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WO2025019173A1 - Revêtements réactifs transparents et incolores antimicrobiens à base de cuivre comprenant du cuivre(i) et des additifs - Google Patents

Revêtements réactifs transparents et incolores antimicrobiens à base de cuivre comprenant du cuivre(i) et des additifs Download PDF

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Publication number
WO2025019173A1
WO2025019173A1 PCT/US2024/037025 US2024037025W WO2025019173A1 WO 2025019173 A1 WO2025019173 A1 WO 2025019173A1 US 2024037025 W US2024037025 W US 2024037025W WO 2025019173 A1 WO2025019173 A1 WO 2025019173A1
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Prior art keywords
copper
alkyl
biocidal
additive
composition
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PCT/US2024/037025
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English (en)
Inventor
Theresa Chang
Sean Nichols SACKS
Joel Teye TETTEH
Shu Yuan
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Corning Inc
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Corning Inc
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • the present disclosure relates to biocidal compositions. More particularly, the disclosure relates to biocidal compositions comprising polyurethanes and/or epoxy resins, or precursors thereof, copper(I) salts, and copper-assisting additives.
  • the availability of copper at a surface may be a challenge.
  • Reactive systems dependent upon cross-linking and curing of reactive precursors, such as polyurethanes and epoxy resins, involve the added challenge of ensuring that copper ligands do not interfere with the curing process so as to retain high durability performance of a highly crosslinked coating material.
  • the transmittance may be within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof without either the copper(I) salt or the copper-assisting additive when measured at a thickness of 40 pm.
  • a method of preparing the biocidal composition may include adding a biocidal additive formulation to a carrier; wherein when the carrier is a polyurethane or an epoxy resin, the biocidal additive formulation includes the copper(I) salt and the copper-assisting additive; wherein when the carrier is a second polyurethane precursor, the biocidal additive formulation includes a first polyurethane precursor, the copper(I) salt, and the copper-assisting additive; and wherein when the carrier is a second epoxy resin precursor, the biocidal additive formulation includes a first epoxy resin precursor, the copper(I) salt, and the copper-assisting additive.
  • L*, a*, and b* are CIE values of the biocidal composition after preparing and then storing the biocidal composition at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L’ control, 3- control, and b” control are CIE values of an otherwise identical composition without either the copper(I) salt or the copper-assisting additive.
  • the biocidal additive formulation may further include an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof.
  • the copper(I) salt may be a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • the copper(I) salt may be copper(I) bromide or copper(I) iodide.
  • the copper-assisting additive may include a phosphite, a phosphine, or a combination thereof.
  • the phosphite may be a compound of formula (I): wherein each R 1 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally fluorosubstituted.
  • the phosphine may be a compound of formula (I): wherein each R 2 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally substituted with a hydroxy group.
  • each R 1 may be independently selected from C2-C13 alkyl and phenyl.
  • each R 2 may be independently selected from C2-C13 alkyl.
  • the biocidal additive formulation may further include a reducing agent.
  • the formulation may be in a sealed container including an inert atmosphere.
  • FIG. 2 illustrates a plot of antimicrobial efficacy for examples of biocidal compositions including two-part polyurethanes as carrier, copper sources such as tetrakis(acetonitrile)copper(I) and CCG, triethyl phosphite (“TEP”) as copper-assisting additive, and also including 2-ethylhexyl phosphate (“EHP”), prepared according to the principles of the present disclosure;
  • copper sources such as tetrakis(acetonitrile)copper(I) and CCG
  • TEP triethyl phosphite
  • EHP 2-ethylhexyl phosphate
  • FIG. 4 illustrates a plot of antimicrobial efficacy for examples of biocidal compositions including two-part polyurethanes as carrier, iodo(triethyl phosphite)copper(I) (“CuI(TEP)”) as copper source, TEP as copper-assisting additive, and also including EHP, prepared according to the principles of the present disclosure;
  • CuI(TEP) iodo(triethyl phosphite)copper(I)
  • TEP copper-assisting additive
  • EHP iodo(triethyl phosphite)copper(I)
  • FIG. 6 illustrates a plot of antimicrobial efficacy for examples of biocidal compositions including epoxy resins as carrier, including iodo(tri ethyl phosphite)copper(I) and various molar ratios of potassium phosphate monobasic, prepared according to the principles of the present disclosure;
  • FIG. 7 illustrates a plot of antimicrobial efficacy for examples of biocidal compositions including two-part polyurethanes as carrier, copper(I) bromide as copper source, TEP as copper-assisting additive, and also including EHP, prepared according to the principles of the present disclosure;
  • FIG. 9 illustrates a plot of antimicrobial efficacy for examples of biocidal compositions including two-part polyurethanes as carrier, copper(I) bromide as copper source, TEP as copper-assisting additive, and varied molar ratios of tributyl citrate or tributyl borate, prepared according to the principles of the present disclosure.
  • FIG. 10 illustrates a plot of antimicrobial efficacy for examples of biocidal compositions including two-part polyurethanes as carrier, copper(I) bromide as copper source, tributyl phosphine (“TBP”) as copper-assisting additive in varying molar ratios relative to copper, and also including EHP, prepared according to the principles of the present disclosure; and
  • the term “antimicrobial” refers to a composition, a material, or a surface of a material, including when such composition or material is in the form of a coating or dry film, that will kill or inhibit the growth of microbes including, but not limited to, bacteria, viruses, mildew, mold, algae, fungi, or any combination thereof.
  • the term “antimicrobial,” as used herein, does not necessarily mean the material or the surface of the material will kill or inhibit the growth of all species of microbes within such families, but that the material or the surface of the material will kill or inhibit the growth of one or more species of microbes from such families.
  • biocidal refers to a composition or material with an active substance that is intended to destroy, deter, render harmless, prevent the action of, or otherwise exert a controlling effect on undesired organisms such as bacteria, viruses, mildew, mold, algae, and/or fungi, and in some aspects a biocidal composition has antimicrobial properties.
  • Examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, ec-butyl, tert-butyl, cyclobutyl, methylcyclopropyl, cyclopropylmethyl, pentyl, neopentyl, hexyl, and cyclohexyl.
  • Other examples are -(Ci-Cis)alkyl, -(Ci-Cis)alkyl, -(Ci-Cio)alkyl, -(Ci-Cs)alkyl, -(Ci- Ce)alkyl, and -(C2-Ce)alkyl.
  • a -(Ci-C3o)alkyl group may not be a -Cialkyl group, and/or may not be a -C2alkyl group, and/or may not be a -Cnalkyl group, and/or may not be a -C4alkyl group, and/or may not be a -Csalkyl group, and/or may not be a -Cealkyl group, and/or may not be a -C?alkyl group, and/or may not be a -Csalkyl group, and/or may not be a -Chalky 1 group, and/or may not be a -Cioalkyl group, and/or may not be a -Cnalkyl group, and/or may
  • aryl(Ci-C4)alkyl refers to a functional group wherein a one to four carbon alkylene chain is attached to an aryl group, for example, -CEh-CEh-phenyl. Examples may include benzyl.
  • carrier may refer to a melamine resin, a polyurethane, a precursor thereof, an epoxy resin, a precursor thereof, or a combination thereof, as described herein.
  • polyurethane refers to a class of polymers, such as alternating copolymers, including organic units joined by carbamate (urethane) links. po yure ane n linkage polyurethane
  • epoxy resin refers to a class of copolymers also known as “polyepoxides.” Examples of commercially available epoxy resins may include WiseBond® Bar & Table Top 1 : 1 Ratio. Examples of epoxy resins may be produced by reacting together two separate epoxy resin precursors. In certain examples, an epoxy resin precursor may include an epoxide functional group. Examples of epoxy resin precursors that include an epoxide functional group may include bisphenol A diglycidyl ether: bisphenol A diglycidyl ether.
  • an epoxy resin precursor may include a polyfunctional amine, carboxylic acid, phenol, alcohol, thiol, or any combination thereof, which may react as a nucleophile with an epoxide-containing monomer to form the epoxy resin, and which may be compatible with examples of copper(I) salts and examples of copper-assisting additives of the present disclosure.
  • halide refers to a negative ion (“anion”) of a halogen atom bearing a -1 formal charge.
  • halides include fluoride (F' 1 ), chloride (Cl -1 ), bromide (Br 1 ), and Iodide (I’ 1 ).
  • copper-assisting additive refers to an additive that promotes the availability and/or persistence of copper(I) ions in a composition or material, including promoting availability of copper(I) at a surface and/or interface of a composition or material, consisting with the following explanation.
  • copper(I) is largely colorless and more antimicrobially efficacious, while copper(II) is typically energetically favorable but produces color and has lower antimicrobial efficacy.
  • copper(I) is generally favored for function and color, but copper(II) is usually more stable.
  • a reducing agent for example, to reduce copper(II) to copper(I), or to reduce other oxidants that may be present
  • an antioxidant for example, to scavenge oxidants either by reduction or by sequestering by coordination or binding so as to make such oxidants unavailable to oxidize copper(II) to copper(I)
  • a ligand with a hydrophobic and/or bulky side chain for example, to limit oxidant access to copper(I) in a copper complex
  • a ligand that favors complexation with copper(I) over copper(II) for example, to energetically favor copper(I) to be maintained
  • a ligand that facilitates migration of copper(I) to a surface and/or interface or any combination thereof.
  • the copper-assisting additive is a reducing agent, an antioxidant, a copper-coordinating ligand (for example, coordinating with copper(I) and/or copper(II)) with one or more hydrophobic side chains, a copper-coordinating ligand (for example, coordinating with copper(I) and/or copper(II)) with one or more bulky side chains, a copper-coordinating ligand (for example, coordinating with copper(I) and/or copper(II)) that complexes with copper(I) preferentially over complexing with copper(II), a copper-coordinating ligand (for example, coordinating with copper(I) and/or copper(II)) that has two or more copper coordination sites, or any combination thereof.
  • a copper-coordinating ligand for example, coordinating with copper(I) and/or copper(II) with one or more hydrophobic side chains
  • a copper-coordinating ligand for example, coordinating with copper(I) and/or copper(II) with one or more bulky side chains
  • the term “at.%” refers to atomic weight percent.
  • “at.%” is used in reference to an amount of copper in a composition.
  • the biocidal composition may include copper in an amount of “X at.%” (where X is a number), and this means the mass of copper atoms (using molecular weight) is summed and expressed as a percent relative to a given basis (for example, based on mass of biocidal composition).
  • the mass of other species in a copper complex or molecule for example, the oxygen atom in CU2O
  • the amount of copper in terms of at.% may be determined by methods known in the art.
  • weight and “mass” are used interchangeably.
  • the naming convention for functional groups containing phosphorus are standardized herein. Generally, the naming convention of a functional group with respect to a given phosphorus atom is determined by how many oxygen atoms are double bonded to a phosphorus atom (“A”), the total number of carbon and hydrogen atoms single-bonded to the phosphorus atom (“B”), and the number of oxygen atoms single-bonded to the phosphorus atom (“C”). In this regard, the coordinate “(A,B,C)” may be employed to identify a phosphorus-containing functional group.
  • a “phosphate” has coordinate (1,0,3); a “phosphite” has coordinate (0,0,3); a “phosphine” has coordinate (0,3,0).
  • Formula (I) is an example of a phosphite.
  • Formula (II) is an example of a phosphine.
  • Formula (III) is an example of a phosphate.
  • ambient temperature refers to the temperature of the atmosphere in the immediate surrounding environment of an objection or equipment.
  • ambient relative humidity refers to an amount of water vapor present in a specific volume of immediately surrounding atmosphere at ambient temperature expressed as a percentage of the amount of water vapor needed for saturation at the same temperature. In certain examples, ambient relative humidity may have a value of 42%.
  • percentage point refers to a unit for an arithmetic difference between two percentages. For example, a difference between transmittance values of 88 percent and 98 percent for a particular measurement is a difference of 10 percentage points on the same measurement scale (calculated by subtracting 98 from 88; or 88 from 98). Percentages, by contrast, indicate the relative or proportionate part of a total; in the above example, 88 constitutes 90% of 98 (calculated by dividing 88 by 98 and multiplying by 100), and 98 constitutes 111% of 88 (calculated by dividing 98 by 88 and multiplying by 100).
  • the present disclosure provides a biocidal composition, including a carrier, a copper(I) salt, and a copper-assisting additive different from the carrier.
  • a molar ratio of the copper-assisting additive to the copper(I) salt is at least 0.5: 1.
  • the copper-assisting additive may be combined with the copper(I) salt and added to a carrier at a sum total concentration of both components of from 1 to 300 grams per liter of biocidal composition.
  • the copper(I) salt may include a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt, or any combination thereof.
  • the copper(I) halide may be copper(I) fluoride, copper(I) chloride, copper(I) bromide, copper(I) iodide, or any combination thereof.
  • the tetrakis(acetonitrile)copper(I) salt may be tetrakis(acetonitrile)copper(I) hexafluorophosphate, tetrakis(acetonitrile)copper(I) tetrafluoroborate, tetrakis(acetonitrile)copper(I) perchlorate, tetrakis(acetonitrile)copper(I) trifluoromethanesulfonate, tetrakis(acetonitrile)copper(I) hydrogen oxalate-oxalic acid-acetonitrile, or any combination thereof.
  • the biocidal composition may include a carrier, a copper(I) salt, and a copper-assisting additive.
  • the carrier may include a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof.
  • the copper(I) salt may be combined with a copper- assisting additive and a carrier while maintaining antimicrobial efficacy (or preventing a decrease in antimicrobial efficacy to below a particular level) and/or stabilizing the color of the carrier when the copper(I) salt is combined with the copper-assisting additive and the carrier or when then copper(I) salt and the copper-assisting additive are combined with the carrier.
  • Examples of the present disclosure may maintain antimicrobial efficacy (or prevent a decrease in antimicrobial efficacy to below a particular level) and/or reduce changes in color of the carrier at the time of combining the copper(I) salt with the copper-assisting additive and the carrier or combining the copper(I) salt and the copper-assisting additive with the carrier.
  • Examples of the present disclosure may reduce changes in the antimicrobial efficacy and/or reduce changes in the color of the carrier between a period of time after combining the copper(I) salt with the copper-assisting additive and the carrier or combining the copper(I) salt and the copper-assisting additive with the carrier and the final antimicrobial efficacy and/or color of the carrier.
  • a material for example, a coating such as a dry film
  • a material may exhibit the logarithmic reductions described herein under one or more of the U.S. Environmental Protection Agency “Test Method of Efficacy of Copper Alloy as a Sanitizer” (2009) (also referred to herein as “the EPA Test”), the Modified Japanese Industrial Standard (JIS) Z 2801 Test for Bacteria and/or the Modified JIS Z 2801 Test for Viruses, for a period of one month or greater or for a period of three months or greater, or any of the other time periods described elsewhere herein.
  • JIS Japanese Industrial Standard
  • the time periods may commence a tor after the application of the material to a surface as a layer.
  • the layer exhibits the logarithmic reductions described herein.
  • Each of the EPA Test, the Modified Japanese Industrial Standard (JIS) Z 2801 Test for Bacteria, and the Modified JIS Z 2801 Test for Viruses are incorporated herein by reference in their entireties.
  • JIS Modified Japanese Industrial Standard
  • JIS Z 2801 Test for Viruses are incorporated herein by reference in their entireties.
  • antimicrobial efficacy of a composition or coating may be maintained, or at least a decrease in antimicrobial efficacy to below a particular level may be prevented, in the biocidal compositions disclosed herein, for example, by use of a copper-assisting additive.
  • the effectiveness of a composition (for example, a coating such as a dry film) of the present disclosure as a biocidal composition may be measured as a function of the logarithmic reduction of the biocidal composition.
  • the logarithmic reduction value of the biocidal composition may be relevant to the ability of the biocidal composition to kill a wide variety of biological organisms to which the biocidal composition is exposed, but may also allow the copper(I) salt to act as a preservative for the composition during storage (for example, in a container such as, but not limited to, a tank, a can, a bucket, a drum, a bottle, or a tube).
  • a logarithmic reduction of the biocidal composition may be at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, in a range from 1 to 10, 3 to 7, 4 to 6, or less than, equal to, or greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the logarithmic reduction may be maintained (for example, prevented from falling below) at or above any of the aforementioned values over a given time period, as described elsewhere herein.
  • the biocidal properties of the composition may make it effective for substantially killing a wide variety of biological organisms including bacteria, viruses, and fungi.
  • suitable examples of bacteria include Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, E. coli, and mixtures thereof.
  • the copper(I) salt exhibits at least a logarithmic reduction, a 4 logarithmic reduction, a 5 logarithmic reduction, or even a 6 logarithmic reduction in the concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E coli under the EP A Test, or a 3 logarithmic reduction or greater, or a 4 logarithmic reduction or greater (for example, 5 logarithmic reduction or greater) under JIS Z 2801 (2000) testing conditions or under the Modified JIS Z 2801 Test for Bacteria.
  • the copper(I) salt exhibits a 2 logarithmic reduction or greater, a 3 logarithmic reduction or greater, a 4 logarithmic reduction or greater, or a 5 logarithmic reduction or greater in the concentration of Murine Novovirus or severe acute respiratory syndrome (“SARS”) coronavirus 2 (“SARS- CoV-2”) under a Modified JIS Z 2801 for Viruses test.
  • SARS Murine Novovirus or severe acute respiratory syndrome
  • SARS- CoV-2 Murine Novovirus or severe acute respiratory syndrome coronavirus 2
  • the procedures for the Modified JIS Z 2801 (2000) Test for Bacteria, and the Modified JIS Z 2801 (2000) Test for Viruses are provided in International Patent Application Pub. No. WO 2021/055300 Al, COLOR STABILIZATION OF BIOCIDAL COATINGS, which is incorporated by reference herein in its entirety.
  • Modified JIS Z 2801 Test for Bacteria includes evaluating the bacteria under the standard JIS Z 2801 (2000) test with modified conditions including heating the glass or article to a temperature of 23 degrees Celsius to 37 degrees Celsius at a humidity of 38 percent to 42 percent for 6 hours.
  • the Modifed JIS Z 2801 (2000) Test for Viruses includes the following procedure.
  • a biocidal composition for example, a biocidal composition, a composition including the copper(I) salt, a composition including the copper- assisting additive, control compositions
  • three samples of the material are each inoculated with a 20 pL aliquot of a test virus (where antimicrobial activity is measured) or a test medium including an organic soil load of 5% fetal bovine serum with or without the test virus (where cytotoxicity is measured).
  • the inoculum is then covered with a film and the film is pressed down so the test virus and/or the test medium spreads over the film, but does not spread past the edge of the film.
  • the exposure time begins when each sample was inoculated.
  • the inoculated samples are transferred to a control chamber set to room temperature or “ambient” temperature (20 °C) in a relative humidity of 42% for 2 hours. Exposure time with respect to control samples are discussed below. Following the 2-hour exposure time, the film is lifted off using sterile forces and a 2.00 mL aliquot of the test virus and/or test medium is pipetted individually onto each sample of material and the underside of the film (or the side of the film exposed to the sample) used to cover each sample. The surface of each sample is individually scraped with a sterile plastic cell scraper to collect the test virus or test medium. The test virus and/or test medium is collected (at 10 2 dilution), mixed using a vortex type mixer and serial 10-fold dilutions are prepared. The dilutions are then assayed for antimicrobial activity and/or cytotoxicity.
  • control sample for testing antimicrobial activity (which are also referred to as “zero time vims controls”) for the Modified JIS Z 2801 Test for Viruses
  • three control samples (contained in individual sterile petri dishes) are each inoculated with a 20 pL aliquot of the test virus.
  • a 2.00 mL aliquot of test virus is pipetted onto each control sample.
  • the surface of each sample was individually scraped with a sterile plastic cell scraper to collect test virus.
  • the test virus is collected (at 10 2 dilution), mixed using a vortex type mixer, and serial 10-fold dilutions were prepared. The dilutions are assayed for antimicrobial activity.
  • control samples for cytotoxicity which are also referred to as “2 hour control virus” for the Modified JIS Z 2801 Test for Viruses
  • one control sample (contained in an individual sterile petri dish) is inoculated with a 20 pL aliquot of a test medium containing an organic soil load (5% fetal bovine serum), without the test virus.
  • the inoculum is covered with a film and the film is pressed so the test medium spreads over the film but does not spread past the edge of the film.
  • the exposure time begins when each control sample is inoculated.
  • the control sample is transferred to a controlled chamber set to room temperature (20 °C) in a relative humidity of 42% for a duration of 2 hours exposure time.
  • test medium is lifted off using sterile forceps and a 2.00 mL aliquot of the test medium is pipetted individually onto each control sample and the underside of the film (the side exposed to the sample). The surface of each sample is individually scraped with a sterile plastic cell scraper to collect the test medium. The test medium is collected (at 10 2 dilution), mixed using a vortex type mixer, and serial 10-fold dilutions were prepared. The dilutions were assayed for cytotoxicity.
  • a representative description of performing the EPA Test is as follows.
  • a copper(I) salt is milled to powder using a 2-inch jet mill.
  • the jet milled powder of the copper(I) salt is then added to a carrier (for example, commercially available Eastwood® two-part urethane) and mixed.
  • Control coupons coated with a carrier without copper(I) salt were prepared alongside coupons coated with the copper(I) salt.
  • a 7-mil wet film thickness drawdown bar was used to form films onto Lenata Scrub Charts (P121-10N). The films were dried for 2 days at ambient lab temperature before the antimicrobial test was conducted. Dry film thickness was around 80 m.
  • 1-Inch x 1-inch square coupons were cut from the center of the painted scrub test panels.
  • Stainless steel carriers used as reference, were cleaned and sterilized by immersion in a 75% ethanol solution following by rinsing with DI water.
  • Vials containing Staphylococcus aureus (ATCC 6538) bacterial stock culture were stored at -80° C until use. 20 pL aliquots of thawed bacterial cultures were added to 10 mL of Tryptic Soy Broth. These bacterial suspensions were serially incubated 3X at 36°C for 18-24 hours in an orbital shaker, and then IX in polypropylene snap tubes for 48 hours. Cultures were subsequently mixed on a vortex mixer and allowed to settle. The upper two-thirds of suspension from each tube was aspirated and ODeoo was measured to estimate bacterial density.
  • the culture was diluted with phosphate buffer saline to achieve a bacterial inoculum concentration near a target value of 1.0- 10 7 CFU/mL. 0.25 mL of 5% fetal bovine serum and 0.05 mL TritonTM X-100 were added to 4.70 mL bacterial suspension to aid in spreading the inoculum.
  • Each test coupon was inoculated with 20 pL of the bacterial test culture. The inoculum volume was spread evenly using bent sterile pipette tips to ensure full and even coverage, spreading as close to the edge of the coupon as possible. Coupons were then incubated in a controlled environment set at 42% relative humidity and 23 °C for a period of 120 minutes.
  • the copper(I) salt with a copper-assisting additive to prevent reduction of antimicrobial efficacy below a certain threshold (for example, less than a 3 logarithmic reduction or any other value disclosed herein) and/or limit the shift of the color of the biocidal composition form the color of a standard carrier (for example, the carrier in the absence of either the copper(I) or the copper-assisting additive).
  • a certain threshold for example, less than a 3 logarithmic reduction or any other value disclosed herein
  • a standard carrier for example, the carrier in the absence of either the copper(I) or the copper-assisting additive
  • a CIE L*a*b* AE* between the observed color and a standard of less than 30, less than 25, less than 20, less than 15, less than 12, less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2, less than 1, in a range of from 1 to 30, 2 to 25, 5 to 15, 3 to 8, 4 to 7, 5 to 6, less than, equal to, or greater than 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30.
  • the CIE L*a*b* color space is a color scale for determining a color.
  • the L* component closely matches human perception of lightness.
  • CIE L*a*b* color space is a cylindrical representation of the three perceptual color correlates: lightness, chroma, and hue.
  • the axial component of CIE L*C*h* is the same lightness attribute L* as CIE L*a*b*
  • the radial component is the chroma
  • the angular component is hue.
  • a biocidal composition including: a carrier; a copper(I) salt; and a copper-assisting additive.
  • the carrier may include a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof.
  • the biocidal composition is in liquid form at ambient conditions (1 atm (-101.3 kPa) and 20 °C).
  • the biocidal composition does not contain (for example, and/or the composition is not in the form of) a polyurethane, and/or does not contain a polyurethane precursor, and/or does not contain an epoxy resin, and/or does not contain an epoxy resin precursor, and/or does not contain a melamine precursor.
  • employing a copper-assisting additive allows the achievement of a desired level of antimicrobial efficacy (for example, via any test disclosed herein, such as the EP A Test).
  • the carrier and the copper-assisting additive are different.
  • “different” means that a given chemical species (for example, a polyurethane) cannot qualify as both the carrier and the copper-assisting additive; rather, if the carrier is, for example, a polyurethane, then the copper assisting additive cannot be a polyurethane but must instead be another chemical species (for example, triethyl phosphite).
  • the biocidal composition includes a polymer, a monomer, a binder, an organic solvent, an inorganic solvent, water, a dispersion of finely divided solids in a liquid medium that may be applied to a surface to form a film, a pigment, a filler, an extender, a drier, a rheology modifier, or any combination thereof.
  • the biocidal composition does not contain (for example, and/or the carrier is not or does not contain) a polymer, and/or does not contain a monomer, and/or does not contain a binder, and/or does not contain an organic solvent, and/or does not contain an inorganic solvent, and/or does not contain water, and/or does not contain a dispersion of finely divided solids in a liquid medium that may be applied to a surface to form a film, and/or does not contain a pigment, and/or does not contain a filler, and/or does not contain an extender, and/or does not contain a drier, and/or does not contain a rheology modifier.
  • a copper-assisting additive is or includes a phosphite, a phosphine, or any combination thereof.
  • the copper-assisting additive may be hydrophobic, hydrophilic, or amphiphilic, and any of the aforementioned copper-assisting additives (or any other copper-assisting additive disclosed herein) may be characterized as hydrophobic, hydrophilic, or amphiphilic.
  • the copper-assisting additive may be or may include a hydrophobic phosphite, a hydrophobic phosphine, or any combination thereof.
  • the biocidal composition does not contain (for example, and/or the copper-assisting additive is not) a phosphite, and/or does not contain a phosphine, and/or does not contain a hydrophobic copper-assisting additive, and/or does not contain a hydrophilic copper-assisting additive, and/or does not contain an amphiphilic copper-assisting additive.
  • a copper-assisting additive is a compound of formula (I), formula (II), or any combination thereof.
  • a copper-assisting additive may be a compound of formula (I): wherein each R 1 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, and of which may be optionally fluorosubstituted.
  • each R 1 is independently selected from Ci-Cs alkyl.
  • each R 1 is independently selected from C1-C5 alkyl.
  • the alpha-carbon of at least one R 1 is a secondary or tertiary carbon.
  • Certain examples of compounds of formula (I) may include particular combinations of R 1 selected independently such that the compounds of formula (I) complex with, interact with, or otherwise affect copper (for example, by affecting the persistence of a given oxidation state, such as copper(I)), but not as desirably or preferably as other particular combinations of R 1 due to the combined effects of chemical phenomena understood by those skilled in the art, including, but not limited to, hydrophobicity, solubility, electronic effects, and/or steric effects resulting from the chemical structure of a particular compound of formula (I).
  • each R 1 independently may not be any one of C1-C20 alkyl, and/or may not be aryl, and/or may not be aryl(Ci-C4)alkyl.
  • a biocidal composition does not include a compound of formula (I) and/or the copper-assisting additive is not a compound of formula (I).
  • Examples of compounds of formula (I) may include trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,2,2-fluoroethyl) phosphite, tris(2-ethylhexyl) phosphite, triisopropyl phosphite, and tris(l,l,l,3,3,3-hexafluoro-2-propyl) phosphite.
  • the biocidal composition does not include (for example, the copper-assisting additive is not) trimethyl phosphite, and/or does not include triethyl phosphite, and/or does not include tris(2,2,2-fluoroethyl) phosphite, and/or does not include tris(2-ethylhexyl) phosphite, triisopropyl phosphite, and/or does not contain tri s( 1,1, 1,3, 3,3 -hexafluoro-2-propyl) phosphite, and/or does not include triphenyl phosphite.
  • Ci- C20 alkyl may include C1-C19 alkyl, Ci-Cis alkyl, C1-C17 alkyl, C1-C16 alkyl, C1-C15 alkyl, Ci- C14 alkyl, C1-C13 alkyl, C1-C12 alkyl, C1-C11 alkyl, C1-C10 alkyl, C1-C9 alkyl, Ci-C 8 alkyl, Ci- C 7 alkyl, Ci-C 6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, C2-C20 alkyl, C2-C19 alkyl, C2-C18 alkyl, C2-C17 alkyl, C2-C16 alkyl, C2-C15 alkyl, C2-C14 alkyl, C
  • each R 1 may not be Ci alkyl, and/or may not be optionally fluorosubstituted Ci alkyl, and/or may not be C 2 alkyl, and/or may not be optionally fluorosubstituted C 2 alkyl, and/or may not be C3 alkyl, and/or may not be optionally fluorosubstituted C3 alkyl, and/or may not be C 4 alkyl, and/or may not be optionally fluorosubstituted C 4 alkyl, and/or may not be C5 alkyl, and/or may not be optionally fluorosubstituted C5 alkyl, and/or may not be Ce alkyl, and/or may not be optionally fluorosubstituted Ce alkyl, and/or may not be C 7 alkyl, and/or may not be optionally fluorosubstituted C 7 alkyl, and/or may not be C
  • a biocidal composition containing a compound of formula (I) or any salt thereof exhibits one or more effects when combined with a copper(I) salt, including maintaining antimicrobial efficacy of a biocidal composition, preventing reduction of antimicrobial efficacy of a biocidal composition below a certain level (for example, less than 3 logarithmic reduction), minimizing color drift of a biocidal composition, or any combination thereof.
  • Antimicrobial efficacy may be measured as described elsewhere herein, such as by using the EPA Test.
  • a copper-assisting additive may be a compound of formula (II) or any salt thereof: wherein each R 2 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally substituted with a hydroxy group.
  • each R 2 is independently selected from C2-C13 alkyl, any of which is optionally substituted with a hydroxy group.
  • each R 2 is independently selected from C1-C10 alkyl, any of which is optionally substituted with a hydroxy group.
  • each R 2 is independently selected from Ci-Ce alkyl, any of which is optionally substituted with a hydroxy group.
  • an alpha-carbon of at least one R 2 is a secondary carbon or a tertiary carbon.
  • Certain examples of compounds of formula (II) may include combinations of R 2 selected independently such that the compounds of formula (II) complex with, interact with, or otherwise affect copper (for example, by affecting the persistence of a given oxidation state, such as copper (I)), but not as desirably or preferably as other particular combinations of R 2 due to the combined effects of chemical phenomena understood by those skilled in the art, including, but not limited to, hydrophobicity, solubility, electronic effects, and/or steric effects resulting from the chemical structure of a particular compound of formula (II).
  • each R 2 independently may not be Ci alkyl, and/or may not be Ci alkyl optionally substituted with a hydroxy group, and/or may not be C2 alkyl, and/or may not be C2 alkyl optionally substituted with a hydroxy group, and/or may not be C3 alkyl, and/or may not be C3 alkyl optionally substituted with a hydroxy group, and/or may not be C4 alkyl, and/or may not be C4 alkyl optionally substituted with a hydroxy group, and/or may not be C5 alkyl, and/or may not be C5 alkyl optionally substituted with a hydroxy group, and/or may not be Ce alkyl, and/or may not be Ce alkyl optionally substituted with a hydroxy group, and/or may not be C7 alkyl, and/or may not be C7 alkyl optionally substituted with a hydroxy group, and/or may not be Cs als alkyl, and/or may not
  • Examples of compounds of formula (II) may include tris(hydroxypropyl) phosphine and tributyl phosphine.
  • the biocidal composition does not include (for example, the copper-assisting additive is not) one or more of tris(hydroxypropyl) phosphine or tributyl phosphine.
  • a biocidal composition of the present disclosure may include a compound of formula (III), (IV), (V), or any combination thereof: wherein each R 3 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-
  • each R 4 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from hydrogen, Ci-
  • each R 3 is independently selected from the group consisting of hydrogen, C1-C13 alkyl, phenyl, and benzyl, provided that all R 3 are not simultaneously hydrogen.
  • the alpha-carbon of at least one R 3 is a secondary or tertiary carbon.
  • Certain examples of compounds of formula (III) may include particular combinations of R 3 selected independently such that the compounds of formula (III) complex with, interact with, or otherwise affect copper (for example, by affecting the persistence of a given oxidation state, such as copper (I)), but not as desirably or preferably as other particular combinations of R 3 due to the combined effects of chemical phenomena understood by those skilled in the art, including, but not limited to, hydrophobicity, solubility, electronic effects, and/or steric effects resulting from the chemical structure of a particular compound of formula (III).
  • each R 3 independently may not be hydrogen, and/or may not be any one of C1-C20 alkyl, and/or may not be aryl, and/or may not be aryl(Ci-C4)alkyl.
  • a biocidal composition does not include a compound of formula (III).
  • Examples of compounds of formula (III) may include 2-ethylhexyl phosphate, bis(2- ethylhexyl)phosphate, tris(2-ethylhexyl)phosphate, methyl phosphate, diethyl phosphate, trimethyl phosphate, butyl phosphate (for example, //-butyl, sec-butyl, or tert-butyl), dibutyl phosphate (for example, //-butyl, sec-butyl, and/or tert-butyl), tributyl phosphate (for example, //-butyl, sec-butyl, and/or tert-butyl), phenyl phosphate, diphenyl phosphate, triphenyl phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, or any combination thereof.
  • the biocidal composition does not include 2-ethylhexyl phosphate, and/or does not include bis(2-ethylhexyl)phosphate, and/or does not include tris(2- ethylhexyl)phosphate, and/or does not include methyl phosphate, and/or does not include dimethyl phosphate, and/or does not include trimethyl phosphate, and/or does not include butyl phosphate (for example, //-butyl, sec-butyl, or tert-butyl), and/or does not include dibutyl phosphate (for example, //-butyl, sec-butyl, or tert-butyl), and/or does not include tributyl phosphate (for example, //-butyl, sec-butyl, or tert-butyl), and/or does not include phenyl phosphate, and/or does not include diphenyl phosphate, and/or does not include triphen
  • each R 3 may not be Ci alkyl, and/or may not be C2 alkyl, and/or may not be C3 alkyl, and/or may not be C4 alkyl, and/or may not be C5 alkyl, and/or may not be Ce alkyl, and/or may not be C7 alkyl, and/or may not be Cs alkyl, and/or may not be C9 alkyl, and/or may not be C10 alkyl, and/or may not be Cn alkyl, and/or may not be C12 alkyl, and/or may not be C13 alkyl, and/or may not be C14 alkyl, and/or may not be C15 alkyl, and/or may not be Ci6 alkyl, and/or may not be C17 alkyl, and/or may not be Cis alkyl, and/or may not be C19 alkyl, and/or may not be C20 alkyl.
  • each R 4 is independently selected from the group consisting of hydrogen, C1-C13 alkyl, phenyl, and benzyl, provided that all R 4 are not all simultaneously hydrogen.
  • the alpha-carbon of at least one R 4 is a secondary or tertiary carbon.
  • Certain examples of compounds of formula (IV) may include particular combinations of R 4 selected independently such that the compounds of formula (IV) complex with, interact with, or otherwise affect copper (for example, by affecting the persistence of a given oxidation state, such as copper(I)), but not as desirably or preferably as other particular combinations of R 4 due to the combined effects of chemical phenomena understood by those skilled in the art, including, but not limited to, hydrophobicity, solubility, electronic effects, and/or steric effects resulting from the chemical structure of a particular compound of formula (IV).
  • each R 4 independently may not be hydrogen, and/or may not be any one of C1-C20 alkyl, and/or may not be aryl, and/or may not be aryl(Ci-C4)alkyl.
  • a biocidal composition does not include a compound of formula (IV).
  • Examples of compounds of formula (IV) may include tributyl borate.
  • the biocidal composition does not include tributyl borate.
  • each R 4 may not be Ci alkyl, and/or may not be C2 alkyl, and/or may not be C3 alkyl, and/or may not be C4 alkyl, and/or may not be C5 alkyl, and/or may not be Ce alkyl, and/or may not be C7 alkyl, and/or may not be Cs alkyl, and/or may not be C9 alkyl, and/or may not be C10 alkyl, and/or may not be Cn alkyl, and/or may not be C12 alkyl, and/or may not be C13 alkyl, and/or may not be C14 alkyl, and/or may not be C15 alkyl, and/or may not be Ci6 alkyl, and/or may not be C17 alkyl, and/or may not be Cis alkyl, and/or may not be C19 alkyl, and/or may not be C20 alkyl.
  • each R 5 is independently selected from the group consisting of hydrogen, C1-C13 alkyl, phenyl, and benzyl, provided that all R 5 are not all simultaneously hydrogen.
  • the alpha-carbon of at least one R 5 is a secondary or tertiary carbon.
  • Certain examples of compounds of formula (V) may include particular combinations of R 5 selected independently such that the compounds of formula (V) complex with, interact with, or otherwise affect copper (for example, by affecting the persistence of a given oxidation state, such as copper(I)), but not as desirably or preferably as other particular combinations of R 5 due to the combined effects of chemical phenomena understood by those skilled in the art, including, but not limited to, hydrophobicity, solubility, electronic effects, and/or steric effects resulting from the chemical structure of a particular compound of formula (V).
  • each R 5 independently may not be hydrogen, and/or may not be any one of C1-C20 alkyl, and/or may not be aryl, and/or may not be aryl(Ci-C4)alkyl.
  • a biocidal composition does not include a compound of formula (V).
  • Examples of compounds of formula (V) may include tributyl citrate.
  • the biocidal composition does not include tributyl citrate.
  • the biocidal composition includes copper in an amount of at least 0.01 at.% based on 100 weight percent of the biocidal composition. In certain examples, the biocidal composition includes copper in an amount of less than 10 at.% based on a total 100 weight percent of the biocidal composition.
  • the biocidal composition includes copper in an amount (at.% based on 100 weight percent of the biocidal composition) of 0.01 - 10, 0.01 - 9, 0.01 - 8, 0.01 - 7, 0.01 - 6, 0.01 - 5, 0.01 - 4, 0.01 - 3, 0.01 - 2, 0.01 - 1, 0.01 - 0.9, 0.01 - 0.8, 0.01 - 0.7, 0.01 - 0.6, 0.01 - 0.5, 0.01 - 0.4, 0.01 - 0.3, 0.01 - 0.2, 0.01 - 0.1, 0.01 - 0.05, 0.02 - 10, 0.02 - 9, 0.02 - 8, 0.02 - 7, 0.02 - 6, 0.02 - 5, 0.02 - 4, 0.02 - 3, 0.02
  • the copper(I) salt alone, the copper-assisting additive alone, or a sum total of both the copper(I) salt and the copper-assisting additive may be described by any of the following numbers and ranges: from 0.01 wt.% based on total 100 wt.% of the carrier or the biocidal composition to 20 wt.% based on weight of the carrier of the biocidal composition, such as, an amount (wt.% based on 100 wt.% of the carrier or the biocidal composition) of 0.01
  • 0.01 - 19 0.01 - 18, 0.01 - 17, 0.01 - 16, 0.01 - 15, 0.01 - 14, 0.01 - 13, 0.01 - 12, 0.01 - 11, 0.01 -10, 0.01 - 9, 0.01 - 8, 0.01 - 7, 0.01 - 6, 0.01 - 5, 0.01 - 4.9, 0.01 - 4.8, 0.01 - 4.7, 0.01 - 4.6, 0.01 - 4.5, 0.01 - 4.4, 0.01 - 4.3, 0.01 - 4.2, 0.01 - 4.1, 0.01 - 4, 0.01 - 3.9, 0.01 - 3.8, 0.01 - 3.7, 0.01 - 3.6, 0.01 - 3.5, 0.01 - 3.4, 0.01 - 3.3, 0.01 - 3.2, 0.01 - 3.1, 0.01 - 3, 0.01 - 2.9, 0.01 - 2.8, 0.01 - 2.7, 0.01 - 2.6, 0.01 - 2.5, 0.01 - 2.4, 0.01
  • Such numbers may refer to the absolute amount present, or to the amount added to a composition.
  • the basis weight may be either the carrier or the biocidal composition, as will be made clear from context because, in certain examples, the carrier is a main component of the biocidal composition. As such, in certain examples, the amount of a given component (or components) relative to either the carrier or the biocidal composition will be a similar value.
  • the copper(I) salt and the copper-assisting additive may be present in a sum total amount of at least 10 grams per liter of carrier (or biocidal composition), or at least 15 grams per liter of carrier (or biocidal composition), or at least 20 grams per liter of carrier (or biocidal composition), or at least 25 grams per liter of carrier (or biocidal composition), or at least 30 grams per liter of carrier (or biocidal composition), or at least 35 grams per liter of carrier (or biocidal composition), or at least 40 grams per liter of carrier (or biocidal composition).
  • the copper(I) salt and copper-assisting additive may be present in a sum total amount (grams per liter of carrier or biocidal composition) of from 1 - 50, 1 - 45, 1 - 40, 1 - 35, 1 - 30, 1 - 25, 1 - 20, 1 - 15, 1 - 10, 1 - 5, 2 - 50, 2 - 45, 2 - 40, 2 - 35, 2 - 30, 2 - 25, 2 - 20, 2 - 15, 2 - 10, 2 - 5, 3 - 50, 3 - 45, 3 - 40, 3 - 35, 3 - 30, 3 - 25, 3 - 20, 3 - 15, 3 - 20, 3 - 15, 3 - 20, 3 - 15, 3 - 20, 3 - 15, 3 - 20, 3 - 15, 3 - 20, 3 - 15, 3
  • the basis may be expressed as either carrier or biocidal composition.
  • the copper(I) salt may be present in the biocidal composition in an amount of at least 1 gram per liter of biocidal composition or carrier. In certain examples, the copper(I) salt may be present in the biocidal composition or carrier in an amount of less than 135 grams per liter of biocidal composition or carrier.
  • the copper(I) salt may be present in the biocidal composition or carrier in an amount (grams per liter of biocidal composition or carrier) of 1 - 135, 1 - 130, 1 - 125, 1 - 120, 1 - 115, 1 - 110, 1 - 105, 1 - 100, 1 - 95, 1 - 90, 1 - 85, 1 - 80, 1 - 75, 1 - 70, 1 - 65, 1 - 60, 1 - 55, 1 - 50, 1 - 45, 1 - 40,
  • the molar ratio of the copper-assisting additive to the copper(I) salt in the biocidal composition may be from 0.1 : 1 to 50: 1, including, for example, from 0.1:1 to 49: 1, from 0.1:1 to 48:1, from 0.1:1 to 47:1, from 0.1:1 to 46:1, from 0.1:1 to 45:1, from 0.1:1 to 44:1, from 0.1:1 to 43:1, from 0.1:1 to 42:1, from 0.1:1 to 41:1, from 0.1:1 to 40:1, from 0.1:1 to 39:1, from 0.1:1 to 38:1, from 0.1:1 to 37:1, from 0.1:1 to 36:1, from 0.1:1 to 35:1, from 0.1:1 to 34:1, from 0.1:1 to 33:1, from 0.1:1 to 32:1, from 0.1:1 to 31:1, from 0.1:1 to 30:1, from 0.1:1 to 29:1, from 0.1:1 to 28:1, from 0.1:1 to 27:
  • the composition for example, biocidal composition
  • the composition may be formed into a desired article or be applied to a surface.
  • the composition includes or is, for example, a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or the like
  • a composition may be applied to a surface as a layer.
  • surfaces to which the biocidal composition may be applied include wood, polymer, metal, glass, ceramic, stone, concrete, cement, mineral, drywall, asphalt, or any combination thereof.
  • Examples of articles that may be formed using the compositions described herein include housings or cases for electronic devices (for example, mobile phones, smart phones, tablets, video players, information terminal devices, laptop computers), architectural structures (for examples, countertops, walls, trim, ceilings, floors, exterior facades, and trim), appliances 9for example, cooktops, refrigerator doors, and dishwasher doors), information displays (for example, whiteboards), automotive components (for example, dashboard panels, windshields, window components), and high touch surfaces (for example, a computer mouse, a computer keyboard, a railing, a door, a doorknob, a door push plate, a phone, a phone button, or an elevator button).
  • electronic devices for example, mobile phones, smart phones, tablets, video players, information terminal devices, laptop computers
  • architectural structures for examples, countertops, walls, trim, ceilings, floors, exterior facades, and trim
  • appliances 9 for example, cooktops, refrigerator doors, and dishwasher doors
  • information displays for example, whiteboards
  • automotive components for example, dashboard panels, windshields, window components
  • Articles may be formed by any method known in the art, such as by molding (for example, injection molding), or otherwise forming the article into a desired shape.
  • an entire article may include the biocidal composition (for example, an entire article is formed from the biocidal composition).
  • a method of forming an article the method including providing a masterbatch of the biocidal composition, and then forming the article therefrom by any known technique, such as by extrusion or molding (for example, injection molding).
  • a method of preparing a masterbatch including mixing a concentrated form of the biocidal composition.
  • compositions described herein may include pigments to impart color. Accordingly, the coatings or layers made from such compositions may exhibit a wide variety of colors, depending on the carrier color, mixtures of carriers, and amount of particle loading. Moreover, it is contemplated that the compositions and/or coatings described herein will show no adverse effect to paint adhesion as measured by ASTM D4541. In certain examples, the adhesion of the composition or coating to an underlying substrate is greater than the cohesive strength of the substrate. In other words, in testing, the adhesion between the coating and the substrate is so strong that the underlying substrate failed before the coating was separated from the surface of the substrate.
  • the biocidal composition may be in the form of an article, a layer, a coating, a dry film, or as a liquid composition including suspensions and solutions, which may be applied on a surface or stored in a container (for example, prior to use).
  • the biocidal composition is not in the form of a molded article, e.g., an injection molded article, or an extruded article.
  • One or more examples of the biocidal compositions of the present disclosure may include the copper(I) salt (which may optionally be pre-treated with a pretreatment solution), a copper-assisting additive, and a carrier with a loading level of the copper(I) salt such that the composition may exhibit resistance or preservation against the presence or growth of foulants (for example, microbes).
  • Foulants include fungi, bacteria, viruses, mold, mildew, algae, and combinations thereof.
  • the presence of foulants in materials, such as polyurethanes, epoxy resins, and the like may cause color changes to the composition, may degrade the integrity of the composition, and may negatively affect various properties of the composition.
  • the foulants may be eliminated or reduced.
  • a minimum loading of copper(I) salt for example, 5 weight % or less, 4 weight % or less, 3 weight % or less, 2 weight % or less, or 1 weight % or less; alternatively, or additionally, in an amount of 0 weight % or more, for example, greater than 0 weight %, 0.01 weight % or more, 0.05 weight % or more, 0.1 weight % or more, 0.5 weight % or more, 1 weight % or more, 2 weight % or more, 3 weight % or more, or 4 weight % or more, based on weight of the carrier or composition) and copper-assisting additive in the carrier, the foulants may be eliminated or reduced.
  • compositions may or may not include certain components, when fouling is eliminated or reduced. Therefore, the formulations used in one or more examples of the compositions described herein may have more flexibility and variations than previously possible, when used in known compositions that do not include the copper(I) salt.
  • a biocidal composition may exhibit one or more of the following effects: (1) a greater than 3 logarithmic reduction in a concentration of a microbe selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, E. coli, SARS-Cov-2, and mixtures thereof; (2) a change in color in the biocidal composition is minimized relative to a change in color of a mixture of the carrier and the copper(I) salt in the absence of the copper-assisting additive or the carrier and the copper-assisting additive absent the copper(I) salt; or (3) any combination thereof.
  • Antimicrobial efficacy may be measured as described elsewhere herein, such as by using the EP A Test.
  • a biocidal composition including a carrier, a copper(I) salt, and a copper- assisting additive has better antimicrobial efficacy over time (for example, for 7 days or at least 7 days, or any other time period disclosed herein, such as 30 days or at least 30 days, or 90 days or or at least 90 days) compared to an otherwise identical composition that does not include the copper-assisting additive or does not include the copper(I) salt (for example, in the amounts specified, such as copper in an amount of 0.01 at.% to 10 at.% or 0.01 at.% to 2 at.%; copper(I) salt in the composition in an amount of 0.01 wt.% to 15 wt.%; and/or a molar ratio of the amount of the copper-assisting additive to the amount of copper is from 0.1 : 1 to 50: 1).
  • such a biocidal composition also has minimized color change (for example, color drift and/or color shift) compared to an otherwise identical composition, as disclosed
  • the biocidal composition when the biocidal composition is formed into a coating (for example, a dry film) within one day of preparing the biocidal composition and the coating is stored at ambient conditions for 7 days or at least 7 days (for example, 10 days or at least 10 days, 15 days or at least 15 days, 20 days or at least 20 days, 25 days or at least 25 days, 30 days or at least 30 days, 40 days or at least 40 days, 50 days or at least 50 days, 60 days or at least 60 days, 75 days or at least 75 days, 90 days or at least 90 days, 100 days or at least 100 days, 120 days or at least 120 days, 150 days or at least 150 days, 180 days or at least 180 days, 365 days or at least 365 days, 2 years or at least 2 years, 3 years or at least 3 years, 4 years or at least 4 years, 5 years or at least 5 years, or 6 years or at least 6 years; alternatively, or additionally, less than 6 years, less than 5 years, less than 4 years, less than 3 years, less than 2 years, less than 2
  • Antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EP A Test.
  • the term “for X days” or “for X years” in which X is a number means that the longevity of a specified property lasts minimally for X days (or for X years). The longevity of the specified property may last for a longer period of time, and after such longer period of time the specified property (e.g., log reduction or color value) may begin to decrease; however, “for X days” (or “for X years”) is met if the specified property was present at X days (or X years).
  • the terms “for X days” and the term “for at least X days” are meant to be synonymous terms.
  • the biocidal composition when stored as a liquid composition, mixture, or suspension at ambient conditions for a period of 7 days or at least 7 days (for example, 10 days or at least 10 days, 15 days or at least 15 days, 20 days or at least 20 days, 25 days or at least 25 days, 30 days or at least 30 days, 40 days or at least 40 days, 50 days or at least 50 days, 60 days or at least 60 days, 75 days or at least 75 days, 90 days or at least 90 days, 100 days or at least 100 days, 120 days or at least 120 days, 150 days or at least 150 days, 180 days or at least 180 days, 365 days or at least 365 days (1 year), 2 years or at least 2 years, 3 years or at least 3 years, 4 years or at least 4 years, 5 years or at least 5 years, or 6 years or at least 6 years; alternatively, or additionally, less than 6 years, less than 5 years, less than 4 years, less than 3 years, less than 2 years, less than 365 days, less than 180 days, less than 150
  • the above feature shows the antimicrobial efficacy of a coating (for example, dry film) or article after the biocidal composition has been stored in liquid form (for example, a can of polyurethane precursor or epoxy resin precursor) for a certain period of time.
  • Antimicrobial efficacy may be measured as described elsewhere herein, such as by using the EPA Test.
  • minimizing a change in color corresponds to a CIE AE* value of the biocidal composition being less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, or less than 3, or less than 2, as measured according to formula (VI): wherein L*, a*, and b* are the CIE L*, a*, and b* values of the biocidal compositions and the L’ control, 3- control, and b* CO ntroi are the CIE L*, a*, and b* values of an otherwise identical composition without either the copper(I) salt or the copper-assisting additive.
  • a biocidal composition or a film prepared from the biocidal composition may exhibit (1) a transmittance as measured at each wavelength from 400 to 700 nm, and/or (2) an average transmittance as measured over the wavelength range of from 400 to 700 nm, of at least 50%, or at least 51%, or at least 52%, or at least 53%, or at least 54%, or at least
  • Average transmittance is calculated by summing the transmittance at each wavelength between 400 and 700 nm and dividing by the total number of such wavelengths.
  • a biocidal composition, or a film thereof may exhibit a transmittance as measured at each wavelength from 400 to 700 nanometers that is within 20 percentage points of a second transmittance of an otherwise identical composition or film thereof without either the copper(I) salt or the copper-assisting additive when measured at a thickness of 40 pm; including, for example, within 19.5 percentage points, or within 19.0 percentage points, or within 18.5 percentage points, or within 18.0 percentage points, or within 17.5 percentage points, or within 17.0 percentage points, or within 16.5 percentage points, or within 16.0 percentage points, or within 15.5 percentage points, or within 15.0 percentage points, or within 14.5 percentage points, or within 14.0 percentage points, or within 13.5 percentage points, or within 13.0 percentage points, or within 12.5 percentage points, or within 12.0 percentage points, or within 11.5 percentage points, or within 11.0 percentage points, or within 10.5 percentage points, or within 10.0 percentage points, or within 9.9 percentage points, or within 9.8 percentage points, or within 9.7 percentage points, or within 9.6 percentage
  • a film of a biocidal composition may have a thickness of from 30 pm to 3000 pm, including, for example, from 40 pm, or from 50 pm, or from 60 pm, or from 70 pm, or from 80 pm, or from 90pm, or from 100 pm, or from 110 pm, or from 120 pm, or from 130 pm, or from 140 pm, or from 150 pm, or from 160 pm, or from 170 pm, or from 180 pm, or from 190 pm, or from 200pm, or from 210 pm, or from 220 pm, or from 230pm, or from 240 pm, or from 250 pm, or from 260 pm, or from 270 pm, or from 280 pm, or from 290 pm, or from 300 pm, or from 310pm, or from 320 pm, or from 330 pm, or from 340pm, or from 350 pm, or from 360 pm, or from 370 pm, or from 380 pm, or from 390 pm, or from 400 pm, or from 410 pm, or from 420pm, or from 430 pm
  • 1050 pm or from 1100 pm, or from 1150 pm, or from 1200 pm, or from 1250 pm, or from 1300 pm, or from 1350 pm, or from 1400 pm, or from 1450 pm, or from 1500 pm, or from 1550 pm, or from 1600 pm, or from 1650 pm, or from 1700 pm, or from 1750 pm, or from 1800 pm, or from 1850 pm, or from 1900 pm, or from 1950 pm, or from 2000 pm, or from 2050 pm, or from 2100 pm, or from 2150 pm, or from 2200 pm, or from 2250 pm, or from 2300 pm, or from 2350 pm, or from 2400 pm, or from 2450 pm, or from 2500 pm, or from 2550 pm, or from 2600 pm, or from 2650 pm, or from 2700 pm, or from 2750 pm, or from
  • a method of preparing a biocidal composition including adding a biocidal additive formulation to a carrier.
  • the biocidal additive formulation may include the copper(I) salt and the copper-assisting additive.
  • the carrier is a polyurethane or an epoxy resin
  • the biocidal additive formulation may include a first polyurethane precursor, the copper(I) salt, and the copper-assisting additive.
  • the carrier is a second epoxy resin precursor
  • the biocidal additive formulation may include a first epoxy resin precursor, the copper(I) salt, and the copper-assisting additive.
  • a method including applying a biocidal composition to a surface may include any of the components described elsewhere herein.
  • the surface is or includes wood polymer (for example, plastic or rubber), metal (for example, steel, iron, copper, gold, silver, aluminum, tin, platinum, alloys thereof, or any combination thereof), glass (for example, lithium aluminosilicate, borosilicate, chemical strengthened, or ion-exchanged), ceramic, glass-ceramic, stone, concrete, cement, mineral, drywall, asphalt, or any combination thereof.
  • the method of applying to a surface may be any suitable method, including spraying, spin coating, dipping, and the like, or any combination thereof.
  • the composition may be sprayed on a surface.
  • the copper(I) species for example, the ion or salt
  • the copper(I) species may be at least partially in a solubilized form (for example, facilitated by complexation with a copper-assisting additive), though such copper(I) species may alternatively or additionally be in a suspension.
  • a method of improving or sustaining antimicrobial efficacy in a biocidal composition including: combining a carrier, a copper(I) salt, and a copper-assisting additive, wherein the biocidal composition includes copper in an amount of 0.01 at.% to 10 at.%, and the carrier and the copper-assisting additive are different.
  • a molar ratio of the amount of copper-assisting additive to the amount of copper is from 0.1 : 1 to 50: 1.
  • the copper(I) salt is first combined with the copper-assisting additive to form a mixture, and the mixture is then combined with the carrier to form the biocidal composition.
  • the color change in the biocidal composition is minimized relative to a change in color of an otherwise identical composition in the absence of the copper-assisting additive, or an otherwise identical composition absent the copper(I) salt, or an otherwise identical composition absent both the copper-assisting additive and the copper(I) salt.
  • the copper-assisting additive is any compound or formula disclosed herein (for example, a compound of formula (I), (II), or any combination thereof), by itself or themselves, or together with a compound of formula (III), (IV), (V), or any combination thereof.
  • a method of minimizing a color change in a biocidal composition wherein the copper-assisting additive is any compound disclosed herein, such as trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphite, tris(2-ethylhexyl) phosphite, triisopropyl phosphite, tris(l,l,l,3,3,3-hexafluoro-2-propyl) phosphite, tris(hydroxylpropyl) phosphine, tributyl phosphine, or any combination thereof, by itself or themselves, or together with a compound such as 2-ethylhexyl phosphate, bis(2-ethylhexyl)phosphate, tris(2- ethylhexyl)phosphate, methyl phosphate,
  • a method of minimizing a color change in a biocidal composition wherein the composition demonstrates a greater than 3 logarithmic reduction in a concentration of a microbe selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, E. coli, SARS-Cov-2, and mixtures thereof.
  • Antimicrobial efficacy may be measured as described elsewhere herein, such as by using the EPA Test.
  • a method of minimizing a color change in a biocidal composition wherein a CIE AE* value of the biocidal material is less than 10, as measured according to formula (VI): wherein L*, a*, and b* are the CIE L*, a*, and b* values of the biocidal material and the L* CO ntroi, a*controi, and b* con troi are the CIE L*, a*, and b* values of an otherwise identical composition without either the copper(I) salt or the copper-assisting additive.
  • a biocidal composition may exhibit a AE of less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, or less than 3, or less than 2, as measured according to formula (VI): wherein L*, a*, and b* are CIE values of the biocidal composition after preparing and then, within one day of preparing, storing the biocidal composition at ambient temperature and ambient relative humidity for 7 days (for example, 10 days, 15 days, 20 days, 25 days, 30 days, 40 days, 50 days, 60 days, 75 days, 90 days, 100 days, 120 days, 150 days, 180 days, 365 days, 2 years, 3 years, 4 years, or 5 years, and the L’ control, 3- control, and b* CO ntroi are CIE values of an otherwise identical composition without either the copper(I) salt or the copper-assisting additive.
  • L*, a*, and b* are CIE values of the biocidal composition after preparing and then, within one day of preparing,
  • the present disclosure provides a biocidal additive formulation that includes a copper(I) salt and a copper-assisting additive.
  • the biocidal additive formulation may be a relatively concentrated formulation to be added to a carrier so as to provide a biocidal composition.
  • the biocidal additive formulation may be in the form of a package that may be added to, for example, a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, or a melamine resin by an end user, so as to make the polyurethane, the polyurethane precursor, the epoxy resin, the epoxy resin precursor, or the melamine resin have antimicrobial properties without substantially impacting color and/or transparency.
  • Such a biocidal additive formulation may also be added by a manufacturer during or after production of a bulk quantity of polyurethane precursor or epoxy resin precursor so as to impart, for example, desired antimicrobial properties.
  • a form of a biocidal additive formulation may include a powder, a slurry, a gel, a liquid, a concentrate, and a solution.
  • the biocidal additive formulation is in liquid form at ambient conditions (1 atm (-101.3 kPa) and 20 °C).
  • the biocidal additive formulation comprises solubilized copper(I) salt in the form of a copper complex, in which the copper(I) salt is coordinated to or otherwise associated with a copper-assisting additive that facilitates the solubility of the copper(I) salt.
  • a biocidal additive formulation for addition to a composition, rather than simply adding a copper salt to a composition, or rather than simply adding a copper salt and a copper-assisting additive separately to a composition.
  • addition of copper salt alone, or addition of copper salt and an additive separately to the same composition (without premixing) may, in some cases, not allow the copper-assisting additive to sufficiently promote the availability and/or persistence of copper(I) ions.
  • separate addition may not allow the copper-assisting additive to find and associate with the copper salt.
  • the biocidal additive formulation may include an antioxidant package.
  • Antioxidant packages may include single components or ternary mixtures.
  • antioxidant packages may include primary antioxidants; phenolics, such as BHT; secondary antioxidants, such as UltranoxTM 626, WestonTM 430 ZP, thioester-based antioxidants (thiosynergists), such as dioctadecyl 3,3 ’-thiodipropionate; ascorbate esters, such as ascorbyl palmitate; or any combination thereof.
  • the biocidal additive formulation may include a reducing agent.
  • reducing agents may include ascorbic acid, hydroxylamine hydrochloride, various phosphines, sulfite compounds, oxalic acid, sodium thiosulfate, or any combination thereof.
  • Examples of a form of a biocidal additive formulation may include a powder, a slurry, a gel, a liquid, a concentrate, and a solution.
  • the biocidal additive formulation may include an antioxidant package.
  • Antioxidant packages may include single components or ternary mixtures. Examples of antioxidant packages may include primary antioxidants; phenolics, such as BHT; secondary antioxidants, such as UltranoxTM 626, WestonTM 430 ZP, thioester-based antioxidants (thiosynergists), such as dioctadecyl 3,3’- thiodipropionate; ascorbate esters, such as ascorbyl palmitate; or any combination thereof.
  • the biocidal additive formulation may include a reducing agent.
  • reducing agents may include ascorbic acid, hydroxylamine hydrochloride, various phosphines, sulfite compounds, oxalic acid, sodium thiosulfate, or any combination thereof.
  • the biocidal additive formulation may be in a sealed container including an inert atmosphere.
  • the biocidal additive formulation has a molarity of the copper(I) salt dissolved in the biocidal additive formulation of from 20 mA/ to 200 mA/, including, for example, from 25 mA/, or from 30 mA/, or from 35 mA/, or from 40 mA/, or from 45 mA/, or from 50 mA/, or from 55 mA/, or from 60 mA/, or from 65 mA/, or from 70 mA/, or from 75 mA/, or from 80 mA/, or from 85 mA/, or from 90 mA/, or from 95 mA/, or from 100 mA/, or from 105 mA/, or from 110 mA/, or from 115 mA/, or from 120 mA/, or from 125 mA/, or from 130 mA/, or from 135 mA/, or from 140 mA/, or from 145
  • the biocidal additive formulation may include a copper-assisting additive at a molarity of the copper-assisting additive in the biocidal additive formulation of from 0.06 mA/ to 0.6 mA/; including, for example, from 0.065 mA/, or from 0.07 mA/, or from 0.075 mA/, or from 0.08 mA/, or from 0.085 mA/, or from 0.09 mA/, or from 0.095 mA/, or from 0.1 mA/, or from 0.105 mA/, or from 0.110 mA/, or from 0.115 mA/, or from 0.120 mA/, or from 0.125 mA/, or from 0.130 mA/, or from 0.135 mA/, or from 0.140 mA/, or from 0.145 mA/, or from 0.150 mA/, or from 0.155 mA/, or from 0.160 mA/, or from 0.165 mA/
  • the biocidal additive formulation may include a copper(I) salt and a copper-assisting additive at any of the ratios disclosed elsewhere herein.
  • the biocidal additive formulation may include a solvent at a molarity of the solvent in the biocidal additive formulation of from 0.8 mA/ to 8.00 mA/, including, for example, from 0.85 mA/, or from 0.90 mA/, or from 0.95 mA/, or from 1.00 mA/, or from 1.05 mA/, or from 1.10 mA/, or from 1.15 mA/, or from 1.20 mA/, or from 1.25 mA/, or from 1.30 mA/, or from 1.35 mA/, or from 1.40 mA/, or from 1.45 mA/, or from 1.50 mA/, or from 1.55 mA/, or from 1.60 mA/, or from 1.65 mA/, or from 1.70 mA/, or from 1.75 mA/, or from 1.80 mA/, or from 1.85 mA/, or from 1.90 mA/, or
  • the present disclosure provides a biocidal composition, including: a carrier, including a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof; a copper(I) salt; and a copper- assisting additive different from the carrier; wherein the copper-assisting additive includes a phosphite, a phosphine, or a combination thereof; and wherein the biocidal composition or a film thereof exhibits an antimicrobial efficacy of at least 3 log kill as measured with an EPA Test after storage of the biocidal composition or the film thereof at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein).
  • the phosphite may be a compound of formula (I): wherein each R 1 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally fluorosubstituted.
  • the phosphine may be a compound of formula (II): wherein each R 2 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally substituted with a hydroxy group.
  • the carrier may include a polyurethane, a polyurethane precursor, or a combination thereof.
  • the carrier may include an epoxy resin, an epoxy resin precursor, or a combination thereof.
  • the carrier may include an organic solvent.
  • the copper(I) salt may be a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • the copper(I) salt may be copper(I) bromide or copper(I) iodide.
  • each R 1 may be independently selected from C2-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, C2-C4 alkyl, or phenyl.
  • each R 2 may be independently selected from C2-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the copper-assisting additive may be triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.
  • a molar ratio of the copper-assisting additive to the copper(I) salt may be at least 0.5: 1.
  • the biocidal composition may further include a compound of formula (III), (IV), (V), or any combination thereof: wherein eachR 3 may be independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci- C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 may be independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 may be independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.
  • each R 3 may be independently selected from C1-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the biocidal composition may further include 2-ethylhexyl phosphate.
  • each R 4 may be independently selected from C1-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the biocidal composition may further include tributyl borate.
  • each R 5 may be independently selected from C1-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the biocidal composition may further include tributyl citrate.
  • the biocidal composition may exhibit a AE of less than 6, as calculated according to wherein L*, a*, and b* are CIE values of the biocidal composition after preparing and then storing the biocidal composition at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L” control, 3- control, and b* CO ntroi are CIE values of an otherwise identical composition without either the copper(I) salt or the copper-assisting additive.
  • the biocidal composition or the film thereof may exhibit a transmittance of at least 98% as measured at each wavelength from 400 to 700 nanometers when measured at a thickness of 40 pm.
  • the transmittance may be within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof without either the copper(I) salt or the copper-assisting additive when measured at a thickness of 40 pm.
  • a method of preparing the biocidal composition may include: adding a biocidal additive formulation to a carrier; wherein when the carrier is a polyurethane or an epoxy resin, the biocidal additive formulation may include the copper(I) salt and the copper-assisting additive; wherein when the carrier is a second polyurethane precursor, the biocidal additive formulation may include a first polyurethane precursor, the copper(I) salt, and the copper-assisting additive; and wherein when the carrier is a second epoxy resin precursor, the biocidal additive formulation may include a first epoxy resin precursor, the copper(I) salt, and the copper-assisting additive.
  • a biocidal additive formulation including: a copper(I) salt; and a copper-assisting additive; wherein a biocidal composition including the biocidal additive formulation and a carrier, or a film of the biocidal composition, exhibits an antimicrobial efficacy of at least 3 log kill as measured with an EPA Test after storage of the biocidal composition or the film thereof at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein); wherein the carrier includes a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof; wherein the biocidal composition exhibits a AE of less than 6, as calculated according to wherein L*, a*, and b* are CIE values of the biocidal composition after preparing and then storing the biocidal composition at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L’ control, 3- control, and
  • the biocidal additive formulation may include an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof.
  • the copper(I) salt may be a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • the copper(I) salt may be copper(I) bromide or copper(I) iodide.
  • the copper-assisting additive may include a phosphite, a phosphine, or a combination thereof.
  • the phosphite may be a compound of formula (I): wherein each R 1 may be independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally fluorosubstituted, provided that all R 1 are not simultaneously hydrogen.
  • the phosphine may be a compound of formula (II): wherein each R 2 may be independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally substituted with a hydroxy group, provided that all R 2 are not simultaneously hydrogen.
  • each R 1 may be independently selected from C2-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl, or phenyl.
  • each R 2 may be independently selected from C2-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the copper-assisting additive may be triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.
  • a molar ratio of the copper-assisting additive to the copper(I) salt may be at least 0.5: 1.
  • the biocidal additive formulation may further include a compound of formula (III), (IV), (V), or any combination thereof: wherein eachR 3 may be independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci- C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 may be independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 may be independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.
  • each R 3 may be independently selected from C1-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the biocidal additive formulation may further include 2-ethylhexyl phosphate.
  • each R 4 may be independently selected from C1-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the biocidal additive formulation may further include tributyl borate.
  • each R 5 may be independently selected from C1-C13 alkyl, Ci-Cs alkyl, Ci-Ce alkyl, C2-C5 alkyl, or C2-C4 alkyl.
  • the biocidal additive formulation may further include tributyl citrate.
  • the biocidal composition or the film thereof may exhibit a transmittance of at least 98% as measured at each wavelength from 400 to 700 nanometers when measured at a thickness of 40 pm.
  • the transmittance may be within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof without either the copper(I) salt or the copper-assisting additive when measured at a thickness of 40 pm.
  • the biocidal additive formulation may further include an antioxidant.
  • the biocidal additive formulation may further include a reducing agent.
  • the formulation may be in a sealed container including an inert atmosphere.
  • a first aspect relates to a biocidal composition, comprising: a carrier, comprising a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof; a copper(I) salt; and a copper-assisting additive different from the carrier; wherein the copper-assisting additive comprises a phosphite, a phosphine, or a combination thereof; and wherein the biocidal composition or a film thereof exhibits an antimicrobial efficacy of at least 3 log kill as measured with an EPA Test after storage of the biocidal composition or the film thereof at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein).
  • a second aspect relates to the biocidal composition of aspect 1, or any preceding aspect, wherein the phosphite is a compound of formula (I): wherein each R 1 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally fluorosubstituted.
  • a third aspect relates to the biocidal composition of any preceding aspect, wherein the phosphine is a compound of formula (II): wherein each R 2 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally substituted with a hydroxy group.
  • a fourth aspect relates to the biocidal composition of any preceding aspect, wherein the carrier comprises a polyurethane, a polyurethane precursor, or a combination thereof.
  • a fifth aspect relates to the biocidal composition of aspects 1 to 3, or any preceding aspect, wherein the carrier comprises an epoxy resin, an epoxy resin precursor, or a combination thereof.
  • a sixth aspect relates to the biocidal composition of any preceding aspect, wherein the carrier comprises an organic solvent.
  • a seventh aspect relates to the biocidal composition of any preceding aspect, wherein the copper(I) salt is a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • the copper(I) salt is a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • An eighth aspect relates to the biocidal composition of any preceding aspect, wherein the copper(I) salt is copper(I) bromide or copper(I) iodide.
  • a ninth aspect relates to the biocidal composition of aspects 2 to 8, or any preceding aspect, wherein each R 1 is independently selected from C2-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, C2-C4 alkyl), or phenyl.
  • a tenth aspect relates to the biocidal composition of aspects 3 to 9, or any preceding aspect, wherein each R 2 is independently selected from C2-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • An eleventh aspect relates to the biocidal composition of any preceding aspect, wherein the copper-assisting additive is triethyl phosphite, triphenyl phosphite, tributyl phosphine, or any combination thereof.
  • a twelfth aspect relates to the biocidal composition of any preceding aspect, wherein a molar ratio of the copper-assisting additive to the copper(I) salt is at least 0.5: 1.
  • a thirteenth aspect relates to the biocidal composition of any preceding aspect, further comprising a compound of formula (III), (IV), (V), or any combination thereof: wherein each R 3 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci- C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.
  • a fourteenth aspect relates to the biocidal composition of aspect 13, or any preceding aspect, wherein each R 3 is independently selected from C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a fifteenth aspect relates to the biocidal composition of any preceding aspect, further comprising 2-ethylhexyl phosphate.
  • a sixteenth aspect relates to the biocidal composition of aspect 13, or any preceding aspect, wherein each R 4 is independently selected from C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a seventeenth aspect relates to the biocidal composition of any preceding aspect, further comprising tributyl borate.
  • An eighteenth aspect relates to the biocidal composition of aspect 13, or any preceding aspect, wherein each R 5 is independently selected from C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a nineteenth aspect relates to the biocidal composition of any preceding aspect, further comprising tributyl citrate.
  • a twentieth aspect relates to the biocidal composition of any preceding aspect, wherein the biocidal composition exhibits a AE of less than 6, as calculated according to wherein L*, a*, and b* are CIE values of the biocidal composition after preparing and then storing the biocidal composition at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L” control, 3- control, and b* CO ntroi are CIE values of an otherwise identical composition without either the copper(I) salt or the copper-assisting additive.
  • a twenty-first aspect relates to the biocidal composition of any preceding aspect, wherein the biocidal composition or the film thereof exhibits a transmittance of at least 98% as measured at each wavelength from 400 to 700 nanometers when measured at a thickness of 40 pm.
  • a twenty-second aspect relates to the biocidal composition of aspect 21, or any preceding aspect, wherein the transmittance is within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof without either the copper(I) salt or the copper-assisting additive when measured at a thickness of 40 pm.
  • a twenty -third aspect relates to a method of preparing the biocidal composition of any preceding aspect, comprising: adding a biocidal additive formulation to a carrier; wherein when the carrier is a polyurethane or an epoxy resin, the biocidal additive formulation comprises the copper(I) salt and the copper-assisting additive; wherein when the carrier is a second polyurethane precursor, the biocidal additive formulation comprises a first polyurethane precursor, the copper(I) salt, and the copper-assisting additive; and wherein when the carrier is a second epoxy resin precursor, the biocidal additive formulation comprises a first epoxy resin precursor, the copper(I) salt, and the copper-assisting additive.
  • a twenty-fourth aspect relates to a biocidal additive formulation, comprising:a copper(I) salt; and a copper-assisting additive; wherein a biocidal composition comprising the biocidal additive formulation and a carrier, or a film of the biocidal composition, exhibits an antimicrobial efficacy of at least 3 log kill as measured with an EPA Test after storage of the biocidal composition or the film thereof at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein); wherein the carrier comprises a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof; wherein the biocidal composition exhibits a AE of less than 6, as calculated according to wherein L*, a*, and b* are CIE values of the biocidal composition after preparing and then storing the biocidal composition at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L’
  • a twenty-fifth aspect relates to the biocidal additive formulation of aspect 24, or any preceding aspect, further comprising an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof.
  • a twenty-sixth aspect relates to the biocidal additive formulation of aspect 24 or 25, or any preceding aspect, wherein the copper(I) salt is a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • the copper(I) salt is a copper(I) halide, iodo(triethyl phosphite)copper(I), or a tetrakis(acetonitrile)copper(I) salt.
  • a twenty-seventh aspect relates to the biocidal additive formulation of aspects 24 to 26, or any preceding aspect, wherein the copper(I) salt is copper(I) bromide or copper(I) iodide.
  • a twenty-eighth aspect relates to the biocidal additive formulation of aspects 24 to 27, or any preceding aspect, wherein the copper-assisting additive comprises a phosphite, a phosphine, or a combination thereof.
  • a twenty-ninth aspect relates to the biocidal additive formulation of aspect 28, or any preceding aspect, wherein the phosphite is a compound of formula (I): wherein each R 1 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally fluorosubstituted.
  • a thirtieth aspect relates to the biocidal additive formulation of aspect 28, or any preceding aspect, wherein the phosphine is a compound of formula (II): wherein each R 2 is independently selected from C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, any of which is optionally substituted with a hydroxy group.
  • a thirty-first aspect relates to the biocidal additive formulation of aspect 29, or any preceding aspect, wherein each R 1 is independently selected from C2-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a thirty-second aspect relates to the biocidal additive formulation of aspect 30, or any preceding aspect, wherein each R 2 is independently selected from C2-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a thirty-third aspect relates to the biocidal additive formulation of aspects 24 to 32, or any preceding aspect, wherein the copper-assisting additive is triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.
  • a thirty-fourth aspect relates to the biocidal additive formulation of aspects 24 to 33, or any preceding aspect, wherein a molar ratio of the copper-assisting additive to the copper(I) salt is at least 0.5: 1.
  • a thirty-fifth aspect relates to the biocidal additive formulation of aspects 24 to 34, or any preceding aspect, further comprising a compound of formula (III), (IV), (V), or any combination thereof: wherein each R 3 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci- C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.
  • a thirty-sixth aspect relates to the biocidal additive formulation of aspect 35, or any preceding aspect, wherein each R 3 is independently selected from C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a thirty-seventh aspect relates to the biocidal additive formulation of aspects 24 to 34, or any preceding aspect, further comprising 2-ethylhexyl phosphate.
  • a thirty-eighth aspect relates to the biocidal additive formulation of aspect 35, or any preceding aspect, wherein each R 4 is independently selected from C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a thirty-ninth aspect relates to the biocidal additive formulation of aspects 24 to 34, or any preceding aspect, further comprising tributyl borate.
  • a fortieth aspect relates to the biocidal additive formulation of aspect 35, or any preceding aspect, wherein each R 5 is independently selected from C1-C13 alkyl (or Ci-Cs alkyl, or Ci-Ce alkyl, or C2-C5 alkyl, or C2-C4 alkyl).
  • a forty-first aspect relates to the biocidal additive formulation of aspects 24 to 34, or any preceding aspect, further comprising tributyl citrate.
  • a forty-second aspect relates to the biocidal additive formulation of aspects 24 to 41, or any preceding aspect, wherein the biocidal composition or the film thereof exhibits a transmittance of at least 98% as measured at each wavelength from 400 to 700 nanometers when measured at a thickness of 40 pm.
  • a forty-third aspect relates to the biocidal additive formulation of aspect 42, or any preceding aspect, wherein the transmittance is within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof without either the copper(I) salt or the copper-assisting additive when measured at a thickness of 40 pm.
  • a forty-fourth aspect relates to the biocidal additive formulation of aspects 24 to 43, or any preceding aspect, further comprising an antioxidant package.
  • a forty-fifth aspect relates to the biocidal additive formulation of aspects 24 to 43, or any preceding aspect, further comprising a reducing agent.
  • a forty-sixth aspect relates to the biocidal additive formulation of aspects 24 to 45, or any preceding aspect, wherein the formulation is in a sealed container comprising an inert atmosphere.
  • a forty-seventh aspect relates to a combination of any two or more preceding aspects, or any portion(s) thereof.
  • the compositions and methods described above may be better understood in connection with the following Examples, which are non-limiting examples provided as an illustration of the concepts disclosed herein. The illustrated methods are applicable to other examples of biocidal compositions of the present disclosure. The procedures described as general methods describe what is believed will be typically effective to prepare the compositions indicated. However, the person skilled in the art will appreciate that it may be necessary to vary the procedures for nay given example of the present disclosure, for example, vary the order or steps and/or the chemical reagents used.
  • the complexes with copper(I) salts may be compared to mixtures including copper-containing material including a plurality of copper-containing glass or glass-ceramic particles.
  • copper-containing glass is meant to include “copper-containing glass-ceramic” unless clearly contradicted by context.
  • the “ceramic” portion of the copper-containing glass-ceramic may include, in some aspects, cuprite crystals.
  • the copper-containing material may include copper-containing glass or copper-containing glass-ceramic particles.
  • the copper-containing glass or glassceramic particles may be a biocidal inorganic glass or glass-ceramic powder including copper particles.
  • the individual particles of the copper-containing glass particles may be effective as a biocidal agent, such copper-containing glass may have potential drawbacks related to color of the resulting composition and stability of copper(I).
  • the copper-containing glass or glass-ceramic particles may independently include a Cu metal, Cu 1+ , Cu 2+ , or a combination of Cu 1+ and Cu 2+ .
  • the combined total of the Cu species may be 10 weight % or more of the copper-containing material. However, as will be discussed in more detail below, the amount of Cu 2+ may be minimized or reduced such that the copper- containing glass or glass-ceramic particles may be substantially free of Cu 2+ .
  • the copper may be non-complexed or may have a ligand bonded thereto to form a complex.
  • the Cu 1+ ions may be present on or in the surface and/or the bulk of the copper-containing glass or glass-ceramic particles.
  • the copper-containing glass or glass-ceramic particles may include copper- containing glass or glass-ceramic, copper metal, copper(I) oxide, copper(II) oxide, or a combination thereof.
  • the copper-containing glass or glass-ceramic particles may include only one of copper-containing glass or glass-ceramic, copper metal, copper(I) oxide, or copper(II) oxide.
  • the Cu 1+ ions may be present in a glass or glass-ceramic network and/or a glass or glass-ceramic matrix of the copper-containing glass or glass-ceramic particles.
  • the Cu 1+ ions are present in the glass or glass-ceramic network, the Cu 1+ ions and atomically bonded to the atoms in the glass or glass-ceramic mixture.
  • the Cu 1+ ions may be present in the form of Cu 1+ crystals that are dispersed in the glass or glass-ceramic matrix.
  • the Cu 1+ crystals may include cuprite (CU2O).
  • the material may be referred to as a glass-ceramic or ceramic, which is intended to refer to a specific type of glass or glass-ceramic with crystals that may or may not be subjected to a traditional ceramming process by which one or more crystalline phases are introduced and/or generated in the glass or glass-ceramic.
  • the material may be referred to as a copper-containing glass.
  • both Cu 1+ crystals and Cu 1+ ions not associated with a crystal may be present in the copper-containing glasses or glass-ceramics described herein.
  • Copper-containing glasses or glass-ceramics may include a copper-containing oxide in an amount, in mole percent, in the range from 10 to 50, from 10 to 49, from 10 to 48, from 10 to 47, from 10 to 46, from 10 to 45, from 10 to 44, from 10 to 43, from 10 to 42, from 10 to 41, from 10 to 40, from 10 to 39, from 10 to 38, from 10 to 37, from 10 to 36, from 10 to 35, from 10 to 50, from 10 to 49, from 10 to 48, from 10 to 47, from 10 to 46, from 10 to 45, from 10 to 44, from 10 to 43, from 10 to 42, from 10 to 41, from 10 to 40, from 10 to 39, from 10 to 38, from 10 to 37, from 10 to 36, from 10 to 35, from
  • 10 to 34 from 10 to 33, from 10 to 32, from 10 to 31, from 10 to 30, from 10 to 29, from 10 to
  • the copper-containing oxide may be present in the copper-containing glasses or glass-ceramics in an amount of 20 mole percent, 25 mole percent, 30 mole percent, or 35 mole percent.
  • the copper-containing oxide may include CuO, CU2O, and/or combinations thereof.
  • the copper-containing glass or glass-ceramic particles may include cuprous oxide in an amount from 29.0 to 36.0 weight percent of the copper- containing glass or glass-ceramic particles.
  • the copper-containing oxides in the copper- containing glasses or glass-ceramics form the Cu 1+ ions present in the resulting glass or glass- ceramic.
  • Copper may be present in a glass or glass-ceramic, or compositions thereof, in various forms, including Cu°, Cu 1+ , and Cu 2+ .
  • the copper-containing glass or glass-ceramic portion of the individual particles of the copper-containing glass or glass-ceramic particles may be formed from a glass composition that may include, but is not limited to, in mole percent, SiCh in the range from 30 to 70, AI2O3 in the range from 0 to 20, a copper-containing oxide in the range from 10 to 50, CaO in the range from 0 to 15, MgO in the range from 0 to 15, P2O5 in the range from 0 to 25, B2O3 in the range from 0 to 25, K2O in the range from 0 to 20, ZnO in the range from 0 to 5, Na2O in the range from 0 to 20, and/or Fe2O3 in the range from 0 to 5, nanoparticles thereof, and/or a mixture thereof.
  • the amount of the copper-containing oxide is greater than the amount of AI2O3.
  • the glass composition may include a content of R2O, where R may include K, Na, Li, Rb, Cs, and
  • the glass composition may include one or more divalent cation oxides, such as alkaline earth oxides and/or ZnO.
  • the glass composition may include NiO, TiO2, Fe2O3, Cr2O3, or CO3O4 in an amount in the range up to 10 mol %, or from 0.01 mol % to 10 mol %, from 1 mol % to 10 mol %, from 2 mol % to 10 mol %, from 5 mol % to 10 mol %, from 0.01 mol % to 0.8 mol %, or from 0.01 mol % to 5 mol %.
  • the copper-containing glasses or glass-ceramics formed from the glass compositions may include a plurality of Cu 1+ ions. In certain examples, such Cu 1+ ions form part of the glass network. In certain examples, the Cu 1+ ions that are dispersed in the glass matrix are Cu 1+ crystals. The Cu 1+ may be present in the form of cuprite. The cuprite present in the copper- containing glass-ceramic may form a phase distinct from the glass matrix or glass phase. In other examples, the cuprite may form part of or may be associated with one or more glass phases.
  • the copper-containing glass may be produced by any suitable method.
  • the copper-containing glass may be performed using melting tanks that are typically used for melting glass compositions such as soda lime silicate.
  • the copper- containing glass may be formed into a sheet using forming processes known in the art. Forming methods may include float glass processes and down-draw processes such as fusion draw and slot draw. After formation, the copper-containing glass may be formed into sheets and may be shaped, polished, or otherwise processed for a desired end use.
  • the copper- containing glass may be ground to a powder or particulate form. In certain examples, the particulate copper-containing glass may be combined with other materials or carriers.
  • the EPA Test was used to test for antimicrobial efficacy for all examples herein.
  • a commercially available two-part polyurethane (Eastwood® 4: 1 High Solids Urethane Premium Show Clear) was added per the manufacturer’s instructions, using a 4: 1 weight: weight ratio of Part A and Part B.
  • Part A and Part B were mixed together first, and allowed to sit for 45 minutes before addition of copper source and copper-assisting additive.
  • the copper(I) salt and copper-containing glass were prepared first, during which the copper source was dissolved or dispersed in acetonitrile (“ACN”) (with EHP, if used), allowed to rest for 1 hour before addition of triethyl phosphite (“TEP”), and the mixture was added to the polyurethane mixture.
  • ACN acetonitrile
  • TEP triethyl phosphite
  • the resulting material was mixed thoroughly and a film was cast on a sheet of PVC and allowed to cure for 24 hours. Antimicrobial testing was performed on 1” x 1” cutouts of the resulting film.
  • the procedure for two-part polyurethanes and two-part epoxies was as follows: solvent and copper-assisting additive were mixed together into a homogeneous solution and added to copper species. The copper species and additive solution were mixed until the copper species was completely dissolved or a homogeneous liquid phase was formed. Additional additives were added to the mixture if necessary to achieve homogeneity. Prior to the addition of the copper species and additive solution to the two-part polyurethane, the polyurethane precursors were mixed according to the manufacturer’s specified ratio, and the polyurethane mixture was allowed to rest with exposure to air and occasional stirring to allow the polyurethane mixture to begin reacting.
  • the copper species and additive mixture was added to the polyurethane mixture, after filtering solids if necessary, and the entire mixture was stirred until homogeneous.
  • the mixture was applied to a substrate using conventional coating techniques, including spraying, spinning, dipping, and film applicating.
  • film applicating the dosed 2-part polyurethane solution was applied in front of the film applicator using a syringe and the film is drawn down over the substrate with a target wet film thickness between 2 and 10 mil. The film was then allowed to cure in either ambient conditions or elevated temperature according to product specifications. Additional coats may be applied as necessary.
  • An additional copper-assisting additive was used in combination with EHP in an attempt to keep the copper that is extracted by EHP from being oxidized.
  • TEP copper-assisting additive
  • the copper- containing glass achieved antimicrobial efficacy of at least 3 log kill.
  • Antimicrobial efficacy was lower using copper(I) salt as the copper source, a log kill of about 1-2.
  • the same additives in the same stoichiometry, with the same order of addition, were used for both the CCG samples and the copper(I) salt samples.
  • 5% CCG refers to 5 weight % CCG in solution
  • 0.45% Cu(ACN)4 refers to 0.45 weight % copper in solution (5% CCG equates to approximately 0.45 % available copper).
  • the following example illustrates experiments to determine the antimicrobial efficacy of copper(I)-additives complexes in epoxy resin prepared according to the procedure of Example 1 in which iodo(triethyl phosphite)copper(I) was the copper(I) salt.
  • the use of the iodo(triethyl phosphite)copper(I) complex did not yield full kill in epoxy resin, and did not change the antimicrobial efficacy above the base epoxy resin, as illustrated in FIGs. 5 and 6.
  • TEP tetrakis(acetonitrile)copper(I) (3 : 1 molar ratio) or to copper(I) iodide (3:1 molar ratio) illustrates that for epoxy resin, more TEP is required for antimicrobial efficacy as compared to polyurethanes.
  • the addition of more TEP did result in higher antimicrobial efficacy with higher amounts of TEP. While TEP may be a strong copper-assisting additive, there are more amine groups in an epoxy resin relative to binding groups in TEP.
  • An iodo- or bromo(triethyl phosphite)copper(I) complex may be generated in situ without the need for synthesizing the complex first.
  • acetonitrile it was possible to fully dissolve the copper(I) bromide, by addition of three molar equivalents of EHP in addition to 1 equivalent of TEP, resulting in antimicrobial efficacy (full kill) in the amounts according to Table 7 below, as illustrated in FIG. 7. Without addition of TEP, the copper(I) bromide was not solubilized in solution, resulting in no antimicrobial efficacy.
  • the solution of the copper(I) salt and the copper-assisting additive was pre-filtered prior to the addition to the two-part polyurethane, as particulates in the coating would have resulted in a bumpy coating. Incorporation of undissolved copper(I) salts may eventually result in antimicrobial efficacy.
  • SPDB iodine
  • I2 iodine
  • TEP, I2, and SPDB are molar equivalents relative to amount of copper in solution.
  • EHP may be substituted for another solubilizer such as tributyl citrate (“TBC”) or tributyl borate (“TBB”) in the amounts according to Table 9 below, which have both been shown to yield higher antimicrobial efficacy (tributyl citrate full kill, tributyl borate >4 log kill), as illustrated in FIG. 9.
  • TBC tributyl citrate
  • TB tributyl borate
  • TBC, and TBB are molar equivalents relative to amount of copper in solution.
  • TBP Tributyl phosphine

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Abstract

L'invention concerne une composition biocide comprenant un porteur, comprenant un polyuréthane, un précurseur de polyuréthane, une résine époxy, un précurseur de résine époxy, une résine de mélamine, ou toute combinaison de ceux-ci ; un sel de cuivre(I) ; et un additif d'assistance au cuivre différent du porteur comprenant un phosphite, une phosphine, ou une combinaison de ceux-ci ; et la composition biocide ou un film de celle-ci présentant une efficacité antimicrobienne d'au moins 3 log kill après stockage de la composition biocide ou du film de celle-ci à température ambiante et humidité relative ambiante pendant 90 jours. L'invention concerne en outre une formulation d'additif biocide comprenant un sel de cuivre (I) et un additif d'assistance au cuivre, où une composition biocide comprenant la formulation d'additif biocide et un support, ou un film de la composition biocide, présente une efficacité antimicrobienne d'au moins 3 log kill telle que mesurée avec un essai EPA.
PCT/US2024/037025 2023-07-20 2024-07-08 Revêtements réactifs transparents et incolores antimicrobiens à base de cuivre comprenant du cuivre(i) et des additifs Pending WO2025019173A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
KR20180011807A (ko) * 2015-06-08 2018-02-02 마이코 사이언시즈 리미티드 항미생물 및 농화학 조성물
CN110330693A (zh) * 2019-07-30 2019-10-15 安徽正合雅聚新材料科技有限公司 一种金属离子增强的抗菌聚合物及其制备方法
EP3695724A1 (fr) * 2017-10-12 2020-08-19 Ibiden Co., Ltd. Substrat antiviral, composition antivirale, procédé de fabrication de substrat antiviral, substrat antimicrobien, composition antimicrobienne et procédé de fabrication de substrat antimicrobien
CN113712042A (zh) * 2021-05-24 2021-11-30 常州崇高纳米材料有限公司 一种多功能持效抗菌组合物及其制备方法
CN116171302A (zh) * 2020-08-14 2023-05-26 Ppg建筑涂层有限公司 抗微生物涂层

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180011807A (ko) * 2015-06-08 2018-02-02 마이코 사이언시즈 리미티드 항미생물 및 농화학 조성물
EP3695724A1 (fr) * 2017-10-12 2020-08-19 Ibiden Co., Ltd. Substrat antiviral, composition antivirale, procédé de fabrication de substrat antiviral, substrat antimicrobien, composition antimicrobienne et procédé de fabrication de substrat antimicrobien
CN110330693A (zh) * 2019-07-30 2019-10-15 安徽正合雅聚新材料科技有限公司 一种金属离子增强的抗菌聚合物及其制备方法
CN116171302A (zh) * 2020-08-14 2023-05-26 Ppg建筑涂层有限公司 抗微生物涂层
CN113712042A (zh) * 2021-05-24 2021-11-30 常州崇高纳米材料有限公司 一种多功能持效抗菌组合物及其制备方法

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