WO2023027805A1 - Revêtements antimicrobiens à phases séparées et procédés pour les fabriquer et les utiliser - Google Patents

Revêtements antimicrobiens à phases séparées et procédés pour les fabriquer et les utiliser Download PDF

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Publication number
WO2023027805A1
WO2023027805A1 PCT/US2022/035397 US2022035397W WO2023027805A1 WO 2023027805 A1 WO2023027805 A1 WO 2023027805A1 US 2022035397 W US2022035397 W US 2022035397W WO 2023027805 A1 WO2023027805 A1 WO 2023027805A1
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WIPO (PCT)
Prior art keywords
antimicrobial
phase
solid
polymer
antimicrobial agent
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PCT/US2022/035397
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English (en)
Inventor
Adam Gross
Andrew Nowak
Michael Ventuleth
Stella Fors
Jason Graetz
Ashley DUSTIN
John VAJO
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Hrl Laboratories, Llc
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Publication date
Priority claimed from US17/852,307 external-priority patent/US20220361486A1/en
Application filed by Hrl Laboratories, Llc filed Critical Hrl Laboratories, Llc
Priority to EP22861859.1A priority Critical patent/EP4392495A1/fr
Priority to CN202280054421.5A priority patent/CN117813357A/zh
Publication of WO2023027805A1 publication Critical patent/WO2023027805A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/4808—Mixtures of two or more polyetherdiols
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015—Biocides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the present invention generally relates to phase-separated antimicrobial surfaces and coatings, compositions suitable for antimicrobial surfaces and coatings, and methods of making and using antimicrobial surfaces and coatings.
  • Coronavirus disease 2019 (“COVID-19”) is caused by severe acute respiratory syndrome coronavirus 2 (“SARS-CoV-2”).
  • SARS-CoV-2 severe acute respiratory syndrome coronavirus 2
  • the COVID-19 pandemic emphasized the importance of environmental cleanliness and hygiene management involving a wide variety of surfaces. Despite the strict hygiene measures which have been enforced, it has proven to be very difficult to sanitize surfaces all of the time. Even when sanitized, surfaces may get contaminated again.
  • Respiratory secretions or droplets expelled by infected individuals can contaminate surfaces and objects, creating fomites (contaminated surfaces).
  • Viable SARS-CoV-2 virus can be found on contaminated surfaces for periods ranging from hours to many days, depending on the ambient environment (including temperature and humidity) and the type of surface.
  • pathogens such as, but not limited to, SARS-CoV-2
  • One method of reducing pathogen transmission is to reduce the period of human vulnerability to infection by reducing the period of viability of SARS-CoV-2 on solids and surfaces.
  • Biocides in liquids are capable of inactivating at least 99.99% of SARS-CoV-2 in as little as 2 minutes, which is attributed to the rapid diffusion of the biocide to microbes and because water aids microbial dismemberment.
  • these approaches cannot always occur in real-time after a surface is contaminated.
  • antimicrobial coatings may be applied to a surface in order to kill bacteria and/or destroy viruses as they deposit.
  • conventional antimicrobial coatings typically require at least 2 hours, a time scale which is longer than indirect human-to- human interaction time, such as in an aircraft or shared vehicle, for example.
  • Existing solid coatings are limited by a low concentration of biocides at the surface due to slow biocide transport. The slow diffusion of biocides through the solid coating to the surface, competing with the removal of biocides from the surface by human and environmental contact, results in limited availability and requires up to 2 hours to kill 99.9% of bacteria and/or deactivate 99.9% of viruses.
  • an antimicrobial coating that enables fast transport rates of biocides for better effectiveness on deactivating SARS-CoV-2 on surfaces.
  • the coating should be safe, conveniently applied or fabricated, and durable. It is particularly desirable for such a coating to be capable of destroying at least 99%, preferably at least 99.9%, and more preferably at least 99.99% of bacteria and/or viruses in 30 minutes of contact.
  • Antimicrobial coatings including transparent antimicrobial coatings and/or antifouling antimicrobial coatings, are still desired. Antimicrobial coatings that are transparent and not easily stained are particularly of interest.
  • an antimicrobial structure comprising:
  • a discrete solid structural phase comprising a solid structural polymer, wherein the solid structural polymer is characterized by a glass-transition temperature from about 25°C to about 300°C;
  • a continuous transport phase that is interspersed within the discrete solid structural phase, wherein the continuous transport phase comprises a solid transport material;
  • an antimicrobial agent contained within the continuous transport phase wherein the antimicrobial agent is at least partially dissolved in a fluid and/or wherein the antimicrobial agent is in a solid solution with the continuous transport phase, wherein the discrete solid structural phase and the continuous transport phase are separated by an average phase-separation length selected from about 100 nanometers to about 500 microns.
  • the antimicrobial structure may be characterized by an optical transparency of about 80% or greater, such as about 90% or greater.
  • the optical transparency is calculated by averaging the transparency across light wavelengths from 400 nm to 800 nm, through a 100-micron film of the antimicrobial structure at 25°C and 1 bar.
  • the solid structural polymer is covalently bonded to the solid transport material.
  • the solid structural polymer is a non-fluorinated carbon-based polymer.
  • the non-fluorinated carbon-based polymer may be selected from the group consisting of polycarbonates, polyacrylates, polyalkanes, polyurethanes, polyethers, polyureas, polyesters, and combinations thereof.
  • the solid structural polymer is a polycarbonate, a polyacrylate, or a combination thereof.
  • the entire antimicrobial structure is non-fluorinated.
  • the solid transport material may be a hygroscopic solid transport polymer selected from the group consisting of poly(acrylic acid), polyethylene glycol), poly(2-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(2-methyl-2- oxazoline), poly(2-ethyl-2-oxazoline), poly(vinylpyrolidone), modified cellulosic polymers, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and combinations thereof, for example.
  • the solid transport material may be a hydrophobic, non-lipophobic solid transport polymer selected from the group consisting of polypropylene glycol), poly(tetramethylene glycol), polybutadiene, polycarbonate, polycaprolactone, acrylic polyols, and combinations thereof, for example.
  • the solid transport material may be a hydrophilic solid transport polymer with ionic charge, wherein the ionic charge is optionally present within the hydrophilic solid transport polymer as carboxylate groups, amine groups, sulfate groups, or phosphate groups, for example.
  • the solid transport material may be an electrolyte solid transport polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polycarbonates, polysiloxanes, polyvinylidene difluoride, and combinations thereof, for example.
  • the solid transport material is a solid transport polymer.
  • the solid transport polymer may be crosslinked, via a crosslinking molecule, with the solid structural polymer.
  • the crosslinking molecule may include at least one moiety selected from the group consisting of amine, hydroxyl, isocyanate, epoxide, carbodiimide, and combinations thereof, for example.
  • the antimicrobial agent is selected from quaternary ammonium molecules, such as (but not limited to) benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetalkonium chloride, or combinations thereof.
  • the antimicrobial agent is selected from metal ions, such as (but not limited to) silver, copper, zinc, or combinations thereof.
  • the antimicrobial agent is selected from metal oxide nanoparticles, such as (but not limited to) ZnO and/or CuO nanoparticles.
  • the antimicrobial agent is selected from acids, such as (but not limited to) citric acid, acetic acid, peracetic acid, glycolic acid, lactic acid, succinic acid, pyruvic acid, oxalic acid, hydrochloric acid, or combinations thereof.
  • acids such as (but not limited to) citric acid, acetic acid, peracetic acid, glycolic acid, lactic acid, succinic acid, pyruvic acid, oxalic acid, hydrochloric acid, or combinations thereof.
  • the antimicrobial agent is selected from bases, such as (but not limited to) ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, or combinations thereof.
  • the antimicrobial agent is selected from salts, such as (but not limited to) copper chloride, copper nitrate, copper citrate, copper acetate, zinc chloride, zinc nitrate, zinc citrate, zinc acetate, silver chloride, silver nitrate, silver citrate, silver acetate, or combinations thereof.
  • salts such as (but not limited to) copper chloride, copper nitrate, copper citrate, copper acetate, zinc chloride, zinc nitrate, zinc citrate, zinc acetate, silver chloride, silver nitrate, silver citrate, silver acetate, or combinations thereof.
  • the antimicrobial agent is selected from peroxides, such as (but not limited to) hydrogen peroxide, organic peroxides, or combinations thereof.
  • the antimicrobial agent is selected from N- halamines, such as (but not limited to) hydantoin, 4,4-dimethyl-2-oxazalidinone, tetramethyl-2-imidazolidinone, or combinations thereof.
  • the antimicrobial agent is selected from oxidizing molecules, such as (but not limited to) sodium hypochlorite, calcium hypochlorite, hypochlorous acid, hydrogen peroxide, or combinations thereof.
  • the antimicrobial agent may be at least partially dissolved in a fluid that is contained within the continuous transport phase.
  • the fluid may be selected from the group consisting of water, dialkyl carbonate, propylene carbonate, y- butyrolactone, 2-phenoxyethanol, dimethyl sulfoxide, /-butanol, glycerol, propylene glycol, ionic liquids, and combinations thereof, for example.
  • the antimicrobial structure is characterized in that the antimicrobial agent has a diffusion coefficient from about IO -18 m 2 /s to about IO -9 m 2 /s, measured at 25°C and 1 bar, within the continuous transport phase.
  • the antimicrobial agent is electrically or electrochemically rechargeable.
  • the antimicrobial agent may be hypochlorite, hypochlorous acid, hydrogen peroxide, or a combination thereof, wherein the electrodes are configured to generate the antimicrobial agent in situ.
  • the antimicrobial structure may further contain one or more additives selected from the group consisting of buffers, UV stabilizers, fillers, pigments, flattening agents, flame retardants, salts, surfactants, defoamers, dispersants, wetting agents, antioxidants, and combinations thereof, for example.
  • additives selected from the group consisting of buffers, UV stabilizers, fillers, pigments, flattening agents, flame retardants, salts, surfactants, defoamers, dispersants, wetting agents, antioxidants, and combinations thereof, for example.
  • the antimicrobial structure further contains one or more protective layers.
  • the antimicrobial structure may be a coating or may be present in a coating.
  • the antimicrobial structure may be present at a surface of a bulk object.
  • FIG. l is a top view of an antimicrobial structure containing a discrete solid structural phase that provides abrasion resistance, and a continuous transport phase that transports antimicrobial agents to the outer surface to inactivate or kill microbes, in some embodiments.
  • FIG. 2 is a through-thickness side view of a coating or bulk material containing a discrete solid structural phase and a continuous transport phase that stores antimicrobial agents and transports the antimicrobial agents to the outer layer in order to inactivate or kill microbes, in some embodiments.
  • FIG. 3 is a sketch of an antimicrobial structure (through-thickness side view) containing an antimicrobial agent that is rechargeable by applying a voltage between two embedded electrodes of opposite polarity, in some embodiments.
  • FIG. 4 shows the magnitude of impedance spectra (normalized by the film thickness) for six films with various polyethylene glycol (PEG) concentrations (0 vol%, 25 vol%, 40 vol%, 50 vol%, 60 vol%, and 75 vol% PEG, with the remainder poly(tetrahydrofuran) (pTHF) after immersion in a 10% benzalkonium chloride (in water) solution for approximately 2 days, in Example 3.
  • PEG polyethylene glycol
  • FIG. 5 shows a plot of specific conductivity (left axis) and diffusion coefficients (right axis) as a function of PEG concentration (0 vol%, 25 vol%, 40 vol%, 50 vol%, 60 vol%, and 75 vol%) after immersion in a 10 wt% benzalkonium chloride (in water) solution for approximately 2 days, in Example 3.
  • FIG. 6 is a photographic image of a transparent film, in the Comparative Example.
  • FIG. 7 is a photographic image of the Comparative Example film after staining with coffee including cream, followed by attempted subsequent cleaning.
  • FIG. 8 is a photographic image of the Comparative Example film after staining with lipstick, followed by attempted subsequent cleaning.
  • FIG. 9 is a photographic image of the transparent film of Example 4.
  • FIG. 10 is a photographic image of the Example 4 film after staining with coffee including cream, followed by subsequent cleaning.
  • FIG. 11 is a photographic image of the Example 4 film after staining with lipstick, followed by subsequent cleaning.
  • FIG. 12 is an optical micrograph of the Example 4 film, revealing the phase separation between the continuous transport phase (PEG) and the discrete solid structural phase polycarbonate (PC).
  • PEG continuous transport phase
  • PC discrete solid structural phase polycarbonate
  • FIG. 13 is a plot of specific conductivity, measured by electrochemical impedance spectroscopy (EIS), from a series of phase-separated antimicrobial films after immersion in a 10 wt% quat or 10 wt% citric acid solution for about 2 days, in Example 5.
  • EIS electrochemical impedance spectroscopy
  • room temperature should be understood as about 25°C, which for purposes of this patent application means 25°C ⁇ 5°C.
  • Variations of this invention are premised on the discovery of coatings that are stain-resistant without the use of fluorinated polymers or additives.
  • the stain resistance arises from the incorporation of materials with a glass-transition temperature above room temperature, instead of requiring fluorinated materials to avoid soil infiltration.
  • the coatings contain a discrete solid structural phase combined with a continuous transport phase.
  • the discrete solid structural phase provides mechanical integrity and anti-fouling characteristics (stain resistance).
  • the continuous transport phase acts as a medium for the fast diffusion of antimicrobial agents.
  • the stain-resistant coatings are optically transparent.
  • the transparency is unexpected in phase-separated polymers (biphasic polymers) with micron-size phase separation that scatters light off the domain structure. Even when the materials that make up the two domains are similar in index of refraction, small differences normally create a hazy or translucent appearance.
  • a solid structural polymer with T g above room temperature (such as polycarbonate) along with a transport phase, creates transparent and stain-resistant polymers with 1000* greater transport of antimicrobial agents compared to single phase-coatings.
  • the fast transport enables the replenishment of antimicrobial agents in the coating, such as in the time period between coating contacts from different people.
  • Some variations of the invention are predicated on polymeric coatings that are solid but have fast transport rates of antimicrobial agents, enabled by a two- phase architecture with a discrete solid structural phase combined with an antimicrobial-containing continuous transport phase that is phase-separated with the discrete solid structural phase.
  • “fast transport” means a specific conductivity of at least ICT 5 mS/cm.
  • Antimicrobial agents or synonymously “antimicrobial actives” include germicides, bactericides, virucides (antivirals), antifungals, antiprotozoal s, antiparasites, and biocides. In some embodiments, antimicrobial agents are specifically bactericides, such as disinfectants, antiseptics, and/or antibiotics. In some embodiments, antimicrobial agents are specifically virucides, or include virucides.
  • This invention resolves the conventional trade-off between antifouling and fluorinated material content. Fluorinated materials are usually employed in order to reject stains and fluids.
  • the structure disclosed herein employs a biphasic polymer with one component (the solid structural polymer) having a glasstransition temperature above the use temperature. The crystallized nature of the solid structural polymer being below its T g results in the material not being penetrated by stains.
  • a second phase which is a continuous transport phase, enables removal of stains on the surface.
  • This invention also resolves the conventional trade-off between transport of absorbed molecules and transparency.
  • Phase separation of 0.1-500 pm results in up to 1000* faster diffusion compared to nanoscale ( ⁇ 100 nm) phase separation.
  • Fast transport of antimicrobial agents is retained without creating an optically opaque antimicrobial structure.
  • a structural phase with a T g above room temperature inhibits surface staining.
  • an antimicrobial structure comprising:
  • a discrete solid structural phase comprising a solid structural polymer, wherein the solid structural polymer is characterized by a glass-transition temperature from about 25°C to about 300°C;
  • an antimicrobial agent contained within the continuous transport phase wherein the antimicrobial agent is at least partially dissolved in a fluid and/or wherein the antimicrobial agent is in a solid solution with the continuous transport phase, wherein the discrete solid structural phase and the continuous transport phase are separated by an average phase-separation length selected from about 100 nanometers to about 500 microns.
  • the glass-transition temperature T g of a material characterizes temperatures at which a glass transition is observed.
  • a glass transition is the gradual and reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle “glassy” state into a viscous or rubbery state as the temperature is increased.
  • a glass transition generally occurs over a temperature range and depends on the thermal history; therefore, a test method needs to be defined in order to ascertain a value of T g for a given material.
  • the glass-transition temperature T g is measured according to the equal-areas method described in International Standard ISO 11357-2, “Plastics — Differential scanning calorimetry (DSC) — Part 2: Determination of glass transition temperature and step height”, Third Edition, March 2020, which is hereby incorporated by reference.
  • the measurement of T g uses the energy release on heating in differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the change in heat flow rate as a function of temperature is recorded and the glass-transition temperature and step height are determined from the curve thus obtained.
  • the glass transition is assigned to the temperature obtained by drawing a vertical line such that the areas between DSC trace and baselines below and above the curve are equal.
  • the glass-transition temperature depends on the actual used cooling rate and annealing conditions below T g . Unperturbed glass transitions are obtained only if cooling and subsequent heating rate are the same and no significant physical ageing occurred due to annealing below T g . If a sample is cooled significantly slower or annealed below T g , enthalpy relaxations can occur, resulting in endotherm peaks just above T g . Peaks due to enthalpy relaxation will disappear by extrapolating to zero heating rates.
  • the equalareas method provides the best procedure to obtain an accurate T g in the case of occurrence of enthalpy relaxations. The equal-areas method is described in section 10.1.2 of the ISO 11357-2.
  • polymers with T g ⁇ 25°C include silicones, polyvinylidene fluoride, polyvinyl fluoride, polychloroprene, polyethylene, polypropylene, and poly(butyl acrylate). Many examples of polymers with T g > 25°C are provided below.
  • T g > 25°C is based on the use temperature of the antimicrobial structure being about 25°C. If the use temperature is higher, such as 40°C, then the T g of the solid structural polymer may be about 40°C or higher. Likewise, in certain situations where the antimicrobial-structure use temperature is lower, such as 0°C, then the T g of the solid structural polymer may be about 0°C or higher.
  • Reference to a range of T g means that a solid structural polymer may be selected such that its single value of T g , measured pursuant to ISO 11357-2, falls within the specified range.
  • a high glass-transition temperature (i.e., T g > 25°C) of the solid structural polymer improves the anti-fouling performance of the antimicrobial structure (e.g., a coating).
  • Previously used structural phases such as poly(butadiene) or poly(tetrahydrofuran) have T g ⁇ 25°C and require at least 10 vol% of a fluorinated polyol added to the structural phase to reject stains.
  • Non-fluorinated solid structural polymers are preferable for resisting penetration of external soils into the coating, such as a fluorine-free anti-fouling coating.
  • the solid structural polymer is a non-fluorinated carbon-based polymer.
  • the non-fluorinated carbon-based polymer may be selected from the group consisting of polycarbonates, polyacrylates, polyalkanes, polyurethanes, polyethers, polyureas, polyesters, and combinations thereof.
  • the solid structural polymer is a polycarbonate, a polyacrylate, or a combination thereof.
  • the solid structural polymer is a polycarbonate, such as polycarbonate end-terminated with hydroxyl groups (-OH), amino groups (-NH2), and/or epoxide groups (— O— ).
  • the solid structural polymer is a polyacrylate, such as a polyacrylate functionalized with alkanes, alkenes, and/or aromatic groups.
  • the continuous transport phase may include a hygroscopic solid transport polymer as a solid transport material.
  • the solid transport material may be a hygroscopic solid transport polymer selected from the group consisting of poly(acrylic acid), poly(ethylene glycol), poly(2 -hydroxyethyl methacrylate), poly(vinyl imidazole), poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), poly(vinylpyrolidone), modified cellulosic polymers, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and combinations thereof, for example.
  • the continuous transport phase may include a hydrophobic, non- lipophobic solid transport polymer.
  • the solid transport material may be a hydrophobic, non-lipophobic solid transport polymer selected from the group consisting of polypropylene glycol), poly(tetramethylene glycol), polybutadiene (or other unsaturated polyolefins), polycarbonate, polycaprolactone, acrylic polyols, and combinations thereof, for example.
  • the continuous transport phase may include a hydrophilic solid transport polymer with ionic charge.
  • the solid transport material may be a hydrophilic solid transport polymer with ionic charge, wherein the ionic charge is optionally present within the hydrophilic solid transport polymer as carboxylate groups, amine groups, sulfate groups, or phosphate groups, for example.
  • the continuous transport phase may include an electrolyte solid transport polymer.
  • the solid transport material may be an electrolyte solid transport polymer selected from the group consisting of polyethylene oxide, polypropylene oxide, polycarbonates, polysiloxanes, polyvinylidene difluoride, and combinations thereof, for example.
  • a solid transport material is a solid transport polymer.
  • the solid structural polymer may be crosslinked, via a crosslinking molecule, with the solid transport polymer.
  • the crosslinking molecule may include at least one moiety selected from the group consisting of amine, hydroxyl, isocyanate, epoxide, carbodiimide, and combinations thereof, for example.
  • Exemplary isocyanates include Vestanat® 1890 and Desmodur® 3300.
  • the crosslinking molecule may also function as a chain extender. Alternatively, or additionally, a separate chain extender may be used.
  • a crosslinker or chain extender is selected from polyol or polyamine crosslinkers or chain extenders that possess a functionality of 2, 3, or greater.
  • polyol or polyamine crosslinkers or chain extenders are selected from the group consisting of 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, 1,2-ethanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanol amine, di ethanol amine, methyldiethanolamine, phenyldiethanolamine, glycerol, trimethylolpropane, 1,2,6- hexanetriol, triethanolamine, pentaerythritol propoxylate
  • the average phase-separation length, between the discrete solid structural phase and the continuous transport phase, may vary widely. In some embodiments, the average phase-separation length is selected from about 100 nanometers to about 100 microns. In some embodiments, the average phaseseparation length is selected from about 200 nanometers to about 50 microns. In some embodiments, the average phase-separation length is selected from about 1 micron to about 100 microns. In some embodiments, the average phase-separation length is selected from about 1 micron to about 50 microns.
  • the average phase-separation length is selected from about, at least about, or at most about 100 nm, 125 nm, 150 nm, 175 nm, 200 nm, 250 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm, 60 pm, 70 pm, 80 pm, 90 pm, 100 pm, 150 pm, 200 pm, 250 pm, 300 pm, 350 pm, 400 pm, 450 pm, or 500 pm, including any intervening ranges (e.g., 150 nm-5 pm, 500 nm-45 pm, etc.).
  • phase-separation lengths There may be narrow or broad distribution of phase-separation lengths.
  • Exemplary imaging techniques to measure phase separation include, but are not limited to, confocal laser scanning microscopy, scanning electron microscopy, scanning tunneling microscopy, and atomic force microscopy.
  • the antimicrobial structure is preferably transparent or partially transparent for optical frequencies or ordinary light.
  • Transparent antimicrobial coatings are useful because they do not change the appearance of underlying substrates being coated (e.g., a door handle).
  • the optical transparency of the antimicrobial structure may be about, or at least about, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, for example.
  • the optical transparency of an antimicrobial structure is the light transmittance, averaged across light wavelengths from 400 nm to 800 nm, through a 100-micron film of the antimicrobial structure at 25°C and 1 bar.
  • the structure may be characterized as translucent.
  • the optical transparency of the antimicrobial structure is a function of the optical transparency of the nature and extent of individual components — the discrete solid structural phase, the continuous transport phase, the antimicrobial agent, and any other additives.
  • each component is at least partially transparent.
  • Antimicrobial agent liquids or solutions are typically clear. When one component is relatively opaque, the overall antimicrobial structure may still have an acceptable transparency, depending on the amount of the relatively opaque component, for example.
  • different phases of the antimicrobial structure are selected such that the respective refraction indices are matched or substantially similar.
  • polytetrahydrofuran with polypropylene glycol) which are index-matched to within 2%.
  • polycarbonate with poly(ethylene glycol) which are index-matched to within 10%.
  • the continuous transport phase and the discrete solid structural phase are selected such that the index of refraction matches to within ⁇ 10%, preferably within ⁇ 5%, more preferably with ⁇ 2%, and most preferably with ⁇ 1%. Note, however, that refractive-index matching is not a requirement of the present invention.
  • the optical transparency of the antimicrobial structure may temporarily deviate from its initial value when dirt or debris contaminates the surface, before the surface is wiped or cleaned.
  • the antifouling nature of the disclosed antimicrobial structures is important, to avoid permanent decrease in optical transparency in the case of non-cleanable fouling.
  • the antimicrobial agent is selected from quaternary ammonium molecules, such as (but not limited to) benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetalkonium chloride, or combinations thereof.
  • the antimicrobial agent is selected from metal ions, such as (but not limited to) silver, copper, zinc, or combinations thereof.
  • the antimicrobial agent is selected from metal oxide nanoparticles, such as (but not limited to) ZnO and/or CuO nanoparticles.
  • the antimicrobial agent is selected from acids, such as (but not limited to) citric acid, acetic acid, peracetic acid, glycolic acid, lactic acid, succinic acid, pyruvic acid, oxalic acid, hydrochloric acid, or combinations thereof.
  • the antimicrobial agent is selected from bases, such as (but not limited to) ammonia, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, or combinations thereof.
  • the antimicrobial agent is selected from salts, such as (but not limited to) copper chloride, copper nitrate, copper citrate, copper acetate, zinc chloride, zinc nitrate, zinc citrate, zinc acetate, silver chloride, silver nitrate, silver citrate, silver acetate, or combinations thereof.
  • the antimicrobial agent is selected from peroxides, such as (but not limited to) hydrogen peroxide, organic peroxides (e.g., benzoic peroxide), or combinations thereof.
  • the antimicrobial agent is selected from N- halamines, such as (but not limited to) hydantoin, 4,4-dimethyl-2-oxazalidinone, tetramethyl-2-imidazolidinone, or combinations thereof.
  • the antimicrobial agent is selected from oxidizing molecules, such as (but not limited to) sodium hypochlorite, calcium hypochlorite, hypochlorous acid, hydrogen peroxide, or combinations thereof.
  • the antimicrobial agent preferably is not in the form of purely solid particles. In preferred embodiments, the antimicrobial agent is not in the form of solid particles at temperatures of use (e.g., 20-40°C). Quaternary ammonium salts are deliquescent and will form a concentrated solution that does not dry out. Quaternary ammonium salts may absorb moisture from the air or may be dissolved in a solvent, such as ethylene glycol or oligomers thereof.
  • Hypochlorous acid, sodium hypochlorite, calcium hypochlorite, and hydrogen peroxide only exist as solutions or liquids, practically speaking. Hypochlorous acid and sodium hypochlorite are never found dry because they decompose with increasing concentration before they dry out. Hydrogen peroxide is a liquid above -0.4°C at 1 bar pressure.
  • the antimicrobial agent may be at least partially dissolved in a fluid that is contained within the continuous transport phase.
  • the fluid may be selected from the group consisting of water, dialkyl carbonate, propylene carbonate, y- butyrolactone, 2-phenoxyethanol, dimethyl sulfoxide, /-butanol, glycerol, propylene glycol, ionic liquids, and combinations thereof, for example.
  • the antimicrobial structure is characterized in that the antimicrobial agent has a diffusion coefficient from about 10 -18 m 2 /s to about IO -9 m 2 /s, measured at 25°C and 1 bar, within the continuous transport phase. In certain embodiments, the antimicrobial agent has a diffusion coefficient from about IO -16 m 2 /s to about 10 -11 m 2 /s, measured at 25°C and 1 bar, within the continuous transport phase.
  • the antimicrobial agent has a diffusion coefficient, measured at 25°C and 1 bar, within the continuous transport phase, of about, or at least about IO -17 m 2 /s, IO -16 m 2 /s, ICT 15 m 2 /s, IO -14 m 2 /s, ICT 13 m 2 /s, IO -12 m 2 /s, 10 -11 m 2 /s, IO -10 m 2 /s, or IO -9 m 2 /s, including any intervening ranges.
  • the antimicrobial agent is electrically or electrochemically rechargeable.
  • the antimicrobial agent may be hypochlorite, hypochlorous acid, hydrogen peroxide, or a combination thereof, wherein the electrodes are configured to generate the antimicrobial agent in situ.
  • an antimicrobial structure comprising:
  • first and second electrodes wherein the antimicrobial agent is electrically or electrochemically rechargeable when a voltage is applied between the first and second electrodes, and wherein the discrete solid structural phase and the continuous transport phase are separated by an average phase-separation length from about 100 nanometers to about 500 microns.
  • the first and second electrodes are embedded within the discrete solid structural phase. In some embodiments, at least one of the first and second electrodes is an outer layer disposed on the discrete solid structural phase. In some embodiments, the first electrode is a first outer layer disposed on the discrete solid structural phase, and the second electrode is a second outer layer disposed on the discrete solid structural phase. In some embodiments, one of the first and second electrodes is integrated with a base substrate or a wall. One or both of the first and second electrodes may have a non-planar electrode architecture. The electrodes may be fabricated from metal, carbon, or other electrically conductive materials, in the form of grids, meshes, or perforated plates, or other configurations that are electrochemically stable. In certain embodiments, the electrodes contain a catalyst. The catalyst may be selected from the group consisting of Ti, Pt, Ru, Ir, Ta, Rh, Pd, Ag, oxides thereof, or a combination of the foregoing, for example.
  • An antimicrobial structure with embedded electrodes may be used in a method of charging or recharging the antimicrobial structure with an antimicrobial agent, the method comprising:
  • an antimicrobial structure comprising: a discrete solid structural phase comprising a solid structural material; a continuous transport phase that is interspersed within the discrete solid structural phase, wherein the continuous transport phase comprises a solid transport material; and first and second electrodes;
  • the method may be used to initially charge the antimicrobial agent into the antimicrobial structure. Also, the method may be used to recharge the antimicrobial agent into the antimicrobial structure after a period of use.
  • step (ii) the continuous transport phase is wet with a liquid solution containing the antimicrobial agent precursor and/or a liquid electrolyte containing the antimicrobial agent precursor.
  • the antimicrobial agent precursor may be sodium chloride, converting to sodium hypochlorite and/or hypochlorous acid as the antimicrobial agent.
  • the antimicrobial agent precursor may be sodium hypochlorite and/or hypochlorous acid, converting to chlorine-containing A-halamines as the antimicrobial agent.
  • the antimicrobial agent precursor may be water, converting to hydrogen peroxide (H2O2) as the antimicrobial agent.
  • the antimicrobial structure may further contain one or more additives selected from the group consisting of buffers, UV stabilizers, fillers, pigments, flattening agents, flame retardants, salts, surfactants, defoamers, dispersants, wetting agents, antioxidants, and combinations thereof, for example.
  • additives selected from the group consisting of buffers, UV stabilizers, fillers, pigments, flattening agents, flame retardants, salts, surfactants, defoamers, dispersants, wetting agents, antioxidants, and combinations thereof, for example.
  • the entire antimicrobial structure is nonfluorinated, i.e., contains essentially no fluorine (including the discrete solid structural phase, the continuous transport phase, the antimicrobial agent, crosslinking agents, chain extenders, other additives, etc.)
  • the antimicrobial structure further contains one or more protective layers.
  • the protective layers are disposed on the outside of the antimicrobial structure, protecting the structure from the environment.
  • a protective layer may be fabricated from polyurethanes, silicones, epoxy-amine materials, polysulfides, natural or synthetic rubber, fluoropolymers, or combinations thereof, for example.
  • the antimicrobial structure may be a coating or may be present in a coating.
  • the antimicrobial structure may be present at a surface of a bulk object.
  • This invention is capable of resolving the technical tradeoffs between antimicrobial solutions and solid surfaces.
  • Conventional liquid solutions are fast but not persistent. Liquid solutions can reduce the population of bacteria and viruses on a timescale of minutes, but the liquid solutions do not stay on surfaces and have a onetime effect.
  • Conventional solid antimicrobial surfaces reduce bacteria and virus populations quite slowly, causing bacteria and virus to remain on surfaces for extended times. See Behzadinasab et al., “A Surface Coating that Rapidly Inactivates SARS-CoV-2”, ACS AppL Mater. Interfaces 2020, 12, 31, as an example of an antimicrobial coating that requires at least 1 hour for effectiveness.
  • the slow activity of conventional solid antimicrobial materials is due to the time needed for antimicrobial agents to diffuse to the surface. These surfaces also fail to work if they are dirty, because soil blocks the transport of antimicrobial agents to the surface.
  • the material disclosed herein breaks the tradeoff between activity and persistence.
  • the discrete solid structural phase provides persistence on a surface while the continuous transport phase allows antimicrobial agents to move to microbes (e.g., viruses or bacteria) on the surface at order-of-magnitude faster rates than is possible with diffusion through a single solid material.
  • a biphasic structure simultaneously provides durability and fast transport to the surface where antimicrobial agents can kill or deactivate microbes at the surface.
  • the continuous transport phase may contain an aqueous or non-aqueous solvent or electrolyte to further enhance transport rates of antimicrobial agents.
  • the continuous transport phase passively absorbs water from the environment, which water may enhance transport rates of antimicrobial agents and/or improve the effectiveness of the antimicrobial agents.
  • an antimicrobial structure comprising:
  • an antimicrobial structure intended to contain an antimicrobial agent, the antimicrobial structure comprising:
  • a discrete solid structural phase comprising a solid structural material
  • a continuous transport phase that is interspersed within the discrete solid structural phase, wherein the continuous transport phase comprises a solid transport material, and wherein the continuous transport phase is capable of containing an antimicrobial agent (such as at a time of intended use or regeneration), wherein the discrete solid structural phase and the continuous transport phase are separated by an average phase-separation length from about 100 nanometers to about 500 microns.
  • the solid structural material is or includes a solid structural polymer selected from the group consisting of a non-fluorinated carbon-based polymer, a silicone, a fluorinated polymer, and combinations thereof. These types of polymers are preferred when anti-wetting properties (from water or other hydrophilic liquids) are desired for the solid structural material, providing a dryfeel surface.
  • a hydrophobic and/or lyophobic solid structural material prevents or minimizes soil adhesion and penetration of debris into the overall structure.
  • a non-fluorinated carbon-based polymer may be selected from the group consisting of polyalkanes, polyurethanes, polyethers, polyureas, polyesters, and combinations thereof.
  • a silicone may be selected from the group consisting of polydimethyl siloxane, polytrifluoropropylmethyl siloxane, polyaminopropylmethyl siloxane, polyaminoethylaminopropylmethyl siloxane, polyaminoethylaminoisobutylmethyl siloxane, and combinations thereof.
  • a fluorinated polymer may be selected from the group consisting of fluorinated polyols, perfluorocarbons, perfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes, polyvinylidene fluoride, polytrifluoroethylene, and combinations thereof.
  • the solid transport material is or includes a solid transport polymer selected from a hygroscopic polymer, a hydrophobic and non- lipophobic polymer, a hydrophilic polymer, an electrolyte polymer, and combinations thereof.
  • the continuous transport phase may further include a transport-phase liquid, which may be organic or inorganic.
  • the solid transport material is or includes a hygroscopic solid transport polymer.
  • the hygroscopic solid transport polymer may be selected from the group consisting of poly(acrylic acid), polyethylene glycol), poly(2 -hydroxyethyl methacrylate), poly(vinyl imidazole), poly(2-methyl-2- oxazoline), poly(2-ethyl-2-oxazoline), poly(vinylpyrolidone), modified cellulosic polymers, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and combinations thereof, for example.
  • a hygroscopic solid transport polymer may be a crosslinked poly(acrylic acid) emulsion polymer (e.g., Carbopol® polymers) that can bind with antimicrobial agents.
  • the solid transport material is or includes a hydrophobic, non-lipophobic solid transport polymer.
  • the hydrophobic, non- lipophobic solid transport polymer may be selected from the group consisting of polypropylene glycol) (PPG), poly(tetramethylene glycol) (PTMEG, also known as polytetrahydrofuran or polyTHF), polybutadiene, polycarbonate, polycaprolactone, acrylic polyols, and combinations thereof, for example.
  • the solid transport material is or includes a hydrophilic solid transport polymer.
  • the hydrophilic solid transport polymer may be a polymer created with ionic charge that may be present within the hydrophilic solid transport polymer as pendant or main-chain carboxylate groups, amine groups, sulfate groups, or phosphate groups, for example.
  • monomers containing ionic charge are inserted along the polymer backbone.
  • the hydrophilic solid transport polymer may bind with antimicrobial agents.
  • the solid transport material is or includes an electrolyte solid transport polymer.
  • the electrolyte solid transport polymer may be selected from the group consisting of polyethylene oxide, polypropylene oxide, polycarbonates, polysiloxanes, polyvinylidene difluoride, and combinations thereof, for example.
  • the solid structural polymer is covalently bonded to the solid transport material.
  • a solid structural polymer is crosslinked, via a crosslinking molecule, with a solid transport polymer.
  • the crosslinking is preferably covalent crosslinking, but can also be ionic crosslinking.
  • an abrasion-resistant structure is established within the continuous transport phase.
  • the structural polymer and the transport polymer are crosslinked, the length scales of the different phases can be controlled, such as to enhance transport rates of the antimicrobial agent.
  • a crosslinking molecule may include at least one moiety selected from the group consisting of an amine moiety, a hydroxyl moiety, an isocyanate moiety, and a combination thereof, for example. Other crosslinking molecules may be employed. In certain embodiments, at least one moiety is an isocyanate moiety, which may be a blocked isocyanate.
  • the continuous transport phase is a solid solution or solid suspension of the solid transport material and the antimicrobial agent.
  • the continuous transport phase may be a solution of the solid transport material and the antimicrobial agent.
  • the continuous transport phase may be a suspension of the solid transport material and the antimicrobial agent.
  • the continuous transport phase contains a transport-phase liquid that at least partially dissolves the antimicrobial agent.
  • the transport-phase liquid may be selected from the group consisting of water, dialkyl carbonate, propylene carbonate, y-butyrolactone, 2-phenoxyethanol, and combinations thereof.
  • the transport-phase liquid is selected from polar solvents.
  • Polar solvents may be protic polar solvents or aprotic polar solvents.
  • Exemplary polar solvents include, but are not limited to, water, alcohols, ethers, esters, ketones, aldehydes, carbonates, and combinations thereof.
  • the transport-phase liquid is water that is passively incorporated from atmospheric humidity.
  • the transport-phase liquid is selected from ionic liquids.
  • ionic liquids include, but are not limited to, ammonium-based ionic liquids synthesized from substituted quaternary ammonium salts.
  • the antimicrobial agent is selected from quaternary ammonium molecules (whether or not classified as an ionic liquid).
  • quaternary ammonium molecules include, but are not limited to, benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetylpyridinium chloride, cetrimonium, cetrimide, tetraethylammonium bromide, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, and domiphen bromide.
  • Quaternary ammonium molecules or eutectic mixtures of quaternary ammonium molecules that are liquids at room temperature ionic liquids or ionic liquid eutectics, respectively — enable liquid-state rates of transport with negligible vapor pressure.
  • a specific example is tetrabutylammonium heptadecafluorooctanesulfonate (C24H36F17NO3S), which has a melting point ⁇ 5°C.
  • Quaternary ammonium molecules may be mixed with imidazolium-based ionic liquids, pyridinium-based ionic liquids, pyrrolidinium-based ionic liquids, and/or phosphonium-based ionic liquids.
  • the transport-phase liquid contains one or more water-soluble salts, one or more of which may function as an antimicrobial agent.
  • water-soluble salts include, but are not limited to, copper chloride, copper nitrate, zinc chloride, zinc nitrate, silver chloride, silver nitrate, or combinations thereof.
  • Other exemplary water-soluble salts include quaternary ammonium salts, such as (but not limited to) the quaternary ammonium molecules recited above.
  • the transport-phase liquid is a eutectic liquid salt, which is optionally derived from ammonium salts.
  • the eutectic liquid salt may contain an antimicrobial agent or be otherwise antimicrobially active.
  • the antimicrobial agent is selected from N- halamines.
  • A-halamines are compounds that stabilize an oxidizing agent (such as chlorine contained within the A-halamine molecule) and may be used to kill or deactivate microbes.
  • A-halamines remain stable, unlike sodium hypochlorite (bleach), over long time periods and may be recharged by exposure to an oxidizer such as dilute bleach or ozone.
  • Exemplary A-halamines include, but are not limited to, hydantoin (imidazolidine-2, 4-dione); l,3-dichloro-5,5-dimethylhydantoin; 3- bromo-1 -chi oro-5, 5 -dimethylhydantoin; 5, 5 -dimethylhydantoin; 4,4-dimethyl-2- oxazalidinone; tetramethyl-2-imidazolidinone; and 2,2,5,5-tetramethylimidazo-lidin- 4-one.
  • antimicrobial N-hal amines are also disclosed in Lauten et al., Applied and Environmental Microbiology Vol. 58, No. 4, Pages 1240-1243 (1992), which is incorporated by reference.
  • the antimicrobial agent is selected from oxidizing molecules, such as (but not limited to) those selected from the group consisting of sodium hypochlorite, calcium hypochlorite, hypochlorous acid, hydrogen peroxide, and combinations thereof.
  • the antimicrobial agent is selected from metal ions, such as (but not limited to) silver, copper, zinc, cobalt, nickel, or combinations thereof. Any metal ion with at least some antimicrobial activity itself, or which confers antimicrobial activity to a compound which the metal ion binds to, may be employed.
  • the metal ion may be present in a metal complex or a metal salt, for example.
  • Metal ions may be present in oxides.
  • the antimicrobial agent contains a neutral metal (e.g., zero-valent silver, copper, or zinc) which may be dissolved in a liquid and/or may be present as nanoparticles, for example.
  • An electrolyte may be included in the continuous transport phase, to increase transport rates of the antimicrobial agent.
  • An exemplary electrolyte is a complex formed between poly(ethylene oxide) and metal salts, such as poly(ethylene oxide)-Cu(CF3SO3)2 which is a known copper conductor.
  • Cu(CF3SO3)2 is the copper(II) salt of trifluoromethanesulfonic acid. See Bonino et al., “Electrochemical properties of copper-based polymer electrolytes”, Electrochimica Acta, Vol. 37, No. 9, Pages 1711-1713 (1992), which is incorporated by reference.
  • solvents for the electrolyte may be present.
  • Solvents for the electrolyte may be selected from the group consisting of sulfoxide, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxy ethane, 1,2-di ethoxy ethane, y-buterolactone, y- valerolactone, 1,3- dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, proprionitrile, diglyme, triglyme, methyl formate, trimethyl phosphate, triethyl phosphate, and mixtures thereof, for example.
  • an electrolyte When an electrolyte is included in the continuous transport phase, there may be a salt within an aqueous or non-aqueous solvent.
  • exemplary salts are salts of transition metals (e.g., V, Ti, Cr, Co, Ni, Cu, Zn, Tb, W, Ag, Cd, or Au), salts of metalloids (e.g., Al, Ga, Ge, As, Se, Sn, Sb, Te, or Bi), salts of alkali metals (e.g., Li, Na, or K), salts of alkaline earth metals (e.g., Mg or Ca), or a combination thereof.
  • a gel electrolyte is included in the continuous transport phase.
  • a gel electrolyte contains a liquid electrolyte including an aqueous or non-aqueous solvent as well as a salt, in a polymer host.
  • the solvent and salt may be selected from the lists above.
  • the polymer host may be selected from the group consisting of poly(ethylene oxide), poly(vinylidene fluoride), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluori de-hexafluor opropylene) (PVdF-co- HFP), polycarbonate, polysiloxane, and combinations thereof.
  • the antimicrobial structure further contains one or more layers of an antimicrobial-agent storage phase that is distinct from the continuous transport phase and the discrete solid structural phase.
  • the antimicrobial structure further contains inclusions of an antimicrobial-agent storage phase that is distinct from the continuous transport phase and the discrete solid structural phase.
  • An antimicrobial-agent storage phase may be fabricated from the same material as the solid transport material, or from a different material.
  • both the solid transport material and the antimicrobial-agent storage phase (when present) may be made from a hydrophobic, non-lipophobic polymer.
  • the antimicrobial-agent storage phase may contain an antimicrobial agent that is released initially, continuously, or periodically into the continuous transport phase.
  • the antimicrobial structure may further contain one or more additives, such as (but not limited to) salts, buffers, UV stabilizers, fillers, pigments, flattening agents, flame retardants, or combinations thereof.
  • additives such as (but not limited to) salts, buffers, UV stabilizers, fillers, pigments, flattening agents, flame retardants, or combinations thereof.
  • Additives when present, may be incorporated into the discrete solid structural phase, the continuous transport phase, both of these phases, or neither of these phases but within a separate phase.
  • an additive when an additive is a salt, there will be a cation and anion forming the salt.
  • the cation element may be Li, Na, K, Mg, and/or Ca, for example.
  • the anion element or group may be F, Cl, Br, I, SO3, SO4, NO2, NO3, CH3COO, and/or CO3, for example.
  • an additive when it is a buffer, it may be an inorganic or organic molecule that maintains a pH value or pH range via acid-base reactions.
  • a buffer may be discrete or may be bonded to the solid transport material, for example.
  • an additive when it is a UV stabilizer, it may be an antioxidant (e.g., a thiol), a hindered amine (e.g., a derivative of tetramethylpiperidine), UV-absorbing nanoparticles (e.g., TiCh, ZnO, CdS, CdTe, or ZnS-Ag nanoparticles), or a combination thereof, for example.
  • an antioxidant e.g., a thiol
  • a hindered amine e.g., a derivative of tetramethylpiperidine
  • UV-absorbing nanoparticles e.g., TiCh, ZnO, CdS, CdTe, or ZnS-Ag nanoparticles
  • an additive when it is a particulate filler, it may be selected from the group consisting of silica, alumina, silicates, talc, aluminosilicates, barium sulfate, mica, diatomite, calcium carbonate, calcium sulfate, carbon, wollastonite, and a combination thereof, for example.
  • a particulate filler is optionally surface-modified with a compound selected from the group consisting of fatty acids, silanes, alkylsilanes, fluoroalkylsilanes, silicones, alkyl phosphonates, alkyl phosphonic acids, alkyl carboxylates, alkyldisilazanes, and combinations thereof, for example.
  • an additive when it is a pigment, it may be selected from the group consisting of metal-complex pigments, azo pigments, polycyclic pigments, and anthraquinone pigments.
  • Metal-oxide pigments include titanium dioxide, cobalt oxide, and iron oxide, for example.
  • the flame retardant may be selected from the group consisting of ammonium salts, phosphate salts, phosphines, halogenated compounds, carbonate salts, hydroxide salts, borate salts, high-surface- area silicas, expandable graphite, and combinations thereof.
  • flame retardants are ammonium polyphosphate, magnesium hydroxide, zinc hydroxystannate, antimony trioxide, magnesium hydroxycarbonate, zinc borate, magnesium aluminum hydroxycarbonate, aluminum trihydroxide, tetrabromobisphenol A, tetrabromobisphenol A bis(2,3-dibromopropyl ether), bisphenol-A bis(diphenyl phosphate), brominated polyols, melamine resins, chlorinated paraffins, and combinations thereof.
  • FIG. 1 is a top view of the outer surface of the antimicrobial structure 100.
  • FIG. 1 is a top view of the outer surface of the antimicrobial structure 100.
  • the antimicrobial structure 100 is biphasic, containing a discrete solid structural phase 110 that provides abrasion resistance, and a continuous transport phase 120 that stores antimicrobial agents and transports the antimicrobial agents to the outer surface in order to inactivate or kill microbes.
  • An antimicrobial agent (not shown) is preferably contained selectively within the continuous transport phase 120, such that the antimicrobial structure 100 is capable of destroying microbes (e.g., viruses and/or bacteria).
  • the 100-micron scale bar in FIG. 1 is exemplary and indicative of the length scales of the discrete solid structural phase 110, the continuous transport phase 120, and the distance between the phases.
  • the structure 100 may be a coating on a substrate (not shown) or may be a bulk material or object, for example.
  • FIG. 2 is a through-thickness side view of a coating or bulk material.
  • an outer layer 250 that may contain microbes from environmental sources (microbes not depicted) and is generally exposed to the environment.
  • the antimicrobial structure 200 is biphasic, containing a discrete solid structural phase 210 and a continuous transport phase 220 that stores antimicrobial agents and transports the antimicrobial agents to the outer layer 250 in order to inactivate or kill microbes that may be present there.
  • An antimicrobial agent (not shown) is preferably contained selectively within the continuous transport phase 220, such that the antimicrobial structure 200 is capable of destroying microbes (e.g., viruses and/or bacteria) after transport of the antimicrobial agent to the outer layer 250 and/or potentially after diffusion of microbes from the outer layer 250 into the continuous transport phase 220 which exposes the microbes to the antimicrobial agent.
  • the structure 200 may be a coating on a substrate (not shown) or may be a bulk material or object, for example. A substrate, if present, would typically be distally opposite the outer layer 250.
  • the antimicrobial structure contains embedded electrodes in a configuration such that the antimicrobial agent is electrically or electrochemically rechargeable.
  • “rechargeable” refers to being chargeable during use as well as being initially chargeable when first deployed.
  • FIG. 3 is a sketch of an antimicrobial structure 305 (through-thickness side view of coating or material) with a rechargeable antimicrobial agent.
  • the antimicrobial structure 305 includes antimicrobial material 300a/300b/300c which is fabricated from the same components as the structure in FIG. 2, i.e., material 300a/300b/300c includes a discrete solid structural phase (210 in FIG. 2) and a continuous transport phase (220 in FIG. 2), which for purposes of clear illustration are shown in uniform grayscale in FIG. 3 as material 300a/300b/300c.
  • Electrode leads (not shown) will carry electrical current to or from the electrodes.
  • electrodes 330, 340 are depicted as embedded layers, other electrode configurations are possible, including one or both electrodes being outer layers, one of the electrodes being integrated with a base substrate or a wall of an object, or non-planar electrode architectures, for example.
  • FIG. 3 there is an outer layer 350 that may contain microbes from environmental sources (microbes not depicted) and is generally exposed to the environment.
  • the structure 305 may be a coating on a substrate (not shown) or may be a bulk material or object, for example.
  • a substrate, if present, would typically be distally opposite the outer layer 350.
  • a suitable antimicrobial agent may be electrochemically charged or recharged (e.g. after a period of use).
  • the continuous transport phase will typically be wet with a liquid solution containing water or another solvent, and/or a liquid electrolyte (optionally, a gel electrolyte).
  • the liquid solution contains an antimicrobial agent or a precursor to an antimicrobial agent.
  • the liquid solution may contain a salt and/or a pH buffer as well.
  • sodium chloride NaCl
  • a voltage may be applied such that NaCl dissolved in the transport phase within material 300b (between electrodes 330, 340) is electrochemically transformed into sodium hypochlorite and/or hypochlorous acid, depending on the pH.
  • NaOCl and/or HOC1 are antimicrobially active.
  • the NaOCl and/or HOC1 permeates (via the continuous transport phase) throughout the structure 305, i.e., from material 300b into materials 300a and 300c.
  • the desired location is material 300a, especially near or at the outer layer 350, where microbes may be concentrated. Since NaOCl and/or HOC1 present in material 300c will typically not be removed by environmental forces during use, there will normally be a concentration gradient in the direction toward the outer layer 350, which is desired for effective replenishment and thus recharging.
  • a periodic wash or soak with a salt solution and buffer may be used to maintain pH.
  • the salt (e.g., NaCl) solution of a periodic wash or soak may be at a salt concentration from about 200 ppm to about 50,000 ppm, such as from about 1,000 ppm to about 10,000 ppm, for example.
  • a period soak with a liquid electrolyte may be used to enhance transport rates of the antimicrobial agent or precursor thereof.
  • sodium hypochlorite and/or hypochlorous acid may be generated by applying a voltage between electrodes 330, 340 as noted above, wherein the NaOCl and/or HOC1 are antimicrobial agent precursor(s) for recharging A-halamines that form the selected antimicrobial agent.
  • the antimicrobial structural may be configured to generate hydrogen peroxide.
  • Electrochemical methods to generate hydrogen peroxide and catalysts are described in Perry et al., “Electrochemical synthesis of hydrogen peroxide from water and oxygen”, Nature Reviews Chemistry volume 3, pages 442-458 (2019), which is hereby incorporated by reference for its teachings of both methods and catalysts.
  • H2O2 can form at an electrode by oxidizing H2O and/or by partially reducing O2.
  • metal alloys PdvAui-v, 0 ⁇ x ⁇ 1
  • carbon doped carbon (e.g., boron-doped C)
  • BiVO 4 bismutheptane
  • TiO 2 titanium oxides
  • the antimicrobial structure may further contain one or more protective layers, such as environmentally protective layer(s).
  • the antimicrobial structure may be a multilayer structure, which may contain two layers, three layers, four layers, or more. In some embodiments, there is an outer layer to seal the active components from the environment while retaining and diffusing antimicrobial agents over time.
  • microbes e.g., bacteria or viruses
  • microbes may enter through a capping layer to reach the antimicrobial agent under the capping layer.
  • microbes may remain on the capping layer and antimicrobial agent diffuses through the capping layer to reach the microbes.
  • the antimicrobial structure contains a porous top layer and an absorbing inner layer that contains antimicrobial agents.
  • the porous top layer may include a material such as expanded polytetrafluoroethylene (e.g., Gore-Tex®), which allows vapor but not liquid to be exchanged.
  • a bottom sealing layer may be incorporated to prevent the loss of the antimicrobial agents.
  • the antimicrobial structure includes a multilayer sub-structure wherein at least one layer contains the biphasic architecture as disclosed herein, and wherein an internal or encapsulated layer contains antimicrobial agents and/or preferentially traps microbes to enhance antimicrobial effectiveness.
  • the antimicrobial structure may be characterized in that the antimicrobial agent has a diffusion coefficient (diffusivity) between IO -18 m 2 /s and 10 -9 m 2 /s, measured at a temperature of 25°C and a pressure of 1 bar, within the continuous transport phase.
  • the antimicrobial agent diffusion coefficient is about, or at least about, IO -16 m 2 /s, preferably IO -14 m 2 /s, more preferably IO -12 m 2 /s, even more preferably IO -10 m 2 /s, or most preferably IO -9 m 2 /s, measured at 25°C and 1 bar.
  • a diffusion coefficient on the order of 10 -9 m 2 /s is a liquid-like diffusion coefficient and is much higher, generally, than a purely solid- state diffusion coefficient.
  • the antimicrobial structure disclosed herein is not limited to transport of antimicrobial agent exclusively by pure diffusion.
  • the actual transport may occur by various mass-transfer mechanisms including, but not limited to, Fickian diffusion, non-Fickian diffusion permeation, sorption transport, solubilitydiffusion, charge-driven flow, convection, capillary-driven flow, and so on.
  • Fickian diffusion non-Fickian diffusion permeation
  • sorption transport solubilitydiffusion
  • charge-driven flow convection
  • capillary-driven flow and so on.
  • the structure can move around quickly in space such that the antimicrobial agent undergoes some amount of centrifugal convection.
  • the actual transport rate (flux) of antimicrobial agent through the structure depends not only on the diffusion coefficient, but also on the three-dimensional concentration gradient, temperature, and possibly other factors such as pH.
  • the actual flux of antimicrobial agent through the structure is about, or at least about, 2/, 3x, 4*, 5x, 10x, 20x, 30x, 40*, 50*, 100x, 200x, 300x, 400x, 500x, or 1000x higher than the flux through a solid-state material.
  • a person of ordinary skill in the art can calculate or estimate transport fluxes for a given structure geometry and materials, or carry out experiments to determine such fluxes.
  • the antimicrobial structure may be characterized by an original concentration of antimicrobial agent (prior to exposure to microbes).
  • the original concentration of antimicrobial agent may be selected based on the type of antimicrobial agent, and intended use of the antimicrobial structure, and/or other factors.
  • the original concentration of antimicrobial agent is about, at least about, or at most about 0.00001 wt%, 0.0001 wt%, 0.001 wt%, 0.01 wt%, 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%, on the basis of mass of antimicrobial agent divided by total mass of all components within 0.1%, 1%, 5%, or 10% depth from the surface into the bulk structure.
  • the antimicrobial structure may be characterized in that the antimicrobial agent is replenished on an outer surface of the antimicrobial structure to at least 25% of the original concentration of antimicrobial agent, in 100 minutes or less. In various embodiments, the antimicrobial agent is replenished on an outer surface of the antimicrobial structure to at least 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, 99.9%, or 100% of the original concentration of antimicrobial agent, in 100 minutes or less.
  • the antimicrobial agent is replenished on an outer surface of the antimicrobial structure to at least 25% of the original concentration of antimicrobial agent, in 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5, 4, 3, 2, or 1 minutes or less.
  • the antimicrobial agent is replenished on an outer surface of the antimicrobial structure to at least 50% of the original concentration of antimicrobial agent, in 60, 30, 20, 15, 10, 5, 4, 3, 2, or 1 minutes or less.
  • the antimicrobial structure may be a coating or may be present in a coating. Alternatively, or additionally, the antimicrobial structure may be present at a surface of a bulk object. The antimicrobial structure may be the entirety of a bulk object, with no underlying substrate or other solid structure.
  • the antimicrobial structure is a coating disposed on an automotive dash board.
  • the antimicrobial structure is a coating disposed on an overhead stowage bin in an aerospace cabin.
  • the discrete solid structural phase may be fabricated from, or include, an anti-fouling polymer to minimize the presence of dirt and debris (e.g., oil) and to make the surface easier to clean.
  • an anti-fouling polymer is a segmented copolymer, further discussed below.
  • the antimicrobial agent may be included in a coating precursor or may be applied to a coating through a soaking process, for example.
  • an antimicrobial agent is incorporated into the continuous transport phase during synthesis of the antimicrobial structure.
  • an antimicrobial agent is incorporated into the continuous transport phase following synthesis of the antimicrobial structure, such as by infiltrating a liquid containing the antimicrobial agent into the continuous transport phase, or by electrochemically creating the antimicrobial agent in situ using a voltage applied between electrodes, for example.
  • Some embodiments are premised on the preferential incorporation of an antimicrobial agent within one phase of a multiphase polymer coating.
  • the structure of a microphase-separated polymer network provides a reservoir for antimicrobial agents within the continuous phase.
  • microphase-separated means that the first and second solid materials (e.g., soft segments) are physically separated on a microphaseseparation length scale from about 0.1 microns to about 500 microns.
  • phases are in reference to solid phases or fluid phases.
  • a “phase” is a region of space (forming a thermodynamic system), throughout which all physical properties of a material are essentially uniform. Examples of physical properties include density and chemical composition.
  • a solid phase is a region of solid material that is chemically uniform and physically distinct from other regions of solid material (or any liquid or vapor materials that may be present). Solid phases are typically polymeric and may melt or at least undergo a glass transition at elevated temperatures. Reference to multiple solid phases in a composition or microstructure means that there are at least two distinct material phases that are solid, without forming a solid solution or homogeneous mixture.
  • the antimicrobial agent is in a fluid.
  • the fluid is not solely in a vapor phase at 25°C, since vapor is susceptible to leaking from the structure.
  • the fluid may contain vapor in equilibrium with liquid, at 25°C.
  • a fluid is in liquid form at 25°C but at least partially in vapor form at a higher use temperature, such as 30°C, 40°C, 50°C, or higher.
  • a liquid being “disposed in” a solid material it is meant that the liquid is incorporated into the bulk phase of the solid material, and/or onto surfaces of particles of the solid material.
  • the liquid will be in close physical proximity with the solid material, intimately and/or adjacently.
  • the disposition is meant to include various mechanisms of chemical or physical incorporation, including but not limited to, chemical or physical absorption, chemical or physical adsorption, chemical bonding, ion exchange, or reactive inclusion (which may convert at least some of the liquid into another component or a different phase, including potentially a solid).
  • a liquid disposed in a solid material may or may not be in thermodynamic equilibrium with the local composition or the environment. Liquids may or may not be permanently contained in the structure; for example, depending on volatility or other factors, some liquid may be lost to the environment over time.
  • the selectivity into the continuous transport phase is meant that of the antimicrobial agent that is disposed within the structure overall, at least 51%, preferably at least 75%, and more preferably at least 90% of the antimicrobial agent is disposed in only the continuous transport phase .
  • the selectivity into the continuous transport phase is about, or at least about, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, or 100%.
  • a liquid is added to a polymer such as by submerging and soaking into the polymer.
  • the liquid may be absorbed into a solid polymer.
  • the liquid absorption swells a polymer, which means that there is an increase of volume of polymer due to absorption of the liquid.
  • the liquid may be, but does not need to be, classified as a solvent for the solid polymer which it swells.
  • the phase-separated microstructure preferably includes discrete islands of one material (the discrete solid structural phase) within a continuous sea of the other material (the continuous transport phase).
  • the continuous phase provides unbroken channels within the material for transport of mass and/or electrical charge.
  • the discrete solid structural phase and the continuous transport phase may be present as phase-separated regions of a copolymer, such as a block copolymer.
  • a “block copolymer” means a copolymer containing a linear arrangement of blocks, where each block is defined as a portion of a polymer molecule in which the monomeric units have at least one constitutional or configurational feature absent from the adjacent portions. Segmented block copolymers are preferred, providing two (or more) phases.
  • An exemplary segmented copolymer is a urethane-urea copolymer.
  • a segmented polyurethane includes a microphase-separated structure of fluorinated and nonfluorinated species.
  • a segmented copolymer is employed in which first soft segments form a continuous matrix and second soft segments are a plurality of discrete inclusions.
  • the first soft segments are a plurality of discrete inclusions and the second soft segments form a continuous matrix.
  • Segmented copolymers are typically created by combining a flexible oligomeric soft segment terminated with an alcohol or amine reactive groups and a multifunctional isocyanate.
  • a viscous prepolymer mixture with a known chain length distribution is formed. This can then be cured to a high-molecular-weight network through the addition of amine or alcohol reactive groups to bring the ratio of isocyanate to amine/alcohol groups to unity.
  • the product of this reaction is a chain backbone with alternating segments: soft segments of flexible oligomers and hard segments of the reaction product of low-molecular- weight isocyanates and alcohol/amines.
  • the material typically phase-separates on the length scale of these individual molecular blocks, thereby creating a microstructure of flexible regions adjacent to rigid segments strongly associated through hydrogen bonding of the urethane/urea moieties.
  • This combination of flexible and associated elements typically produces a physically crosslinked elastomeric material.
  • segmented copolymer composition comprising:
  • polyesters or polyethers selected from polyesters or polyethers, wherein the polyesters or poly ethers are (a,o)-hydroxyl-terminated, (a,o)-amine- terminated, and/or (a, o)-thiol -terminated;
  • first soft segments and the second soft segments may (in some embodiments) be microphase-separated on a microphase-separation length scale from about 0.1 microns to about 500 microns, and optionally wherein the molar ratio of the second soft segments to the first soft segments is less than 2.0.
  • fluoropolymers are present in the triblock structure: wherein:
  • segmented copolymer composition comprising:
  • polyesters or polyethers selected from polyesters or polyethers, wherein the polyesters or poly ethers are (a,o)-hydroxyl-terminated, (a, co famine- terminated, and/or (a, ofthiol -terminated;
  • SUBSTITUTE SHEET (RULE 26) (d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof, wherein the first soft segments and the second soft segments may (in some embodiments) be microphase-separated on a microphase-separation length scale from about 0.1 microns to about 500 microns.
  • the continuous transport phase includes a polyelectrolyte and a counterion to the polyelectrolyte.
  • the polyelectrolyte may be selected from the group consisting of poly(acrylic acid) or copolymers thereof, cellulose-based polymers, carboxymethyl cellulose, chitosan, poly(styrene sulfonate) or copolymers thereof, poly(acrylic acid) or copolymers thereof, poly(methacrylic acid) or copolymers thereof, poly(allylamine), and combinations thereof, for example.
  • the counterion may be selected from the group consisting of H + , Li + , Na + , K + , Ag + , Ca 2+ , Mg 2+ , La 3+ , CI 6 N + , F”, Cl”, Br”, L, BF 4 “, SO 4 2 ’, PO 4 2 ’, C12SO3-, and combinations thereof, for example.
  • ionic species may be employed as well in the continuous transport phase.
  • ionic species may be selected from the group consisting of an ionizable salt, an ionizable molecule, a zwitterionic component, a polyelectrolyte, an ionomer, and combinations thereof.
  • An “ionomer” is a polymer composed of ionomer molecules.
  • An “ionomer molecule” is a macromolecule in which a significant (e.g., greater than 1, 2, 5, 10, 15, 20, or 25 mol%) proportion of the constitutional units have ionizable or ionic groups, or both.
  • polyelectrolytes also have ionic groups covalently bonded to the polymer backbone, but have a higher ionic group molar substitution level (such as greater than 50 mol%, usually greater than 80 mol%).
  • Polyelectrolytes are polymers whose repeating units bear an electrolyte group. Polyelectrolyte properties are thus similar to both electrolytes (salts) and polymers. Like salts, their solutions are electrically conductive. Like polymers, their solutions are often viscous.
  • the continuous transport phase includes a polymer such as a polyurethane, a polyurea, a polysiloxane, or a combination thereof, with at least some charge along the polymer backbone.
  • Polymer charge may be achieved through the incorporation of ionic monomers such as dimethylolpropionic acid, or another ionic species.
  • the degree of polymer charge may vary, such as about, or at least about, 1, 2, 5, 10, 15, 20, or 25 mol% of the polymer repeat units being ionic repeat units.
  • the continuous transport phase includes an ionic species selected from the group consisting of (2,2-bis-(l-(l-methyl imidazolium)- methylpropane- 1,3 -diol bromide), l,2-bis(2'-hydroxyethyl)imidazolium bromide, (3- hydroxy-2-(hydroxymethyl)-2-methylpropyl)-3-methyl- l H-3z.
  • an ionic species selected from the group consisting of (2,2-bis-(l-(l-methyl imidazolium)- methylpropane- 1,3 -diol bromide), l,2-bis(2'-hydroxyethyl)imidazolium bromide, (3- hydroxy-2-(hydroxymethyl)-2-methylpropyl)-3-methyl- l H-3z.
  • a liquid may be introduced into the continuous transport phase actively, passively, or a combination thereof.
  • a liquid is actively introduced to the continuous transport phase by spraying of the liquid, deposition from a vapor phase derived from the liquid, liquid injection, bath immersion, or other techniques.
  • a liquid is passively introduced to the continuous transport phase by letting the liquid naturally be extracted from the normal atmosphere, or from a local atmosphere adjusted to contain one or more desired liquids in vapor or droplet (e.g., mist) form.
  • a desired additive is normally a solid at room temperature and is first dissolved or suspended in a liquid that is then disposed in the continuous transport phase.
  • a desired additive is normally a solid at room temperature and is first melted to produce a liquid that is then disposed in the continuous transport phase.
  • the desired additive may partially or completely solidify back to a solid, or may form a multiphase material, for example.
  • Some potential additives contain reactive groups that unintentionally react with chemical groups contained in the polymer precursors. Therefore, in some cases, there exists an incompatibility of liquid species in the resin during chemical synthesis and polymerization. Addition of reactive fluid additives into the reaction mixture during synthesis can dramatically alter stoichiometry and backbone structure, while modifying physical and mechanical properties.
  • One strategy to circumvent this problem is to block the reactive groups (e.g., alcohols, amines, and/or thiols) in the fluid additive with chemical protecting groups to render them inert to reaction with other reactive chemical groups (e.g., isocyanates) in the coating precursors.
  • an additive contains alcohol, amine, and/or thiol groups
  • the additive thus contains chemical protecting groups to prevent or inhibit reaction of the alcohol, amine, and/or thiol groups with isocyanates.
  • the protecting groups may be designed to undergo deprotection upon reaction with atmospheric moisture, for example.
  • the protecting groups may be selected from the silyl ether class of alcohol protecting groups.
  • the protecting groups may be selected from the group consisting of trimethyl silyl ether, isopropyldimethylsilyl ether, tert-butyldimethylsilyl ether, tert- butyldiphenylsilyl ether, tribenzyl silyl ether, triisopropyl silyl ether, and combinations thereof.
  • the protecting groups to protect alcohol may be selected from the group consisting of 2,2,2-trichloroethyl carbonate, 2- methoxyethoxymethyl ether, 2-naphthylmethyl ether, 4-methoxybenzyl ether, acetate, benzoate, benzyl ether, benzyloxymethyl acetal, ethoxyethyl acetal, methoxymethyl acetal, methoxypropyl acetal, methyl ether, tetrahydropyranyl acetal, triethylsilyl ether, and combinations thereof.
  • the protecting groups may be selected from the carbamate class of amine protecting groups, such as (but not limited to) vinyl carbamate. Alternatively, or additionally, the protecting groups may be selected from the ketamine class of amine protecting groups. In these or other embodiments, the protecting groups to protect amine may be selected from the group consisting of 1-chloroethyl carbamate, 4-methoxybenzenesulfonamide, acetamide, benzylamine, benzyloxy carbamate, formamide, methyl carbamate, trifluoroacetamide, tert-butoxy carbamate, and combinations thereof.
  • the protecting groups may be selected from S-2,4-dinitrophenyl thioether and/or S-2-nitro-l -phenylethyl thioether, for example.
  • the typical reaction mechanism when water is the deprotecting reagent is simple hydrolysis. Water is often nucleophilic enough to kick off a leaving group and deprotect a species.
  • One example of this is the protection of an amine with a ketone to form a ketamine. These can be mixed with isocyanates when the amine alone would react so quickly as to not be able to be practically mixed. Instead the ketamine reagent is inert but after mixing and casting as a film, atmospheric moisture will diffuse into the coating, remove the ketone (which vaporizes itself) and leaves the amine to rapidly react with neighboring isocyanates in situ.
  • a chemical deprotection step is actively conducted, such as by introducing a deprotection agent and/or adjusting mixture conditions such as temperature, pressure, pH, solvents, electromagnetic field, or other parameters.
  • hygroscopic means that a material is capable of attracting and holding water molecules from the surrounding environment.
  • the water uptake of various polymers is described in Thijs et al., “Water uptake of hydrophilic polymers determined by a thermal gravimetric analyzer with a controlled humidity chamber” J. Mater. Chem., (17) 2007, 4864-4871, which is hereby incorporated by reference herein.
  • a hygroscopic material is characterized by a water absorption capacity, at 90% relative humidity and 30°C, of at least 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 wt% uptake of H 2 O.
  • one of the first soft segments and second soft segments is oleophobic.
  • An oleophobic material has a poor affinity for oils.
  • the term “oleophobic” means a material with a contact angle of hexadecane greater than 90°.
  • An oleophobic material may also be classified as lipophobic.
  • one of the first soft segments and the second soft segments may be a “low-surface-energy polymer” which means a polymer, or a polymer-containing material, with a surface energy of no greater than 50 mJ/m 2 .
  • one of the first soft segments and the second soft segments has a surface energy from about 5 mJ/m 2 to about 50 mJ/m 2 .
  • the first soft segments or the second soft segments may be or include a fluoropolymer, such as (but not limited to) a fluoropolymer selected from the group consisting of polyfluoroethers, perfluoropolyethers, fluoroacrylates, fluorosilicones, polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polyvinylfluoride (PVF), polychlorotrifluoroethylene (PCTFE), copolymers of ethylene and trifluoroethylene, copolymers of ethylene and chlorotrifluoroethylene, and combinations thereof.
  • a fluoropolymer such as (but not limited to) a fluoropolymer selected from the group consisting of polyfluoroethers, perfluoropolyethers, fluoroacrylates, fluorosilicones, polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), polyviny
  • the first soft segments or the second soft segments may be or include a siloxane.
  • a siloxane contains at least one Si-O-Si linkage.
  • the siloxane may consist of polymerized siloxanes or polysiloxanes (also known as silicones). One example is polydimethylsiloxane.
  • the molar ratio of the second soft segments to the first soft segments is about 2.0 or less. In various embodiments, the molar ratio of the second soft segments to the first soft segments is about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 1.95.
  • (a,o)-terminated polymers are terminated at each end of the polymer.
  • the a -termination may be the same or different than the o- termination on the opposite end.
  • the fluoropolymers and/or the polyesters or poly ethers may terminated with a combination of hydroxyl groups, amine groups, and thiol groups, among other possible termination groups.
  • thiols can react with an -NCO group (usually catalyzed by tertiary amines) to generate a thiourethane.
  • (a,o)-termination includes branching at the ends, so that the number of terminations may be greater than 2 per polymer molecule.
  • the polymers herein may be linear or branched, and there may be various terminations and functional groups within the polymer chain, besides the end (a,o) terminations.
  • Polyols are polymers with on average two or more hydroxyl groups per molecule.
  • a,o-hydroxyl-terminated perfluoropoly ether is a type of polyol.
  • Isocyanate functionality refers to the number of isocyanate reactive sites on a molecule. For example, diisocyanates have two isocyanate reactive sites and therefore an isocyanate functionality of 2. Triisocyanates have three isocyanate reactive sites and therefore an isocyanate functionality of 3.
  • Polyfluoroether refers to a class of polymers that contain an ether group — an oxygen atom connected to two alkyl or aryl groups, where at least one hydrogen atom is replaced by a fluorine atom in an alkyl or aryl group.
  • PFPE Perfluoropoly ether
  • Polyureas are generally produced by reacting an isocyanate containing two or more isocyanate groups per molecule with one or more multifunctional amines (e.g., diamines) containing on average two or more amine groups per molecule, optionally in the presence of a catalyst.
  • a “chain extender or crosslinker” is a compound (or mixture of compounds) that link long molecules together and thereby complete a polymer reaction. Chain extenders or crosslinkers are also known as curing agents, curatives, or hardeners. In polyurethane/urea systems, a curative is typically comprised of hydroxyl-terminated or amine-terminated compounds which react with isocyanate groups present in the mixture. Diols as curatives form urethane linkages, while diamines as curatives form urea linkages. The choice of chain extender or crosslinker may be determined by end groups present on a given prepolymer.
  • curing can be accomplished through chain extension using multifunctional amines or alcohols, for example.
  • Chain extenders or crosslinkers can have an average functionality greater than 2 (such as 2.5, 3.0, or greater), i.e. beyond diols or diamines.
  • polyesters or polyethers are selected from the group consisting of poly(oxymethylene), poly(ethylene glycol), polypropylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), poly(ethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), and combinations thereof.
  • the isocyanate species is selected from the group consisting of 4,4'-methylenebis(cyclohexyl isocyanate), hexamethylene diisocyanate, cycloalkyl-based diisocyanates, tolylene-2,4-diisocyanate, 4,4'- methylenebis(phenyl isocyanate), isophorone diisocyanate, and combinations or derivatives thereof.
  • the polyol or polyamine chain extender or crosslinker possesses a functionality of 2 or greater, in some embodiments.
  • At least one polyol or polyamine chain extender or crosslinker may be selected from the group consisting of 1,4- butanediol, 1,3-propanediol, 1,2-ethanediol, glycerol, trimethylolpropane, ethylenediamine, isophoronediamine, diaminocyclohexane, and homologues, derivatives, or combinations thereof.
  • polymeric forms of polyol chain extenders or crosslinkers are utilized, typically hydrocarbon or acrylic backbones with hydroxyl groups distributed along the side groups.
  • the one or more chain extenders or crosslinkers may be present in a concentration, in the segmented copolymer composition, from about 0.01 wt% to about 25 wt%, such as from about 0.05 wt% to about 10 wt%.
  • First soft segments may be present in a concentration from about 5 wt% to about 95 wt% based on total weight of the composition. In various embodiments, the first soft segments may be present in a concentration of about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95 wt% based on total weight of the composition.
  • Second soft segments may be present in a concentration from about 5 wt% to about 95 wt% based on total weight of the composition. In various embodiments, the second soft segments may be present in a concentration of about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95 wt% based on total weight of the composition.
  • fluorinated polyurethane oligomers are terminated with silane groups. The end groups on the oligomers (in the prepolymer) may be modified from isocyanate to silyl ethers.
  • an isocyanate-reactive silane species e.g., aminopropyltriethoxysilane
  • Such an approach eliminates the need for addition of a stoichiometric amount of curative to form strongly associative hard segments, while replacing the curative with species that possess the ability to form a covalently crosslinked network under the influence of moisture or heat.
  • Such chemistry has been shown to preserve beneficial aspects of urethane coatings while boosting scratch resistance.
  • the reactivity of the terminal silane groups allows for additional functionality in the form of complimentary silanes blended with the prepolymer mixture.
  • the silanes are able to condense into the hydrolysable network upon curing. This strategy allows for discrete domains of distinct composition.
  • a specific embodiment relevant to anti-fouling involves the combination of fluorocontaining urethane prepolymer that is endcapped by silane reactive groups with additional alkyl silanes.
  • the microphase-separated microstructure containing the first and second soft segments may be characterized as an inhomogeneous microstructure.
  • phase inhomogeneity means that a multiphase microstructure is present in which there are at least two discrete phases that are separated from each other.
  • the two phases may be one discrete solid structural phase in a continuous solid phase, two co-continuous solid phases, or two discrete solid structural phases in a third continuous solid phase, for example.
  • the length scale of phase inhomogeneity refers to the average size (e.g., effective diameter) of discrete inclusions of one phase dispersed in a continuous phase. In some embodiments, the length scale of phase inhomogeneity refers to the average center-to-center distance between nearest-neighbor inclusions of the same phase.
  • the average length scale of phase inhomogeneity (which may also be referred to as an average phase-separation length) may generally be from about 0.1 microns to about 500 microns. In some embodiments, the average length scale of phase inhomogeneity is from about 0.5 microns to about 100 microns, such as about 1 micron to about 50 microns.
  • the average length scale of phase inhomogeneity is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, or 500 microns, including any intermediate values not explicitly recited, and ranges starting, ending, or encompassing such intermediate values.
  • “about 0.1 microns” is intended to encompass 0.05-0.149 microns (50-149 nanometers), i.e. ordinary rounding.
  • the antimicrobial structure may also be characterized by hierarchical phase separation.
  • first soft segments and second soft segments in addition to being microphase-separated — are typically nanophase-separated.
  • two materials being “nanophase- separated” means that the two materials are separated from each other on a length scale from about 1 nanometer to about 100 nanometers.
  • the nanophaseseparation length scale may be from about 10 nanometers to about 100 nanometers.
  • the nanophase separation between first solid material (or phase) and second solid material (or phase) may be caused by the presence of a third solid material (or phase) disposed between regions of the first and second solid materials.
  • the nanophase separation may be driven by intermolecular association of hydrogen-bonded, dense hard segments.
  • the first soft segments and the hard segments are nanophase-separated on an average nanophase-separation length scale from about 10 nanometers to less than 100 nanometers.
  • the second soft segments and the hard segments may be nanophase-separated on an average nanophase-separation length scale from about 10 nanometers to less than 100 nanometers.
  • the first and second soft segments themselves may also be nanophase- separated on an average nanophase-separation length scale from about 10 nanometers to less than 100 nanometers, i.e., the length scale of the individual polymer molecules.
  • the nanophase-separation length scale is hierarchically distinct from the microphase-separation length scale. With traditional phase separation in block copolymers, the blocks chemically segregate at the molecular level, resulting in regions of segregation on the length scale of the molecules, such as a nanophaseseparation length scale from about 10 nanometers to about 100 nanometers. See Petrovic et al., “POLYURETHANE ELASTOMERS” Prog. Polym. Set., Vol.
  • the extreme difference of the two soft segments means that in the reaction pot the soft segments do not mix homogeneously and so create discrete region that are rich in fluoropolymer or rich in non-fluoropolymer (e.g., PEG) components, distinct from the molecular-level segregation.
  • PEG non-fluoropolymer
  • These emulsion droplets contain a large amount of polymer chains and are thus in the micron length-scale range. These length scales survive the curing process, so that the final material contains the microphase separation that was set-up from the emulsion, in addition to the molecular-level (nanoscale) segregation.
  • the larger length scale of separation (0.1-500 microns) is driven by an emulsion process, which provides microphase separation that is in addition to classic molecular-level phase separation.
  • Chen et al. “Structure and morphology of segmented polyurethanes: 2. Influence of reactant incompatibility” POLYMER, 1983, Vol. 24, pages 1333-1340, is hereby incorporated by reference herein for its teachings about microphase separation that can arise from an emulsion-based procedure.
  • discrete inclusions have an average size (e.g., effective diameter) from about 50 nm to about 150 pm, such as from about 100 nm to about 100 pm. In various embodiments, discrete inclusions have an average size (e.g., effective diameter) of about 50 nm, 100 nm, 200 nm, 500 nm, 1 pm, 2 pm, 5 pm, 10 pm, 50 pm, 100 pm, or 200 pm.
  • discrete inclusions (of discrete solid structural phase) have an average center-to-center spacing between adjacent inclusions, through a continuous matrix (of continuous transport phase), from about 50 nm to about 150 pin, such as from about 100 nm to about 100 pm.
  • discrete inclusions have an average center-to-center spacing between adjacent inclusions of about 50 nm, 100 nm, 200 nm, 500 nm, 1 pm, 2 pm, 5 pm, 10 pm, 50 pm, 100 pm, or 200 pm.
  • the antimicrobial structure forms a coating disposed on a substrate.
  • the coating may have a thickness from about 1 pm to about 10 mm, for example.
  • the coating thickness is about, at least about, or at most about 100 nm, 1 pm, 10 pm, 100 pm, 1 mm, or 10 mm, including any intervening ranges. Thicker coatings provide the benefit that even after surface abrasion, the coating still functions because the entire depth of the coating (not just the outer surface) contains the functional materials.
  • the coating thickness will generally depend on the specific application.
  • An optional substrate may be disposed on the back side of the antimicrobial structure.
  • a substrate will be present when the material forms a coating or a portion of a coating (e.g., one layer of a multilayer coating).
  • Many substrates are possible, such as a metal, polymer, wood, or glass substrate.
  • the substrate may be any material or object for which antimicrobial protection is desirable.
  • an adhesion layer is disposed on a substrate, wherein the adhesion layer is configured to promote adhesion of the antimicrobial structure to the selected substrate.
  • An adhesion layer contains one or more adhesionpromoting materials, such as (but not limited to) primers (e.g., carboxylated styrenebutadiene polymers), alkoxysilanes, zirconates, and titanium alkoxides.
  • the antimicrobial structure is in the form of an applique that may be adhered to a surface at the point of use.
  • a precursor composition Prior to formation of the final antimicrobial structure, a precursor composition may be provided.
  • the precursor composition may be waterborne, solventborne, or a combination thereof.
  • first or second soft segments may be derived from an aqueous dispersion of a linear crosslinkable polyurethane containing charged groups, and the other soft segments may be derived from a crosslinking agent containing charged groups, for example.
  • a precursor includes a silane, a silyl ether, a silanol, an alcohol, or a combination or reaction product thereof, and optionally further includes a protecting group that protects the precursor from reacting with other components.
  • Some embodiments employ waterborne polyurethane dispersions.
  • a successful waterborne polyurethane dispersion sometimes requires the specific components to contain ionic groups to aid in stabilizing the emulsion.
  • Other factors contributing to the formulation of a stable dispersion include the concentration of ionic groups, concentration of water or solvent, and rate of water addition and mixing during the inversion process.
  • An isocyanate prepolymer may be dispersed in water.
  • a curative component may be dispersed in water. Water evaporation then promotes the formation of a microphase-separated polyurethane material.
  • a composition or precursor composition may generally be formed from a precursor material (or combination of materials) that may be provided, obtained, or fabricated from starting components.
  • the precursor material is capable of hardening or curing in some fashion, to form a precursor composition containing the first soft segments and second soft segments, microphase-separated on a microphase-separation length scale from about 0.1 microns to about 500 microns.
  • the precursor material may be a liquid; a multiphase liquid; a multiphase slurry, emulsion, or suspension; a gel; or a dissolved solid (in solvent), for example.
  • an emulsion sets up in the reaction mixture based on incompatibility between the two blocks (e.g., PEG and PC).
  • the emulsion provides microphase separation in the precursor material.
  • the precursor material is then cured from casting or spraying.
  • the microphase separation survives the curing process (even if the length scales change somewhat during curing), providing the benefits in the final materials (or precursor compositions) as described herein.
  • the microphase separation in this invention is not associated with molecular length-scale separation (5-50 nm) that many classic block-copolymer systems exhibit. Rather, the larger length scales of microphase separation, i.e. 0.1-500 pm, arise from the emulsion that was set-up prior to curing.
  • a precursor material is applied to a substrate and allowed to react, cure, or harden to form a final composition (e.g., coating).
  • a precursor material is prepared and then dispensed (deposited) over an area of interest. Any known methods to deposit precursor materials may be employed.
  • a fluid precursor material allows for convenient dispensing using spray coating or casting techniques.
  • the fluid precursor material may be applied to a surface using any coating technique, such as (but not limited to) spray coating, dip coating, doctor-blade coating, air knife coating, curtain coating, single and multilayer slide coating, gap coating, knife-over-roll coating, metering rod (Meyer bar) coating, reverse roll coating, rotary screen coating, extrusion coating, casting, or printing. Because relatively simple coating processes may be employed, rather than lithography or vacuum-based techniques, the fluid precursor material may be rapidly sprayed or cast in thin layers over large areas (such as multiple square meters).
  • any coating technique such as (but not limited to) spray coating, dip coating, doctor-blade coating, air knife coating, curtain coating, single and multilayer slide coating, gap coating, knife-over-roll coating, metering rod (Meyer bar) coating, reverse roll coating, rotary screen coating, extrusion coating, casting, or printing. Because relatively simple coating processes may be employed, rather than lithography or vacuum-based techniques, the fluid precursor material may be rapidly sprayed or cast in thin layers over large areas
  • the solvent or carrier fluid may include one or more compounds selected from the group consisting of water, alcohols (such as methanol, ethanol, isopropanol, or tertbutanol), ketones (such as acetone, methyl ethyl ketone, or methyl isobutyl ketone), hydrocarbons (e.g., toluene), acetates (such as tert-butyl acetate), acids (such as organic acids), bases, and any mixtures thereof.
  • a solvent or carrier fluid may be in a concentration of from about 10 wt% to about 99 wt% or higher, for example.
  • the precursor material may be converted to an intermediate material or the final composition using any one or more of curing or other chemical reactions, or separations such as removal of solvent or carrier fluid, monomer, water, or vapor.
  • Curing refers to toughening or hardening of a polymeric material by physical crosslinking, covalent crosslinking, and/or covalent bonding of polymer chains, assisted by electromagnetic waves, electron beams, heat, and/or chemical additives. Chemical removal may be accomplished by heating/flashing, vacuum extraction, solvent extraction, centrifugation, etc. Physical transformations may also be involved to transfer precursor material into a mold, for example. Additives may be introduced during the hardening process, if desired, to adjust pH, stability, density, viscosity, color, or other properties, for functional, ornamental, safety, or other reasons.
  • a discrete solid structural phase comprising a solid structural polymer, wherein the solid structural polymer is characterized by a glass-transition temperature from about 25°C to about 300°C;
  • a continuous transport phase that is interspersed within the discrete solid structural phase, wherein the continuous transport phase comprises a solid transport material, wherein the discrete solid structural phase and the continuous transport phase are separated by an average phase-separation length selected from about 100 nanometers to about 500 microns.
  • the disclosed materials are useful as fluorine-free antifouling coatings.
  • the biphasic structure may contain one phase that avoids wetting (the high-T g structural phase) and a second phase to enable cleaning fluids to get under the stain (the transport phase, such as PEG or another polyalkene oxide).
  • the transport phase such as PEG or another polyalkene oxide.
  • no antimicrobial active is needed in the transport or continuous phase.
  • the disclosed materials are also useful as icephobic materials.
  • the biphasic structure may contain one phase that avoids wetting (the high-Tg phase) and a second phase to inhibit the freezing of water (the transport phase, such as PEG). In these embodiments, no antimicrobial active is needed in the transport or continuous phase.
  • the disclosed materials are also useful as anticorrosion materials.
  • the biphasic structure may contain one phase that avoids wetting (the high-T g phase) and a second phase containing a corrosion inhibitor (the transport phase, such as PEG).
  • the transport phase such as PEG
  • no antimicrobial active is needed in the transport or continuous phase.
  • Example 1 Synthesis of Polymeric Antimicrobial Structure.
  • Mylar biaxially-oriented polyethylene terephthalate
  • Example 3 Electrochemical Impedance Spectroscopy (EIS) of Antimicrobial Agent Transport in Polymer Films.
  • the transport rate of a selected antimicrobial agent (10% benzalkonium chloride in water) is measured in a series of PEG-pTHF films using electrochemical impedance spectroscopy (EIS).
  • EIS electrochemical impedance spectroscopy
  • the typical film surface area is 1.08 cm 2 with a thickness of about 0.02 cm. Measurements are performed in a two- electrode electrochemical cell at frequencies between 10 2 Hz and 5 * 10 6 Hz.
  • FIG. 4 shows the magnitude of the impedance spectra (normalized by the film thickness) for six films with various PEG concentrations (0 vol%, 25 vol%, 40 vol%, 50 vol%, 60 vol%, and 75 vol% PEG, with the remainder pTHF) after immersion in a 10% benzalkonium chloride (in water) solution for approximately 2 days.
  • the normalized impedance spectra for a pure solution of 10% benzalkonium chloride in water is also shown.
  • “quat” refers to 10% benzalkonium chloride.
  • Specific conductivity and diffusion coefficients are measured from the impedance at 10 4 Hz (dashed vertical line in FIG. 4).
  • FIG. 5 shows a plot of the specific conductivity (left axis) and diffusion coefficients (right axis) as a function of PEG concentration (0 vol%, 25 vol%, 40 vol%, 50 vol%, 60 vol%, and 75 vol%) after immersion in a 10 wt% benzalkonium chloride (in water) solution for approximately 2 days. Conductivity and diffusion coefficients are determined from the impedance at 10 kHz. The dashed near at the top of FIG. 5 represents the conductivity and diffusion coefficient of a pure solution of 10 wt% benzalkonium chloride in water.
  • the specific conductivity of the benzalkonium chloride in the film with 25 vol% PEG is about 400* greater than that of the pure pTHF film. This measurement suggests a small amount of a transport phase (e.g., PEG) is sufficient to achieve rapid transport of benzalkonium chloride in these films.
  • the transport rate of the benzalkonium chloride (the conductivity) increase with PEG concentration, increasing an additional 30* at 75 vol% PEG.
  • Comparative Example Transparent and Easily Stained 16/49/35 PEG/pTHF/HS.
  • PEG polyethylene glycol
  • pTHF poly(tetrahydrofuran)
  • HS hard segment (urethane bonds).
  • a polymer is prepared by adding PEG 600 (5.00 g), pTHF 650 (13.10 g), dibutyltin dilaurate (0.058 g, -2000 ppm), and 2-butanone (29.09 g) into a mixer cup followed by centrifugal mixing for one minute at 2000 revolutions per minute (rpm). Desmodur 3300 (10.99 g) is added and the solution is mixed for one minute at 2000 rpm. The resulting solution is sprayed onto aluminum with an LPH-80 Anest Iwata HVLP spray gun in 4 passes (30 seconds between passes). The film is allowed to cure overnight at room temperature (about 25°C). The cured film is approximately 4 mils thick.
  • FIG. 6 is a photographic image of the transparent Comparative Example film. The background is clearly visible, showing the transparency.
  • FIG. 7 is a photographic image of the Comparative Example film after staining with coffee including cream, followed by attempted subsequent cleaning.
  • FIG. 8 is a photographic image of the Comparative Example film after staining with lipstick, followed by attempted subsequent cleaning.
  • the Comparative Example film stains easily as shown by the result of leaving coffee and cream (FIG. 7) or lipstick (FIG. 8) on the surface for 2 hours and then an attempt at cleaning with a hard surface cleaner. Cleaning is not fully effective, due to staining from the coffee/cream and lipstick. The staining is believed to be due to the pTHF having a glass-transition temperature below room temperature.
  • Example 4 Transparent and Antifouling 17/33/50 PEG/PC/HS.
  • PEG polyethylene glycol
  • PC polycarbonate
  • HS hard segment (urethane bonds).
  • the PEG is the continuous transport phase.
  • the PC is the discrete solid structural phase.
  • the hard segments contain a trifunctional crosslinker and amine-terminated chain extenders that improve coating hardness.
  • a polymer is prepared by adding polycarbonate polyol CPX-2012 (10.4 g), PEG 600 (5.00 g) and Ethacure 100 (2.46 g) to a mixer cup, heating to a flowable viscosity, and mixing for one minute at 2000 rpm. 2-butanone (3.04 g) is added and the solution and mixed at 2000 rpm for one minute. Desmodur 3300 (12.55 g) and dibutyltin dilaurate (0.121 g, ⁇ 4000 ppm) are added and the solution and mixed for 10 seconds at 2000 rpm before casting with a doctor blade at 70°C.
  • FIG. 9 is a photographic image of the transparent Example 4 film. The background is clearly visible, showing the transparency.
  • FIG. 10 is a photographic image of the Example 4 film after staining with coffee including cream, followed by subsequent cleaning. No staining is visible in FIG. 10.
  • FIG. 11 is a photographic image of the Example 4 film after staining with lipstick, followed by subsequent cleaning. No staining is visible in FIG. 11. Based on these results, the Example 4 film is transparent and resists staining by coffee or lipstick.
  • Optical microscopy is utilized to examine the Example 4 film, to reveal the phase separation between the continuous transport phase (PEG) and the discrete solid structural phase (PC).
  • the phase-separation length is from about 1 micron to about 50 microns. Because the phase-separation length exceeds the wavelength of light, film transparency is surprising.
  • the refractive index of PEG is 1.46 and the refractive index of PC is 1.59, a difference of almost 10%. It is hypothesized, without limitation, that the materials are mixed at the domain boundaries to provide a graded interface that does not significantly scatter light.
  • Example 5 Specific Conductivity of PEG/pTHF/HS, PEG/pTHF/PFPE/HS, and PEG/PC/HS Antimicrobial Films.
  • PEG polyethylene glycol
  • PC polycarbonate
  • pTHF poly(tetrahydrofuran)
  • PFPE perfluoropolyether (Solvay 5158x PEG-terminated perfluoropolyether)
  • HS hard segment (urethane bonds).
  • the transport rate (specific conductivity) of an antimicrobial agent is measured in a series of phase-separated antimicrobial films (PEG/pTHF/HS, PEG/pTHF/PFPE/HS, and PEG/PC/HS) using electrochemical impedance spectroscopy (EIS).
  • the antimicrobial agent is either 10 wt% benzalkonium chloride (“quat”) in water or 10 wt% citric acid in water.
  • the specific conductivity is calculated from the film resistance determined from a fit to the EIS data.
  • the typical film surface area is 1.08 cm 2 with a thickness of about 0.02 cm. Measurements are performed in a two-electrode electrochemical cell at frequencies between 10 2 Hz and 5 * 10 6 Hz. Specific conductivity is measured from the impedance at 10 4 Hz.
  • FIG. 13 is a plot of specific conductivity, measured by EIS, from a series of phase-separated antimicrobial films after immersion in a 10 wt% quat or 10 wt% citric acid solution for about 2 days.
  • the dashed line represents the conductivity of a pure solution of 10 wt% quat in water (no film).
  • FIG. 13 shows the dependence of the specific conductivity on the volume fraction of the transport phase (PEG). At low PEG concentrations, the specific conductivity increases rapidly with increasing transport phase. The conductivity starts to saturate above a PEG volume fraction of about 0.35 where the conductivity in the film approaches the conductivity of 10 wt% quat in water.
  • Example 6 PEG/PC/HS Antimicrobial Structure.
  • Molten CPX-2012 (7.19 g) polycarbonate polyol is transferred to a mixing cup along with PEG 600 (3.50 g). This solution is centrifugally mixed for one minute at 2000 rpm before being reheated up to 75°C. 2-Butanone (11.64 g) and BYK-054 defoamer (0.04 g) are added and mixed for one minute at 2000 rpm. Pentaerythritol propoxylate (1.91 g) and 2-butanone (20.00 g) are added and the solution and mixed for one minute at 2000 rpm.
  • Desmodur 3300 (8.49 g) and dibutyltin dilaurate (0.08 g, 4000 ppm) are added and the solution is mixed for one minute at 2000 rpm.
  • the resulting solution is sprayed using an LPH-80 Anest Iwata HVLP spray gun in six passes (30 seconds between passes). The sample is allowed to rest for five minutes at room temperature before curing in an oven at 60°C for four hours.
  • the cured film is approximately 75 microns thick.
  • Example 7 Use of Antimicrobial Structure.
  • This example illustrates one antimicrobial structure and one commercial method of using the antimicrobial structure.
  • the structure and method of using it are not intended to limit the scope of the invention in any way.
  • An antimicrobial structure is fabricated according to one of Examples 1, 2, 4, 6, or an embodiment of the specification.
  • a shared vehicle such as a taxi incorporates a disclosed antimicrobial structure as a seat coating.
  • a first occupant enters the vehicle and, in the process of entering, removes a portion of the antimicrobial agent at that surface. Less than an hour later, a second occupant coughs and deposits an amount of active virus onto the seat surface.
  • the seat surface was quickly and automatically replenished of antimicrobial agent (quaternary ammonium biocides) according to the principles set forth in this disclosure, due to fast transport from the continuous transport phase.
  • the antimicrobial agent inactivates the virus from the second occupant.
  • a third occupant enters the same shared vehicle and touches the same surface, but the third occupant does not become infected since the viral load at the seat surface has been reduced to very low levels that are no longer infectious to humans.

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Abstract

L'invention concerne des revêtements antimicrobiens qui sont transparents et ne se colorent pas facilement. Certaines variantes concernent une structure antimicrobienne transparente comprenant : une phase structurelle solide discrète comprenant un polymère structurel solide ayant une température de transition vitreuse dans la plage de 25 °C à 300 °C ; une phase de transport continue intercalée à l'intérieur de la phase structurelle solide discrète, la phase de transport continue comprenant un matériau de transport solide ; et un agent antimicrobien contenu à l'intérieur de la phase de transport continue, l'agent antimicrobien étant dissous dans un fluide et/ou dans une solution solide avec la phase de transport continue. La phase structurelle solide discrète et la phase de transport continue sont séparées par une longueur moyenne de séparation de phase choisie dans la plage de 100 nanomètres à 500 micromètres. La présente invention résout le compromis entre antisalissure et teneur en matière fluorée. La présente invention résout également le compromis entre transport de molécules absorbées et transparence. En conséquence, une structure antimicrobienne améliorée qui est à la fois antisalissure et transparente est obtenue.
PCT/US2022/035397 2021-08-24 2022-06-29 Revêtements antimicrobiens à phases séparées et procédés pour les fabriquer et les utiliser WO2023027805A1 (fr)

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EP22861859.1A EP4392495A1 (fr) 2021-08-24 2022-06-29 Revêtements antimicrobiens à phases séparées et procédés pour les fabriquer et les utiliser
CN202280054421.5A CN117813357A (zh) 2021-08-24 2022-06-29 相分离的抗微生物涂层及其制备和使用方法

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US202163236311P 2021-08-24 2021-08-24
US63/236,311 2021-08-24
US17/852,307 2022-06-28
US17/852,307 US20220361486A1 (en) 2020-06-11 2022-06-28 Phase-separated antimicrobial coatings, and methods of making and using the same

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005107455A2 (fr) * 2004-04-29 2005-11-17 Bacterin International, Inc. Revetement antimicrobien permettant d'inhiber une adhesion bacterienne et la formation d'un biofilm
US20090155451A1 (en) * 2005-12-14 2009-06-18 Ylitalo Caroline M Antimicrobial coating system
WO2014100778A1 (fr) * 2012-12-20 2014-06-26 Quick-Med Technologies, Inc. Régénération de revêtements antimicrobiens contenant des dérivés de métal par exposition à du peroxyde d'hydrogène aqueux
US20190048223A1 (en) * 2017-08-10 2019-02-14 Hrl Laboratories, Llc Multiphase coatings with separated functional particles, and methods of making and using the same
US20190177572A1 (en) * 2015-12-18 2019-06-13 Hrl Laboratories, Llc Anti-fouling coatings fabricated from polymers containing ionic species

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005107455A2 (fr) * 2004-04-29 2005-11-17 Bacterin International, Inc. Revetement antimicrobien permettant d'inhiber une adhesion bacterienne et la formation d'un biofilm
US20090155451A1 (en) * 2005-12-14 2009-06-18 Ylitalo Caroline M Antimicrobial coating system
WO2014100778A1 (fr) * 2012-12-20 2014-06-26 Quick-Med Technologies, Inc. Régénération de revêtements antimicrobiens contenant des dérivés de métal par exposition à du peroxyde d'hydrogène aqueux
US20190177572A1 (en) * 2015-12-18 2019-06-13 Hrl Laboratories, Llc Anti-fouling coatings fabricated from polymers containing ionic species
US20190048223A1 (en) * 2017-08-10 2019-02-14 Hrl Laboratories, Llc Multiphase coatings with separated functional particles, and methods of making and using the same

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