or equal to about 5 CFU/carrier (with a limit of detection of about 5 CFU/carrier) over a period of about 24 hours. In some embodiments, as shown in Table 2, relative to a control, the coating reduces the amount of bacteria from about 9.5×106 colony forming units (CFU)/carrier (on a control surface) to about 0 CFU/carrier and/or less than or equal to about 5 CFU/carrier (with a limit of detection of about 5 CFU/carrier) over a period of about 24 hours. In some embodiments, the coating has the above described antimicrobial effects on one or more bacteria selected from Streptococcus pneumoniae, Haemophilus influenzae, Moraxella catarrhalis, S. aureus, E. coli, or the like. In some embodiments, the coating has antimicrobial effects on gram positive and/or gram negative bacteria.


Features of Certain Antimicrobial Coatings

As described above, the antimicrobial coating can be applied to household goods. In some embodiments, the coating is sufficiently durable for long-term use (e.g., is able to maintain integrity and substantially unreduced efficacy over a period of at least one year with regular and normal usage). In some variants, the look of the household good remains substantially unchanged and/or the antimicrobial properties remain substantially unchanged during long term use (e.g., for periods of one, two, three, four or more years as could be measured over time or with accelerated stress conditions).


In some embodiments, the coating is sufficiently durable to withstand repeated cleanings or washings. For instance, because household goods such as trashcans and sink accessories are typically washed repeatedly over their lifetimes, in certain variants, the coating is configured to maintain its antimicrobial properties after repeated cleanings that include scrubbing and washing with soapy water. In some embodiments, a durable coating maintains its antimicrobial properties after at least about 25, at least about 50, at least about 100, or more washes with a standard wash cloth and soapy water. In certain variants, the coating maintains its antimicrobial activity after at least about 25, at least about 50, at least about 100, or more washes with a paper towel and a household cleaner (e.g., bleach, an ammonia-based cleaner (e.g., WINDEX® cleaner), etc.).


In some variants, the coating maintains its antimicrobial properties under accelerated wear conditions (e.g., under heat stress, increased humidity, exposure simulated sunlight, etc.) intended to simulate the lifetime of the good. In some embodiments, the coating maintains its antimicrobial properties after being abraded (e.g., abrasions or scratches caused by steel wool or other abrading agents). In some variants, the coating maintains its antimicrobial properties after about 1000 wipes using a dry kimwipe. In some embodiments, a product that maintains its antimicrobial properties includes products that retain at least about 75%, at least about 85%, at least about 90%, at least about 95%, at least about 99%, or more of its initial antimicrobial property before use.


In some embodiments, the durability of the coating can be measured using the contact angle of a droplet of water or oil on the coating surface. In certain variants, the contact angle of a droplet of water on the coating changes less than about 10% under one or more of the washing and wear conditions described above. In some embodiments, the contact angle of a droplet of water on the coating changes less than about 20% and/or less than about 40% under one or more of the washing and wear conditions described above. In some embodiments, the contact angle of a droplet of oil on the coating changes less than about 10% under one or more of the washing and wear conditions described above. In some embodiments, the contact angle of a droplet of oil on the coating changes less than about 20% or less than about 40% under one or more of the washing and wear conditions described above.


In some embodiments, the coating maintains its antimicrobial activity even after polishing and/or drawing. Polishing can include abrasion with a cloth and a polishing agent under typical polishing conditions. In certain implementations, the coatings provided herein advantageously protect the appearance of metal goods, making polishing of the surfaces of the household good unnecessary. In some embodiments, this property can advantageously give products even longer lasting antimicrobial properties.


In some embodiments, the antimicrobial properties of the coatings are accomplished without leaching of copper from the coating. In some embodiments, the antimicrobial properties of the coatings are accomplished without leaching of silver from the coating. In some embodiments, the antimicrobial properties of the coatings are accomplished without leaching of copper and/or ammonium from the coating.


In some embodiments, the coating is fingerprint or smudge resistant. The terms “fingerprint resistant,” or “smudge resistant” refer to the ability of a surface to resist the visible transfer of residue from physical interactions with a user, the minimization, hiding, or obscuring of tactilely-transferable residue on a surface, and/or combinations thereof. In certain implementations, a fingerprint-resistant surface is substantially resistant to both water-based material and oil-based material transfer when contacted by a user. In some embodiments, a fingerprint-resistant surface is substantially resistant to one or more of inorganic-based material and organic-based material transfer when contacted by a user. In some embodiments, fingerprint resistance is measured using the amount of transferred residue after a user makes physical contact with the household good. For instance, after physical contact (e.g., from the skin of a user), some amount of residue can transfer to the household good. The mass of the residue on the coated household good after each interaction can be quantified, for example, by weighing the mass (or by weighing the mass of a representative test sheet of that material). In some embodiments, the mass transferred from a user to the coated household good is less than or equal to: about 1 mg, about 0.02 mg, or 0.001 mg per instance of physical contact (for instance by dragging a hand across the test surface) to a portion of the household good that is sized 4″×4″. In some embodiments, the fingerprint resistance is qualitatively measured using the human eye and a fingerprint/smudge resistant material shows less visible residue after physical contact than a non-resistant surface. In some embodiments, the fingerprint resistance of a material is measured by determining the reflectivity before contact (e.g., when clean) or after one or more instances of physical contact (as described above). In some implementations, when the fingerprint resistant material is coated on a mirrored-surface (or a chromed-surface, stainless steel, or another otherwise reflective surface of a household good), the fingerprint resistant material maintains at least about 75%, at least about 95%, or at least about 99% of the reflectance of the surface compared to that before an instance of physical contact. In some embodiments, coatings that are fingerprint or smudge resistant are advantageously more desirable to consumers for aesthetic reasons.


In certain implementations, the antimicrobial agent is deposited directly into a fingerprint mitigating (fingerprint resistant) material to form the coating material and the two are added to any surface of the household good together. In some embodiments, the fingerprint resistant material (e.g., compound) is applied separately (before or after) the antimicrobial compound. In some embodiments, antimicrobial coatings and fingerprint resisting coatings are added as separate layers that can be sandwiched on top of one another. A plurality of layers can be added by exposing sheets of, for example, metal to antimicrobial coating and fingerprint proof coating conditions repetitively. In certain implementations, the antimicrobial agent and the fingerprint resistant material are added in patterns on a surface (e.g., patches, stripes, etc.) that give the household good both antimicrobial and fingerprint resistant properties on substantially the entire coated surface.


Certain Methods Related to the Antimicrobial Coating

Some embodiments pertain to methods of preparing a coated household good. A flow chart describing an embodiment of a method 700 is provided in FIG. 7. As shown, in certain variants, the antimicrobial agent is dispersed within a solution, such as a solution of polymer and solvent 701. This mixture is agitated to form a substantially uniform slurry 702. After the slurry is formed, a sheet of material is obtained 703 and the slurry it is layered onto a sheet of material to form a coated sheet 704. For example, the slurry can be applied to a sheet of metal, such as stainless steel 704. In some embodiments, the sheet can be cured for a period of time to afford a coated sheet 705. In certain implementations, the dried coated sheet can then be cut and shaped in appropriate ways to form walls, lids, foot pedals, and handles for metal household goods including trashcans.


In some embodiments, prior to application to the sheet, the antimicrobial agent is slurried with the polymer in a solvent to form a mixture. In some variants, the slurry is agitated continuously prior to application to the metal sheet in order to maintain a homogenous dispersion. In some embodiments, the dispersion is distributed into a coating device that spreads an even layer of the slurry onto the sheet. The solvent can then be evaporated from the slurry, leaving an antimicrobial surface on the sheet that comprises a smooth layer of polymer with the antimicrobial agent dispersed within it. In some embodiments, the evaporation of the solvent cures the polymer/antimicrobial agent. In certain implementations, after curing, at least a portion of the antimicrobial agent protrudes from the substrate and is available to directly interact with microbes on the surface of a coated household good. In some embodiments, the antimicrobial agent can diffuse over time to the surface of the coating to interact directly with microbes on the surface of the household good. In certain implementations, the antimicrobial agent is consumed during the killing of microbes, while in other embodiments it is not. In some embodiments, direct contact with the microbe and the antibacterial agent is not necessary.


It has been found that several coating techniques for surfaces are not amenable to distributing streak-free antimicrobial coatings. For instance, coatings applied using a metered-rolling process result in streaked coatings (see FIGS. 3A and 4A). In a metered-rolling process, a rolling element rolls in the direction of a sheet that passes over the rolling element. In a metered-rolling device, the rolling element is at least partially submerged in a reservoir of a coating agent. As the rolling element rolls, it draws coating agent from this reservoir and deposits it on a sheet as the sheet moves by. This process coats the sheet as the sheet travels along in the direction of rolling.


In contrast, in various embodiments described herein, the coating device uses a non-metered-rolling process (e.g., a reverse-rolling technique) to apply the slurry to the sheet. FIG. 8 shows an embodiment of a system 800 that can be used to apply a coating 810 by reverse-rolling. For instance, in certain variants, in the non-metered, reverse-rolling process, the metal sheet 820 is drawn below a first rolling element 830 (e.g., a coating roller) of the coating device in a first direction 822. The first rolling element 830 is in fluidic communication with a reservoir 840 containing a slurry of antimicrobial agent, polymer, and/or solvent that is formed between the first rolling element 830 and a second rolling element 832 (e.g., a doctor roll). The first rolling element 830 draws the slurried mixture from the reservoir 840 and deposits it on a surface of the first rolling element 831 which distributes the slurried mixture to the sheet as the sheet passes below the first rolling element 830. During reverse-rolling, the region of the first rolling element 830 that is approximately adjacent to the sheet 820 travels (e.g., rolls) in a second direction 834, which is opposite to the first direction 822 (the direction of movement of the sheet). In some implementations, when reverse-rolling is used, the final coating is substantially or completely streak-free to the unaided eye (see, e.g., FIGS. 3B and 4B).


Without being bound to any particular mechanism, it is believed that the antimicrobial agent adds contrast the coating. If applied using certain methods, the contrast of a coating having an antimicrobial agent, as disclosed herein, becomes large enough to be visible by the naked eye. In some embodiments, whether a coating is streak-free can be measured using the naked eye. In some implementations, whether a coating is streak-free can be quantified. In some embodiments, for instance, streak-free coatings are those having a transmittance variation between any two points on the surface that varies by less than: about 75%, about 50%, about 30%, about 20%, about 10%, about 5%, about 2%, or about 1% transmittance. In some embodiments, for instance, streak-free coatings are those having a reflectance variation between any two points on the surface that varies by less than: about 50%, about 25%, or about 5% reflectance. In certain implementations, the coating is applied using other solution-based techniques (e.g., spray coating, spin-coating, dip-coating, inkjetting, or the like) that result in streak-free materials.


In some embodiments, as the slurry cures, it forms a homogeneous distribution of antimicrobial agent within the coating. In some embodiments, a gradient of antimicrobial agent can be formed in the coating by, for example, depositing additional layers of slurry (with different concentrations of antimicrobial agent) onto the sheet. In some embodiments, a gradient can be formed by changing the curing rate (e.g., by slowing or increasing the curing speed using lower or higher cure temperatures etc.). In some embodiments, a gradient can be formed by depositing additional layers of higher or lower concentration slurry over partially cured other layers of slurry. In some embodiments, a gradient can be formed by changing the concentration of antimicrobial agent and/or polymer in solution. For example, in certain implementations, in more dilute solutions, the cure rate can be slowed so that more of the antimicrobial agent can settle in the direction of gravity during the curing process, forming a more concentrated layer in that direction. Any of the methods described in this specification can be used to form antimicrobial agent gradients that are either more concentrated at the surface of the coating or more concentrated at the surface of the household good (which can be especially useful in applications where, for example, the antimicrobial diffuses towards the surface of the coating over time). In some variants, gradients can be used to advantageously maintain or increase antimicrobial effect over time.


In some embodiments, uneven application of coatings to surfaces is reduced or minimized using the disclosed methods and/or substantially even (or uniform) coatings result. In certain implementations, visible streaking in the coating can be caused by the uneven application of the coating to the surface of the trashcan. In certain implementations, the methods used to deposit the coating result in a substantially uniform coating thickness on the sheet material. In certain implementations, the thickness of the coating can be equal to or greater than about 10 μm and/or less than or equal to about 20 μm. In some embodiments, the thickness can be less than or equal to: about 100 μm, about 80 μm, about 70 μm, about 60 μm, about 50 μm, about 40 μm about 30 μm, about 20 μm, about 10 μm, about 5 μm, values between the aforementioned values, ranges spanning those values, or otherwise. In some embodiments, the coating is of substantially uniform thickness. In some embodiments, the thickness of the coating varies by less than or equal to: about 100%, about 90%, about 80%, about 70%, about 60%, about 50%, about 40%, about 30%, about 20%, about 10%, about 5%, about 2%, values between the aforementioned values, ranges spanning those values, or otherwise as measured between any two points on a coated surface. In some embodiments, this level of uniformity results in a coating that appears substantially streak-free. In some embodiments, the coating is generally planar, substantially flat, substantially smooth and uniform, and/or substantially contiguous, such that streaks are not generally visible upon casual visual observation.


In some embodiments, the methods described herein result in a material that is substantially optically transparent. For example, in certain implementations, the optical transmittance of the coating over the visible spectrum is at least: about 65%, about 75%, about 85%, about 95%, about 98%, values between the aforementioned values, ranges spanning those values, or otherwise.


Certain Protective Coverings

Some embodiments pertain to protective coverings for the coatings disclosed herein. A flow chart describing an embodiment of a method 900 is provided in FIG. 9. As shown, in certain variants, a plurality of metal sheets is obtained 901. In some embodiments, sheets of a different material can be used (plastic, composite, etc.). A slurry of antimicrobial agent in a polymer/solvent solution is layered onto a plurality of metal sheets 902 which are then cured to form a coated sheets 903. A protective film is then adhered to the coated sheets using an adhesive 904. The sheets are then stacked 905 and transported to a fabricating facility 906. At the facility, the protective films and adhesive is removed without leaving residue from the adhesive on the coated sheet 907. The sheets are then cut and shaped to form household goods 908. In certain implementations, as described above, the dried coated sheet be cut and shaped in appropriate ways to form walls, lids, foot pedals, and handles for metal household goods including trashcans. In some implementations, finished goods can be protected by applying an adhesive and a protective film to antimicrobially coated household goods.


During shipping of sheets to make a household good or a household good itself, the surfaces of the sheet or sheet good can be protected by depositing films onto those surfaces. Rubber adhesives can be used to adhere protective films onto portions of the sheets or household goods. However, it has been found that some rubber adhesives leave deposits (e.g., residue, etc.) on the coatings (see FIG. 10A). This can result in streaks and other visual imperfections 1020 on the coating 1001 after the protective film 1010 is removed, as is pointed-to by the arrow in FIG. 10A. In certain instances, the residue can leave an unwanted sticky region on the coating. In certain instances, these residues cannot be readily washed away from the coatings.


Certain embodiments are configured to ameliorate at least one of these problems, or other problems. For example, some embodiments adhere or otherwise connect a protective film to a coated sheet of material such that removal of the film does not leave an appreciable residue on the coated material. In some embodiments, acrylic or silicone rubber adhesive is used to adhere the film to the coated sheet of material, which has been found to reduce or eliminate appreciable residue on the coating 1001 after removal of the film 1011 (see FIG. 10B which lacks residue). In certain implementations, the use of acrylic or silicone or rubber adhesive leads to a more visually appealing result once the protective film is removed. In some variants, the substantially complete removal of residue helps avoid areas (e.g., on top of the residue) where the antimicrobial activity of the coating could be blocked. In some embodiments, rubber may be used as an adhesive (with or without one or more other adhesives).


Some embodiments pertain to methods of applying protective films to antimicrobial coatings. In certain implementations, the adhesive is applied to a coated sheet of material using a solution-based technique (e.g., spray coating, spin-coating, dip-coating, inkjetting, rolling, or the like). Once applied, a protective film (e.g., a polymeric material) is deposited onto the adhesive, such as by rolling the film onto the coated sheet of material.


Summary

Several illustrative embodiments of coatings and methods of coating have been disclosed. Although this disclosure has been described in terms of certain illustrative embodiments and uses, other embodiments and other uses, including embodiments and uses which do not provide all of the features and advantages set forth herein, are also within the scope of this disclosure. Components, elements, features, acts, or steps can be arranged or performed differently than described and components, elements, features, acts, or steps can be combined, merged, added, or left out in various embodiments. All possible combinations and subcombinations of elements and components described herein are intended to be included in this disclosure. No single feature or group of features is necessary or indispensable.


Certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation also can be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can in some cases be excised from the combination, and the combination may be claimed as a subcombination or variation of a subcombination.


Any portion of any of the steps, processes, structures, and/or devices disclosed or illustrated in one embodiment, flowchart, or example in this disclosure can be combined or used with (or instead of) any other portion of any of the steps, processes, structures, and/or devices disclosed or illustrated in a different embodiment, flowchart, or example. The embodiments and examples described herein are not intended to be discrete and separate from each other. Combinations, variations, and other implementations of the disclosed features are within the scope of this disclosure.


The terms “approximately,” “about,” and “substantially” as used herein represent an amount close to the stated amount that still performs a desired function or achieves a desired result. For example, in some embodiments, as the context may dictate, the terms “approximately”, “about”, and “substantially” may refer to an amount that is within less than or equal to 10% of the stated amount. The term “generally” as used herein represents a value, amount, or characteristic that predominantly includes or tends toward a particular value, amount, or characteristic.


Some embodiments have been described in connection with the accompanying drawings. Moreover, while operations may be depicted in the drawings or described in the specification in a particular order, such operations need not be performed in the particular order shown or in sequential order, or that all operations be performed, to achieve desirable results. Other operations that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional operations can be performed before, after, simultaneously, or between any of the described operations. Additionally, the operations may be rearranged or reordered in other implementations. Also, the separation of various components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. Additionally, other implementations are within the scope of this disclosure.


Conditional language used herein, such as, among others, “can,” “could,” “might,” “may,” “e.g.,” and the like, unless specifically stated otherwise or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or steps. Thus, such conditional language is not generally intended to imply that features, elements and/or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without author input or prompting, whether these features, elements and/or steps are included or are to be performed in any particular embodiment. The terms “comprising,” “including,” “having,” and the like are synonymous and are used inclusively, in an open-ended fashion, and do not exclude additional elements, features, acts, operations, and so forth. Also, the term “or” is used in its inclusive sense (and not in its exclusive sense) so that when used, for example, to connect a list of elements, the term “or” means one, some, or all of the elements in the list.


Conjunctive language such as the phrase “at least one of X, Y, and Z,” unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.


Further, while illustrative embodiments have been described, any embodiments having equivalent elements, modifications, omissions, and/or combinations are also within the scope of this disclosure. Moreover, although certain aspects, advantages, and novel features are described herein, not necessarily all such advantages may be achieved in accordance with any particular embodiment. For example, some embodiments within the scope of this disclosure achieve one advantage, or a group of advantages, as taught herein without necessarily achieving other advantages taught or suggested herein. Further, some embodiments may achieve different advantages than those taught or suggested herein.


In summary, various embodiments and examples of antimicrobial coatings and protective films have been disclosed. This disclosure extends beyond the specifically disclosed embodiments and examples to other alternative embodiments and/or other uses of the embodiments, as well as to certain modifications and equivalents thereof. Moreover, this disclosure expressly contemplates that various features and aspects of the disclosed embodiments can be combined with, or substituted for, one another. Accordingly, the scope of this disclosure should not be limited by the particular disclosed embodiments described above, but should be determined only by a fair reading of the claims.


EXAMPLES
Example 1: Fabrication of Coated Metal

Coatings were prepared using a metered-rolling process and a reverse-rolling technique. Prior to coating, a slurry of polyethylene polymer and solvent was prepared. To this solution was added 1.25 wt % of AC10D grade AGION® (relative to the dry weight of polyethylene) forming a mixture. This mixture was stirred to achieve a uniform slurry. Once a uniform was achieved, it was added to the reservoir of a metered-rolling device which distributed the slurry on a stainless steel sheet via a roller rotating in the same direction of the sheet movement. The sheet was allowed to cure. FIGS. 3A and 4A show the resultant coated sheet.


A second slurry was formed using the same ingredients and techniques described above. This mixture was added to the reservoir of a reverse-rolling device which distributed the slurry on a stainless steel sheet via a roller rotating in the direction opposite the direction of the sheet. The sheet was allowed to cure. FIGS. 3B and 4B show the resultant coated sheet.


As shown in the figures, the reverse-rolling technique resulted in an antimicrobial coating that was streak-free and uniform relative to the antimicrobial coating formed using the metered-rolling technique.


Example 2: Antimicrobial Testing

Several experiments were performed using the Japanese Industrial Standard (“JIS”) method Z 2801 antimicrobial evaluation method to show the antimicrobial activity of a sheet metal coated using the reverse-rolling process described in Example 1. The JIS method Z 2801 is a quantitative test designed to assess the performance of antimicrobial finishes on hard, non-porous surfaces. The method can be conducted using contact times ranging from ten minutes up to 24 hours. For a JIS Z 2801 test, non-antimicrobial control surfaces are used as the baseline for calculations of microbial reduction. The method can be used to determine the antimicrobial activity of a diverse array of surfaces including plastics, metals, and ceramics. The test microorganism(s) selected for this test were Escherichia coli 8739 (a Gram-negative bacteria) and Staphylococcus aureus 6538 (a Gram-positive bacteria).


Testing Method

The test microorganism was prepared by growth in a Tryptic Soy Broth. The suspension of test microorganism was standardized by dilution in a nutritive broth (this affords microorganisms the opportunity to proliferate during the test). Control and test substances were wiped clean with 70% ethanol and allowed to dry prior to testing. Control and test surfaces (50 mm×50 mm) were inoculated with microorganisms (where the testing parameter was 0.400 mL at a concentration of 4×105 CFU/Carrier), and then the microbial inoculum was covered with a thin, sterile film (40 mm×40 mm). Covering the inoculum spreads it, prevents it from evaporating, and ensures close contact with the antimicrobial surface. Microbial concentrations were determined at “time zero” by elution followed by dilution and plating to Tryptic Soy Agar. A control was run to verify that the neutralization/elution method effectively neutralizes the antimicrobial agent in the antimicrobial surface being tested. Inoculated, covered control and antimicrobial test surfaces were allowed to incubate undisturbed in a humid environment for 24 hours, at 36° C.±1° C.


After incubation, microbial concentrations were determined. Reduction of microorganisms relative to the control surface were calculated. The neutralizer was D/E Broth (10 mL). The enumeration plate media was tryptic soy agar. The enumeration plate was incubated for 24±6 hours at 36° C.±1° C.


Results were calculated using the following formulae:







Percent


Reduction

=


(


B
-
A

B

)

×
100






Where B=Number of viable test microorganisms on the control carriers after the contact time;


and A=Number of viable test microorganisms on the test carriers after the contact time.








Log
10



Reduction

=

Log

(

B
A

)






Where B=Number of viable test microorganisms on the control carriers after the contact time; and A=Number of viable test microorganisms on the test carriers after the contact time.


Results of E. Coli Testing














TABLE 1









Percent
Log10






Reduction
Reduction






Compared
Compared






to
to


Test



Control at
Control at


Micro-
Contact
Carrier
CFU/
Contact
Contact


organism
Time
Type
Carrier
Time
Time




















E. coli

Time
Inoculum
 2.30E+05
N/A


8739
Zero
Only













24
Control
 2.35E+07





Hours
B 1.50
<5.00E+00
>99.99998%
>6.67




E 1.25
<5.00E+00
>99.99998%
>6.67










The data collected using E. Coli on 50 mm×50 mm carriers (covered by 40 mm×40 mm films) is shown in Table 1. FIG. 5 shows a graph plotting E. Coli CFU/Carrier against the control and experimental samples. The limit of detection for this study is 5 CFU/Carrier. Values less than the limit of detection are shown as <5.00E+00 on the table and zero on the graph.


Results of S. Aureus Testing














TABLE 2









Percent
Log10






Reduction
Reduction






Compared
Compared






to
to


Test



Control at
Control at


Micro-
Contact
Carrier
CFU/
Contact
Contact


organism
Time
Type
Carrier
Time
Time




















S. aureus

Time
Inoculum
3.85E+05
N/A


6538
Zero
Only













24
Control
9.50E+06





Hours
B 1.50
5.00E+00
99.99995%
6.28




E 1.25
<5.00E+00 
>99.99995%
>6.28










The data collected using S. Aureus on 50 mm×50 mm carriers (covered by 40 mm×40 mm films) is shown in Table 2. FIG. 6 shows a graph plotting S. Aureus CFU/Carrier against the control and experimental samples. The limit of detection for this study is 5 CFU/Carrier. Values less than the limit of detection are shown as <5.00E+00 on the table and zero on the graph.


Example 3: Antimicrobial Testing

Below are experiments performed using the Sciessent LLC antimicrobial evaluation methods to show the antimicrobial activity of a sheet metal (2″×2″) coated using the reverse-rolling process described in Example 1. Certain samples were abraded before testing. The bacteria used were E. coli and S. Aureus.









TABLE 3








E. Coli (ATCC#: 25922) Testing











Organism Count (CFU/ml)












Zero
24 Hours




Contact
Contact
Percent


Sample Identification
Time
Time
Reduction**





Assay (+)
2.5 × 105
2.0 × 107
No Reduction


Assay (−)
<10*
<10*
N/A


Untreated coated metal samples

4.6 × 107
No Reduction


Sciessent ID# 150811-1A


Coaled metal samples (1.5% AC10D in coating)

3.2 × 104
99.93%


Sciessent ID# 150806-3B, Rep 1


Coated metal samples (1.5% AC10D in coating)

2.8 × 104
99.94%


Sciessent ID# 150806-3B, Rep 2


Coated metal samples (1.5% AC10D in coating) - Abraded

1.04 × 102
99.99%


Sciessent ID# 150806-3B, Rep 1


Coated metal samples (1.5% AC10D in coating) - Abraded

5.4 × 102
99.999%


Sciessent ID# 150806-3B, Rep 2





Testing was performed in accordance with standard operating procedures of Sciessent LLC.


*≤10 = Limits of Detection;


**is percent reduction calculated using: untreated T24 contact time.













TABLE 4








S. Aureus (ATCC#: 6538) Testing











Organism Count (CFU/ml)












Zero
24 Hours




Contact
Contact
Percent


Sample Identification
Time
Time
Reduction**





Assay (+)
2.3 × 105
6.5 × 106
No Reduction


Assay (−)
<10*
<10*
N/A


Untreated coated metal samples

5.0 × 107
No Reduction


Sciessent ID# 150811-1A


Coated metal samples (1.5% AC10D in coating)

7.8 × 104
99.84%


Sciessent ID# 150806-3B, Rep 1


Coated metal samples (1.5% AC10D in coating)

5.9 × 104
99.90%


Sciessent ID# 150806-3B, Rep 2


Coated metal samples (1.5% AC10D in coating)

3.3 × 104
99.93%


Sciessent ID# 150806-3B, Rep 3


Coated metal samples (1.5% AC10D in coating) - Abraded

7.0 × 101
99.9999%


Sciessent ID# 150806-3B, Rep 1


Coated metal samples (1.5% AC10D in coating) - Abraded

<10*
99.9999%


Sciessent ID# 150806-3B, Rep 2


Coated metal samples (1.5% AC10D in coating) - Abraded

<10*
99.9999%


Sciessent ID# 150806-3B, Rep 3





Testing was performed in accordance with standard operating procedures of Sciessent LLC.


*≤10 = Limits of Detection;


**is percent reduction calculated using: untreated T24 contact time.






Example 4: Application of Protective Film to Coated Sheets

Protective film coatings were applied to a portion of sheet metal coated using the reverse-rolling process described in Example 1. In one experiment, to the coated sheet was sprayed a rubber adhesive (coinciding to FIG. 10A). In a second experiment, to the coated sheet was sprayed an acrylic and/or silicone rubber adhesive (coinciding to FIG. 10B). Soon after application of each adhesive, film protective layers were applied to the adhesives on the coated sheets. After 24 hours, the protective films were removed. After removal of the protective film, a residue was noted on the coated sheet where a rubber adhesive was used. The residue was washed several times with ethanol but remained on the coated surface (see FIG. 10A). No such residue was noted on the coated sheet where an acrylic and/or silicone rubber adhesive was used (FIG. 10B).

Claims
  • 1. A method of manufacturing a trashcan, comprising: providing a metal to be shaped into a container that is configured to receive at least a portion of refuse;applying a slurry comprising a solvent, a substrate material comprising a polymeric material, and an antimicrobial agent comprising a sub-support to the metal using a reverse-rolling device to form a coating deposited directly on the surface of the metal;forming a smooth and substantially streak-free coated sheet; andshaping the smooth and substantially streak-free coated sheet to form a trashcan,wherein at least a portion of the antimicrobial agent is exposed on an outside surface of the coating and is available to directly contact microbes on the surface of the coating after application of the coating to the metal.
  • 2. The method of claim 1, wherein the coating comprises a fingerprint resistant material.
  • 3. The method of claim 2, wherein the fingerprint resistant material allows fingerprints to be removed by wiping without using a liquid solution.
  • 4. The method of claim 1, wherein the smooth and substantially streak-free coated sheet is substantially resistant to water-based material transfer.
  • 5. The method of claim 1, wherein the substantially streak-free coated sheet appears substantially flat.
  • 6. The method of claim 1, wherein the polymeric material comprises polyethylene.
  • 7. The method of claim 1, wherein the sub-support comprises a zeolite.
  • 8. The method of claim 1, wherein the antimicrobial agent comprises ionic silver, ionic copper, and ammonium.
  • 9. The method of claim 1, wherein the antimicrobial agent is supported on a nanoparticle.
  • 10. The method of claim 1, wherein the metal is a stainless steel metal sheet.
  • 11. The method of claim 1, wherein 24 hours after an initial bacterial exposure to the coating, an amount of bacteria remaining on the coating is at least about 95% less than at the initial bacterial exposure.
  • 12. The method of claim 1, wherein the coating reduces an amount of E. coli from about 2.3×105 colony forming units (CFU) per 50 mm×50 mm carrier to less than about 5 CFU/carrier over a period of about 24 hours.
  • 13. The method of claim 1, wherein the coating reduces an amount of S. aureus from about 3.85×105 CFU per 50 mm×50 mm carrier to less than about 5 CFU/carrier over a period of about 24 hours.
  • 14. The method of claim 1, wherein the sub-support comprises an average particle size from about 1 μm to about 10 μm.
  • 15. The method of claim 1, wherein the antimicrobial agent comprises from about 2% to about 5% ionic silver by weight.
  • 16. The method of claim 1, wherein the antimicrobial agent comprises from about 4% to about 7% ionic copper by weight.
  • 17. The method of claim 1, wherein the antimicrobial agent is present in an amount of about 1.25 wt % relative to the substrate.
  • 18. A method of manufacturing a trashcan, comprising: providing a stainless steel metal to be shaped into a container that is configured to receive refuse;applying a slurry comprising a solvent, a substrate material comprising a polymeric material, and an antimicrobial agent comprising a sub-support to the stainless steel metal using a reverse-rolling device to form a coating deposited directly on the surface of the stainless steel metal, such that the stainless steel metal is coated with a substrate comprising the polymeric material and the antimicrobial agent dispersed within the substrate to form a smooth and substantially streak-free coated sheet, wherein the antimicrobial agent comprises a sub-support;drying the substrate on the smooth and substantially streak-free coated sheet; andshaping the smooth and substantially streak-free coated sheet to form a trashcan;wherein at least a portion of the antimicrobial agent is exposed on an outside surface of the coating and is available to directly contact microbes on the surface of the coating after application of the coating to the stainless steel metal sheet,wherein the coating is smooth and substantially fingerprint resistant to oil-based material transfer and resists a visible transfer of residue after physical interaction.
  • 19. The method of claim 18, wherein the fingerprint resistant material allows fingerprints to be removed by wiping without using a liquid solution.
  • 20. The method of claim 18, wherein the substrate comprises polyethylene.
  • 21. The method of claim 18, wherein the antimicrobial agent comprises a zeolite.
CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No. 17/560,056, filed Dec. 22, 2021, which is a continuation of U.S. application Ser. No. 15/343,899, filed Nov. 4, 2016, which issued as U.S. Pat. No. 11,242,198 on Feb. 8, 2022, which claims the benefit of priority to U.S. Provisional Application No. 62/253,612, filed Nov. 10, 2015. Each of the foregoing applications is fully incorporated herein by reference in its entirety for all purposes.

US Referenced Citations (570)
Number Name Date Kind
830182 Skov Sep 1906 A
1426211 Pausin Aug 1922 A
1461253 Owen Jul 1923 A
1754802 Raster Apr 1930 A
1820555 Buschman Aug 1931 A
1891651 Padelford et al. Dec 1932 A
1922729 Geibel Aug 1933 A
1923742 Nesbitt Aug 1933 A
1980938 Geibel Nov 1934 A
2046777 Geibel Jul 1936 A
2308326 Ambrose Jan 1943 A
D148825 Snider Feb 1948 S
2457274 Rifken Dec 1948 A
2593455 James Apr 1952 A
2759625 Ritter Aug 1956 A
2796309 Taylor Jun 1957 A
2842092 Pomper Jul 1958 A
2888307 Graves et al. May 1959 A
2946474 Knapp Jul 1960 A
3008604 Garner Nov 1961 A
3023922 Arrington et al. Mar 1962 A
3137408 Taylor Jun 1964 A
3300082 Patterson Jan 1967 A
3392825 Gale et al. Jul 1968 A
3451453 Heck Jun 1969 A
3654534 Fischer Apr 1972 A
3800503 Maki Apr 1974 A
3820200 Myers Jun 1974 A
3825150 Taylor Jul 1974 A
3825215 Borglum Jul 1974 A
3886425 Weiss May 1975 A
3888406 Nippes Jun 1975 A
3891115 Ono Jun 1975 A
4014457 Hodge Mar 1977 A
4027774 Cote Jun 1977 A
4081105 Dagonnet et al. Mar 1978 A
4189808 Brown Feb 1980 A
4200197 Meyer et al. Apr 1980 A
4217616 Jessup Aug 1980 A
4303174 Anderson Dec 1981 A
4320851 Montoya Mar 1982 A
4349123 Yang Sep 1982 A
4357740 Brown Nov 1982 A
4416197 Kehl Nov 1983 A
4417669 Knowles et al. Nov 1983 A
4457483 Gagne Jul 1984 A
4535911 Goulter Aug 1985 A
4570304 Montreuil et al. Feb 1986 A
4576310 Isgar et al. Mar 1986 A
D284320 Kubic et al. Jun 1986 S
4609117 Pamment Sep 1986 A
4630332 Bisbing Dec 1986 A
4630752 DeMars Dec 1986 A
4664347 Brown et al. May 1987 A
4697312 Freyer Oct 1987 A
4711161 Swin et al. Dec 1987 A
4729490 Ziegenbein Mar 1988 A
4753367 Miller et al. Jun 1988 A
4763808 Guhl et al. Aug 1988 A
4765548 Sing Aug 1988 A
4765579 Robbins, III et al. Aug 1988 A
4785964 Miller et al. Nov 1988 A
4792039 Dayton Dec 1988 A
4794973 Perisic Jan 1989 A
4813592 Stolzman Mar 1989 A
4823979 Clark, Jr. Apr 1989 A
4834260 Auten May 1989 A
4863053 Oberg Sep 1989 A
4867339 Hahn Sep 1989 A
4869391 Farrington Sep 1989 A
4884717 Bussard et al. Dec 1989 A
4888532 Josson Dec 1989 A
4892223 DeMent Jan 1990 A
4892224 Graham Jan 1990 A
D307344 Massonnet Apr 1990 S
4913308 Culbertson Apr 1990 A
4915347 Iqbal et al. Apr 1990 A
4918568 Stone et al. Apr 1990 A
D308272 Koepsell May 1990 S
4923087 Burrows May 1990 A
4944419 Chandler Jul 1990 A
4948004 Chich Aug 1990 A
4964523 Bieltvedt et al. Oct 1990 A
4972966 Craft, Jr. Nov 1990 A
4996467 Day Feb 1991 A
5031793 Chen et al. Jul 1991 A
5048903 Loblein Sep 1991 A
5054724 Hutcheson Oct 1991 A
5065272 Owen et al. Nov 1991 A
5065891 Casey Nov 1991 A
D322350 Craft, Jr. et al. Dec 1991 S
5076462 Perrone Dec 1991 A
D323573 Schneider Jan 1992 S
5090585 Power Feb 1992 A
5090785 Stamp Feb 1992 A
5100087 Ashby Mar 1992 A
5111958 Witthoeft May 1992 A
D327760 Donnelly Jul 1992 S
D329929 Knoedler et al. Sep 1992 S
5147055 Samson et al. Sep 1992 A
5156290 Rodrigues Oct 1992 A
D331097 Sieren Nov 1992 S
5170904 Neuhaus Dec 1992 A
5174462 Hames Dec 1992 A
D332852 Delmerico Jan 1993 S
D335562 Evans May 1993 S
5213272 Gallagher et al. May 1993 A
5222704 Light Jun 1993 A
D337181 Warman Jul 1993 S
5226558 Whitney et al. Jul 1993 A
5230525 Delmerico et al. Jul 1993 A
5242074 Conaway et al. Sep 1993 A
D340333 Duran et al. Oct 1993 S
5249693 Gillispie et al. Oct 1993 A
5261553 Mueller et al. Nov 1993 A
5265511 Itzov Nov 1993 A
5295607 Chang Mar 1994 A
5305916 Suzuki et al. Apr 1994 A
5314151 Carter-Mann May 1994 A
5322179 Ting Jun 1994 A
5329212 Feigleson Jul 1994 A
5348222 Patey Sep 1994 A
5353950 Taylor et al. Oct 1994 A
5372272 Jennings Dec 1994 A
5381588 Nelson Jan 1995 A
5385258 Sutherlin Jan 1995 A
5390818 LaBuda Feb 1995 A
5404621 Heinke Apr 1995 A
5407089 Bird et al. Apr 1995 A
5419452 Mueller et al. May 1995 A
5471708 Lynch Dec 1995 A
5474201 Liu Dec 1995 A
5474797 Sioshansi et al. Dec 1995 A
5501358 Hobday Mar 1996 A
5520067 Gaba May 1996 A
5520303 Bernstein et al. May 1996 A
5527840 Chutko et al. Jun 1996 A
5531348 Baker et al. Jul 1996 A
5535913 Asbach et al. Jul 1996 A
5558254 Anderson et al. Sep 1996 A
5560283 Hannig Oct 1996 A
5584412 Wang Dec 1996 A
D377554 Adriaansen Jan 1997 S
5611507 Smith Mar 1997 A
5628424 Gola May 1997 A
5632401 Hurd May 1997 A
5636416 Anderson Jun 1997 A
5636761 Diamond et al. Jun 1997 A
5644111 Cerny et al. Jul 1997 A
5645186 Powers et al. Jul 1997 A
5650680 Chula Jul 1997 A
D383277 Peters Sep 1997 S
5662235 Nieto Sep 1997 A
5671847 Pedersen et al. Sep 1997 A
5690247 Boover Nov 1997 A
5695088 Kasbohm Dec 1997 A
5699929 Ouno Dec 1997 A
D388922 Peters Jan 1998 S
D389631 Peters Jan 1998 S
5704511 Kellams Jan 1998 A
5724837 Shin Mar 1998 A
5730312 Hung Mar 1998 A
5732845 Armaly, Jr. Mar 1998 A
5735495 Kubota Apr 1998 A
5738239 Triglia Apr 1998 A
5770935 Smith et al. Jun 1998 A
5799909 Ziegler Sep 1998 A
5816431 Giannopoulos Oct 1998 A
5816640 Nishimura Oct 1998 A
D401383 Gish Nov 1998 S
D401719 Van Leeuwen et al. Nov 1998 S
5873643 Burgess, Jr. et al. Feb 1999 A
5881896 Presnell et al. Mar 1999 A
5881901 Hampton Mar 1999 A
5884237 Kanki et al. Mar 1999 A
5887748 Nguyen Mar 1999 A
D412552 Burrows Aug 1999 S
5961105 Ehrnsberger et al. Oct 1999 A
5967392 Niemi et al. Oct 1999 A
5987708 Newton Nov 1999 A
6000569 Liu Dec 1999 A
6010024 Wang Jan 2000 A
6024238 Jaros Feb 2000 A
6036050 Ruane Mar 2000 A
6102239 Wien Aug 2000 A
6105859 Stafford Aug 2000 A
6123215 Windle Sep 2000 A
D431700 Roudebush Oct 2000 S
6126031 Reason Oct 2000 A
6129233 Schiller Oct 2000 A
6131861 Fortier, Jr. et al. Oct 2000 A
D435951 Yang et al. Jan 2001 S
6209744 Gill Apr 2001 B1
6211637 Studer Apr 2001 B1
6234339 Thomas May 2001 B1
6250492 Verbeek Jun 2001 B1
D445980 Tjugum Jul 2001 S
6286706 Tucker Sep 2001 B1
6328320 Walski et al. Dec 2001 B1
6345725 Lin Feb 2002 B1
6364147 Meinzinger et al. Apr 2002 B1
6386386 George May 2002 B1
6390321 Wang May 2002 B1
6401958 Foss et al. Jun 2002 B1
6519130 Breslow Feb 2003 B1
6557716 Chan May 2003 B1
D476456 Englert et al. Jun 2003 S
6596983 Brent Jul 2003 B2
6612099 Stravitz Sep 2003 B2
6626316 Yang Sep 2003 B2
6626317 Pfiefer et al. Sep 2003 B2
6632064 Walker et al. Oct 2003 B1
D481846 Lin Nov 2003 S
D482169 Lin Nov 2003 S
6659407 Asaro Dec 2003 B2
6681950 Miller, Jr. et al. Jan 2004 B2
D488604 Yang et al. Apr 2004 S
D488903 Yang et al. Apr 2004 S
D489503 Lin May 2004 S
D489857 Yang et al. May 2004 S
D490583 Yang et al. May 2004 S
D490954 Brand Jun 2004 S
D491706 Yang et al. Jun 2004 S
6758366 Bourgund et al. Jul 2004 B2
D493930 Wang Aug 2004 S
D494723 Lin Aug 2004 S
6774586 Shih Aug 2004 B1
6785912 Julio Sep 2004 B1
6812655 Wang et al. Nov 2004 B1
6814249 Lin Nov 2004 B2
D499450 Goodman et al. Dec 2004 S
6837393 Kuo Jan 2005 B1
6857538 Lin Feb 2005 B2
6859005 Boliver Feb 2005 B2
D503021 Yang et al. Mar 2005 S
6866826 Moore et al. Mar 2005 B2
6883676 Lin Apr 2005 B2
D507090 Yang et al. Jul 2005 S
6920994 Lin Jul 2005 B2
6974948 Brent Dec 2005 B1
D513445 Lin Jan 2006 S
6981606 Yang et al. Jan 2006 B2
D517764 Wang Mar 2006 S
D517767 Yang et al. Mar 2006 S
D518266 Yang et al. Mar 2006 S
7017773 Gruber et al. Mar 2006 B2
7044323 Yang et al. May 2006 B2
D525756 Yang et al. Jul 2006 S
7073677 Richardson et al. Jul 2006 B2
7077283 Yang et al. Jul 2006 B2
7080750 Wein et al. Jul 2006 B2
7086550 Yang et al. Aug 2006 B2
D528726 Lin Sep 2006 S
7121421 Yang et al. Oct 2006 B2
D531499 Zaidman Nov 2006 S
D535799 Epps Jan 2007 S
D535800 Yang et al. Jan 2007 S
7163591 Kim et al. Jan 2007 B2
7168591 Miller Jan 2007 B1
D537223 Lin Feb 2007 S
D537599 Lin Feb 2007 S
D537601 Lin Feb 2007 S
D537999 Lin Mar 2007 S
D538995 Lin Mar 2007 S
D539498 Yang et al. Mar 2007 S
D539499 Yang et al. Mar 2007 S
D540001 Zimmerman Apr 2007 S
D542001 Yang et al. May 2007 S
D542995 Lin May 2007 S
D543673 Yang et al. May 2007 S
D544170 Lin Jun 2007 S
D544171 Lin Jun 2007 S
D544671 Saunders et al. Jun 2007 S
D545024 Liao Jun 2007 S
7225943 Yang et al. Jun 2007 B2
D547020 Chen Jul 2007 S
7243811 Ramsey Jul 2007 B1
D550918 Wang et al. Sep 2007 S
D552319 Gusdorf Oct 2007 S
D552321 Yang et al. Oct 2007 S
D552823 Yang et al. Oct 2007 S
D552824 Zimmerman Oct 2007 S
D552825 Yang et al. Oct 2007 S
D555320 Yang et al. Nov 2007 S
D557869 Hawker et al. Dec 2007 S
D559494 Yang et al. Jan 2008 S
D559495 Yang et al. Jan 2008 S
D562522 Daams Feb 2008 S
7328842 Wagner et al. Feb 2008 B2
D564169 Wang Mar 2008 S
D564723 Yang et al. Mar 2008 S
D566367 Lin Apr 2008 S
D566369 Shek Apr 2008 S
D566923 Lin Apr 2008 S
D567468 Yang et al. Apr 2008 S
D568572 Yang et al. May 2008 S
D569720 Lablaine May 2008 S
7374060 Yang et al. May 2008 B2
D571520 Lin Jun 2008 S
7395990 Stevens Jul 2008 B1
7398913 McClure Jul 2008 B2
7404499 Ramsey Jul 2008 B1
D574569 Yang et al. Aug 2008 S
D576371 Zimmerman Sep 2008 S
D578265 Presnell Oct 2008 S
D578266 Yang et al. Oct 2008 S
D578268 Yang et al. Oct 2008 S
D578722 Yang et al. Oct 2008 S
7438199 Tidrick Oct 2008 B1
D580120 Lin Nov 2008 S
D580613 Yang et al. Nov 2008 S
D580615 Yang et al. Nov 2008 S
D581622 Presnell et al. Nov 2008 S
D584470 Bizzell et al. Jan 2009 S
D585171 Bizzell et al. Jan 2009 S
D585618 Yang et al. Jan 2009 S
D586070 Lin Feb 2009 S
7494021 Yang et al. Feb 2009 B2
D587874 Lin Mar 2009 S
D593271 Yang et al. May 2009 S
7530578 Niemeyer et al. May 2009 B2
7540396 Yang et al. Jun 2009 B2
7543716 Lin Jun 2009 B2
7559433 Yang et al. Jul 2009 B2
D599074 Bizzell et al. Aug 2009 S
D603119 Yang et al. Oct 2009 S
7607552 Efstathiou Oct 2009 B2
D604472 Blanks et al. Nov 2009 S
7614519 Krauth et al. Nov 2009 B2
7621420 Bandoh et al. Nov 2009 B2
7656109 Yang et al. Feb 2010 B2
D611216 Yang et al. Mar 2010 S
D611217 Bizzell et al. Mar 2010 S
D611671 Yang et al. Mar 2010 S
7694838 Yang et al. Apr 2010 B2
7703622 Bynoe Apr 2010 B1
D615270 Yang et al. May 2010 S
D615722 Yang et al. May 2010 S
7712285 Stravitz et al. May 2010 B2
7741801 Fukuizumi Jun 2010 B2
7748556 Yang et al. Jul 2010 B2
7781995 Yang et al. Aug 2010 B2
D623817 Yang et al. Sep 2010 S
D625068 Shannon Oct 2010 S
7806285 Yang et al. Oct 2010 B2
D627533 Yang et al. Nov 2010 S
D627944 Wang et al. Nov 2010 S
D629172 Liao Dec 2010 S
D630404 Yang et al. Jan 2011 S
D631221 Yang et al. Jan 2011 S
D632039 Yang et al. Feb 2011 S
D632864 Yang et al. Feb 2011 S
D634911 Yang et al. Mar 2011 S
D635319 Meyerhoffer Mar 2011 S
7896187 Haibel Mar 2011 B2
7922024 Yang et al. Apr 2011 B2
7950543 Yang et al. May 2011 B2
D644390 Smeets et al. Aug 2011 S
7992742 Kim Aug 2011 B1
8006857 Lin Aug 2011 B2
D644806 Yang et al. Sep 2011 S
D644807 Yang et al. Sep 2011 S
D649728 Campbell Nov 2011 S
8074833 Yang et al. Dec 2011 B2
8096445 Yang et al. Jan 2012 B2
D655061 Scaturro Feb 2012 S
8136688 Lee et al. Mar 2012 B2
D657108 Yang et al. Apr 2012 S
D657109 Liao Apr 2012 S
8297470 Yang et al. Oct 2012 B2
8317055 Zawrotny et al. Nov 2012 B2
D672520 Yang et al. Dec 2012 S
D673750 Quan Jan 2013 S
D675802 Yang et al. Feb 2013 S
D675803 Yang et al. Feb 2013 S
8393489 Stravitz Mar 2013 B1
8418869 Yang et al. Apr 2013 B2
D689255 Sun Ting Kung et al. Sep 2013 S
8567630 Yang et al. Oct 2013 B2
8569980 Yang et al. Oct 2013 B2
8575537 Yao et al. Nov 2013 B2
8607932 Cooper et al. Dec 2013 B2
8672171 Wynn et al. Mar 2014 B2
8678219 Wang et al. Mar 2014 B1
8686676 Yang et al. Apr 2014 B2
D704406 Kern May 2014 S
8716969 Yang et al. May 2014 B2
8720728 Yang et al. May 2014 B2
D709662 Yang et al. Jul 2014 S
8766582 Yang et al. Jul 2014 B2
8807378 Kaberna Aug 2014 B2
8807379 Hammond Aug 2014 B1
D714510 Yang et al. Sep 2014 S
D715575 Williams et al. Oct 2014 S
D716015 van de Leest Oct 2014 S
8851316 Barrett et al. Oct 2014 B2
8872459 Yang et al. Oct 2014 B2
D725860 Spivey et al. Mar 2015 S
D725861 Yang et al. Mar 2015 S
D730008 Yang et al. May 2015 S
9051093 Yang et al. Jun 2015 B2
D755461 Wall May 2016 S
D758686 Beumer Jun 2016 S
D759934 Yang et al. Jun 2016 S
D762037 Chen Jul 2016 S
D765937 Chen Sep 2016 S
D766998 Kao et al. Sep 2016 S
9434538 Yang et al. Sep 2016 B2
D770121 Chen Oct 2016 S
D771344 Yang et al. Nov 2016 S
D773145 Yang et al. Nov 2016 S
9481515 Yang et al. Nov 2016 B2
D773769 Chen Dec 2016 S
9573759 Yang et al. Feb 2017 B2
9586755 Yang et al. Mar 2017 B1
D787828 Thoma et al. May 2017 S
D790145 Chen Jun 2017 S
D793642 Yang et al. Aug 2017 S
D798016 Yang et al. Sep 2017 S
D804133 Yang et al. Sep 2017 S
9751692 Yang et al. Sep 2017 B2
9790025 Yang et al. Oct 2017 B2
9856080 Yang et al. Jan 2018 B2
D820544 Joseph Jun 2018 S
D825876 Chen Aug 2018 S
D827968 Chen Sep 2018 S
D829400 Yang et al. Sep 2018 S
D830029 Greenspoon et al. Oct 2018 S
D835374 Yang et al. Dec 2018 S
D835376 Yang et al. Dec 2018 S
D836278 Berberet et al. Dec 2018 S
10279996 Yang et al. May 2019 B2
10279997 Yang et al. May 2019 B2
D855919 Yang et al. Aug 2019 S
D858024 Yang et al. Aug 2019 S
D858923 Yang et al. Sep 2019 S
D861076 Chen Sep 2019 S
10472170 Yang et al. Nov 2019 B2
10494175 Yang et al. Dec 2019 B2
D874776 Spadotto Feb 2020 S
10683165 Yang et al. Jun 2020 B2
10723549 Yang et al. Jul 2020 B2
D901815 Yang et al. Nov 2020 S
11242198 Yang et al. Feb 2022 B2
20010002690 Rosky Jun 2001 A1
20010020619 Pfeifer et al. Sep 2001 A1
20010045512 Brent Nov 2001 A1
20020009567 Brand Jan 2002 A1
20020066736 Pyles Jun 2002 A1
20020092853 Wang Jul 2002 A1
20020096523 Pyles Jul 2002 A1
20020096524 Hardesty Jul 2002 A1
20020100758 Pyles Aug 2002 A1
20020104266 Ranaudo Aug 2002 A1
20020116924 Winkelmann et al. Aug 2002 A1
20020185199 Myers Dec 2002 A1
20030089719 Berger May 2003 A1
20030102316 Forest Jun 2003 A1
20030201265 Lin Oct 2003 A1
20030205979 Papari et al. Nov 2003 A1
20030230576 Lin Dec 2003 A1
20040016756 Lin Jan 2004 A1
20040028572 Sham et al. Feb 2004 A1
20040134924 Hansen et al. Jul 2004 A1
20040140782 Okabe et al. Jul 2004 A1
20040164077 Kuo Aug 2004 A1
20040174268 Scott et al. Sep 2004 A1
20040175303 Lin Sep 2004 A1
20040199401 Wagner Oct 2004 A1
20040200938 Forlivio Oct 2004 A1
20040206758 Lin Oct 2004 A1
20040206760 Gagnebin Oct 2004 A1
20040250711 Ernst Dec 2004 A1
20040251746 Ichimaru et al. Dec 2004 A1
20050017006 Kuo Jan 2005 A1
20050017010 Siegel et al. Jan 2005 A1
20050029281 Westermann et al. Feb 2005 A1
20050129803 Umeda et al. Jun 2005 A1
20050258177 Woodson Nov 2005 A1
20050258794 Fukuizumi Nov 2005 A1
20060027579 Yang et al. Feb 2006 A1
20060103086 Niemeyer et al. May 2006 A1
20060110537 Huang et al. May 2006 A1
20060118566 Lin Jun 2006 A1
20060138149 Tracy Jun 2006 A1
20060156948 Hendriks et al. Jul 2006 A1
20060163257 Golbert Jul 2006 A1
20060175336 Wang Aug 2006 A1
20060186121 Yang et al. Aug 2006 A1
20060196874 Yang Sep 2006 A1
20060237641 Moeller et al. Oct 2006 A1
20060249510 Lin Nov 2006 A1
20060278643 Chiou Dec 2006 A1
20070012699 Yang et al. Jan 2007 A1
20070034334 Ramsey et al. Feb 2007 A1
20070045326 Tramontina et al. Mar 2007 A1
20070090112 Kalman et al. Apr 2007 A1
20070114847 Ichimaru et al. May 2007 A1
20070181579 Kuo et al. Aug 2007 A1
20070209846 Wilson Sep 2007 A1
20070215622 Perez Sep 2007 A1
20070241109 Lin Oct 2007 A1
20070266637 McGowan Nov 2007 A1
20070272691 Wang et al. Nov 2007 A1
20070289972 Wynn et al. Dec 2007 A1
20080011754 Ramsey Jan 2008 A1
20080011910 Ramsey Jan 2008 A1
20080041863 Forest Feb 2008 A1
20080083756 Daniels Apr 2008 A1
20080083757 Parker et al. Apr 2008 A1
20080099274 Seel May 2008 A1
20080128428 Beckerman Jun 2008 A1
20080164257 Boll et al. Jul 2008 A1
20080236275 Breed et al. Oct 2008 A1
20080257889 Kovacevich et al. Oct 2008 A1
20080257890 Kovacevich et al. Oct 2008 A1
20080257891 Kovacevich et al. Oct 2008 A1
20080264948 Kovacevich et al. Oct 2008 A1
20080264950 Kovacevich et al. Oct 2008 A1
20080272119 Efstathiou Nov 2008 A1
20080272127 Kovacevich et al. Nov 2008 A1
20090071959 Cheung Mar 2009 A1
20090084788 Yang et al. Apr 2009 A1
20090136341 Kenyon May 2009 A1
20090214606 Bujard et al. Aug 2009 A1
20090230131 McDuffie et al. Sep 2009 A1
20090261105 Cunningham et al. Oct 2009 A1
20090266836 Mobley Oct 2009 A1
20100006572 Chiou Jan 2010 A1
20100084235 Lu Apr 2010 A1
20100096894 Fukai Apr 2010 A1
20100122985 Peters et al. May 2010 A1
20100147865 Yang et al. Jun 2010 A1
20100170904 Kalman et al. Jul 2010 A1
20100178105 Monneret Jul 2010 A1
20100193518 Tontarelli Aug 2010 A1
20100237074 Yang et al. Sep 2010 A1
20100252557 Clements Oct 2010 A1
20100294769 Lee et al. Nov 2010 A1
20110017735 Wang et al. Jan 2011 A1
20110049149 Shih Mar 2011 A1
20110056952 Borowski et al. Mar 2011 A1
20110139781 Jin et al. Jun 2011 A1
20110272409 Kasbohm Nov 2011 A1
20120145932 Yao et al. Jun 2012 A1
20120234849 Hughes et al. Sep 2012 A1
20120261423 Zawrotny et al. Oct 2012 A1
20130048641 Romano Feb 2013 A1
20130097809 Weber et al. Apr 2013 A1
20130105487 Baik May 2013 A1
20130240592 Woodruff Sep 2013 A1
20130248535 Wolfe et al. Sep 2013 A1
20130300119 Anzalon et al. Nov 2013 A1
20140183193 Hammond et al. Jul 2014 A1
20140238989 Wang et al. Aug 2014 A1
20140271757 Agrawal Sep 2014 A1
20140305946 Han Oct 2014 A1
20140345453 Oh et al. Nov 2014 A1
20150251849 Yang et al. Sep 2015 A1
20150321841 Salas et al. Nov 2015 A1
20160200508 Thoma et al. Jul 2016 A1
20170050404 Henken et al. Feb 2017 A1
20170127669 Yang et al. May 2017 A1
20170166167 Heller et al. Jun 2017 A1
20190077595 Wang et al. Mar 2019 A1
20190185263 Yang et al. Jun 2019 A1
20190276232 Yang et al. Sep 2019 A1
20200148467 Yang et al. May 2020 A1
20200307907 Yang et al. Oct 2020 A1
20200407159 Yang et al. Dec 2020 A1
Foreign Referenced Citations (164)
Number Date Country
622536 Apr 1992 AU
365296 Nov 2015 AU
201614908 Nov 2016 AU
201614909 Nov 2016 AU
2182840 Sep 1997 CA
2519295 Mar 2007 CA
132181 Jun 2010 CA
136938 May 2011 CA
141819 Apr 2012 CA
146601 Feb 2013 CA
152797 Apr 2014 CA
158595 Apr 2015 CA
158685 Apr 2015 CA
164264 Oct 2016 CA
164265 Oct 2016 CA
167073 Oct 2016 CA
170360 Mar 2017 CA
170399 Mar 2017 CA
168936 Oct 2017 CA
2075182 Apr 1991 CN
1570196 Jan 2005 CN
1918002 Feb 2007 CN
200964993 Oct 2007 CN
101177946 May 2008 CN
201105898 Aug 2008 CN
101509131 Aug 2009 CN
201372076 Dec 2009 CN
201447201 May 2010 CN
201512253 Jun 2010 CN
201597962 Oct 2010 CN
102190144 Sep 2011 CN
301947175 Jun 2012 CN
103072348 May 2013 CN
103207416 Jul 2013 CN
103300590 Sep 2013 CN
103303618 Sep 2013 CN
103381944 Nov 2013 CN
302771721 Mar 2014 CN
104016030 Sep 2014 CN
303188855 Apr 2015 CN
303206241 May 2015 CN
204587817 Aug 2015 CN
105015986 Nov 2015 CN
303611394 Mar 2016 CN
303622098 Mar 2016 CN
205169479 Apr 2016 CN
106103299 Nov 2016 CN
303967208 Dec 2016 CN
304018339 Jan 2017 CN
304018340 Jan 2017 CN
106546203 Mar 2017 CN
107032015 Aug 2017 CN
201310076306.0 Dec 2017 CN
201580000648.1 Jan 2018 CN
201730168630.4 Feb 2018 CN
1610087 Jul 1950 DE
822376 Nov 1951 DE
1283741 Jul 1966 DE
8436939 Mar 1985 DE
9108341 Oct 1991 DE
4225936 Feb 1994 DE
19525885 Mar 1997 DE
19617823 Nov 1997 DE
19809331 May 1999 DE
29918687 Mar 2000 DE
19933180 Jan 2001 DE
10148997 Apr 2003 DE
20217561 Mar 2004 DE
10337806 Mar 2005 DE
0582240 Jul 1993 EP
0903305 Mar 1999 EP
0906876 Apr 1999 EP
1094017 Apr 2001 EP
1162161 Dec 2001 EP
1361176 Nov 2003 EP
1136393 Apr 2004 EP
1447342 Aug 2004 EP
1600373 Nov 2005 EP
1647503 Apr 2006 EP
1686073 Aug 2006 EP
1918223 May 2008 EP
1700799 Aug 2009 EP
001164826-0001 Sep 2009 EP
001232904-0001 Oct 2010 EP
2343250 Jul 2011 EP
001908575-0001 Aug 2011 EP
001317416-0001 Apr 2012 EP
001317416-0002 Apr 2012 EP
001335285-0001 Jul 2012 EP
001335293-0001 Jul 2012 EP
001381636-0001 Aug 2013 EP
001381792-0001 Aug 2013 EP
2636611 Sep 2013 EP
3144251 Mar 2014 EP
001420590-0001 Sep 2014 EP
2772454 Sep 2014 EP
2915763 Sep 2015 EP
2918518 Sep 2015 EP
002766782-0001 Nov 2015 EP
002766782-0002 Nov 2015 EP
002766881-0001 Nov 2015 EP
2364932 Apr 2016 EP
3042864 Jul 2016 EP
003177500-0001 Sep 2016 EP
003177500-0002 Sep 2016 EP
003362235-0001 Oct 2016 EP
003362052-0001 Nov 2016 EP
003996339-0001 May 2017 EP
003996339-0002 May 2017 EP
3214019 Sep 2017 EP
004554889-0001 Dec 2017 EP
2887152 Dec 2006 FR
191004921 Jun 1910 GB
1555543 Nov 1979 GB
2384418 Jul 2003 GB
02-152670 Jun 1990 JP
H06-56011 Aug 1994 JP
06-272888 Sep 1994 JP
2004-106713 Apr 2004 JP
2004-231237 Aug 2004 JP
D1300450 May 2007 JP
D1300451 May 2007 JP
D1322056 Feb 2008 JP
D1398668 Oct 2010 JP
D1550907 Apr 2016 JP
D1551184 Apr 2016 JP
1585339 Aug 2017 JP
20040087306 Oct 2004 KR
3003841370000 Jun 2005 KR
3004095430000 Mar 2006 KR
3004095430001 Jul 2006 KR
6908550 Dec 1970 NL
183920 May 1992 TW
230977 Sep 1994 TW
395392 Jun 2000 TW
D112733 Sep 2006 TW
D129485 Jul 2009 TW
D133382 Feb 2010 TW
D133678 Mar 2010 TW
145989 Mar 2012 TW
D147147 May 2012 TW
D154797 Jul 2013 TW
D158187 Jan 2014 TW
D161587 Jul 2014 TW
D162495 Aug 2014 TW
D168957 Jul 2015 TW
D170334 Sep 2015 TW
201538406 Oct 2015 TW
201544405 Dec 2015 TW
D176312 Jun 2016 TW
D176313 Jun 2016 TW
201720729 Jun 2017 TW
D183552 Jun 2017 TW
D184449 Jul 2017 TW
I670213 Sep 2019 TW
WO 9202430 Feb 1992 WO
WO 9633671 Oct 1996 WO
WO 2005080232 Sep 2005 WO
WO 2006079263 Aug 2006 WO
WO 2007139570 Dec 2007 WO
WO 2009114495 Sep 2009 WO
WO 2015134902 Sep 2015 WO
WO 2015138625 Sep 2015 WO
WO 2016054109 Apr 2016 WO
Non-Patent Literature Citations (9)
Entry
Trento Corner 23 Trash Can, Hailo product webpage, May 2008, http://www.hailo.de/html/default.asp?site=12_71_107&lang=en.
Schaefer, http://www.schaeferco.com/about_rollcoaters.html, 2007, in 12 pages.
Simplehuman Liner Rim Dual Bucket Rectangular Recycler with Liner Pocket, Stainless Steel, 58 Liter / 15 Gallon, Item No. CW2025, www.Amazon.com, site visited Dec. 29, 2015.
Web page showing picture of Hero Bullet trash can, archived Nov. 17, 2004, downloaded from http://web.archive.org/web/20041117003115/http://www.simplehuman.com/images/hero_bullet.jpg.
Agion Product Information Bulletin Regarding Agion Antimicrobial Type AC; publicly available at least as early as Oct. 2015 (in two pages).
Agion Material Safety Data Sheet; Agion Antimicrobial Type AC; publicly available at least as early as Oct. 2015 (in three pages).
Solomons, T.W. Graham, “Organic Chemistry” 6th ed. ISBN 0-471-01342-0 (1996) in 12 pages.
Wikipedia—Chromate and Dichromate, https://en.wikipedia.org/wiki/Chromate_and_dichromate, accessed Aug. 27, 2021, printed Aug. 27, 2021 in 5 pages.
Agion Product Information Bulletin, Agion Antimicrobial Type AC; publicly available at least as early as May 2020 (in two pages).
Related Publications (1)
Number Date Country
20230382638 A1 Nov 2023 US
Provisional Applications (1)
Number Date Country
62253612 Nov 2015 US
Continuations (2)
Number Date Country
Parent 17560056 Dec 2021 US
Child 18363302 US
Parent 15343899 Nov 2016 US
Child 17560056 US