Copper-based antimicrobial transparent colorless reactive coating comprising copper (i) and additives

Abstract

There is provided 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 auxiliary additive different from the carrier, the copper auxiliary additive comprising a phosphite, a phosphine, or a combination thereof; and wherein the biocidal composition or the film thereof exhibits an antimicrobial efficacy of at least 3 logarithm killing after storage of the biocidal composition or the film thereof at ambient temperature and ambient relative humidity for 90 days. Further provided is a biocidal additive formulation comprising a copper (I) salt and a copper auxiliary 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 logarithm killing, as measured by the EPA test.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 527,973, filed July 20, 2023, which is incorporated herein by reference in its entirety for all purposes. Technical Field

[0003] This disclosure relates to biocidal compositions. More specifically, this disclosure relates to biocidal compositions comprising polyurethane and / or epoxy resins or precursors thereof, copper (I) salts, and copper auxiliary additives. Background Technology

[0004] The composition may be in the form of an article, layer, or coating, or in the form of a liquid composition comprising suspensions and solutions, which may be applied to a surface or (e.g., stored in a container before use). Copper-containing compositions that initially possess antimicrobial efficacy and / or color stability may experience a decrease in antimicrobial efficacy and / or color variation over time, which may render the composition visually unappealing or unsuitable for a particular purpose. For example, although copper(I) ions and complexes may be colorless and possess effective antimicrobial properties, over time, copper(I) may be oxidized to copper(II) which has a green or blue / green hue and is less effective in antimicrobial properties. Such changes are generally undesirable. Additionally, in some compositions, the availability of copper at a surface (e.g., the surface of an article) can be a challenge. Reactive systems that rely on reactive precursors (such as polyurethanes and epoxy resins) for crosslinking and curing involve the additional challenge of ensuring that copper ligands do not interfere with the curing process to maintain the high durability of highly crosslinked coating materials.

[0005] Therefore, there is a need for copper-containing compositions comprising polyurethane and / or epoxy resins or their precursors that have improved copper (e.g., copper(I)) availability. Summary of the Invention

[0006] In one example, this disclosure provides 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 auxiliary additive derived from the carrier. The copper auxiliary additive comprises a phosphite, a phosphine, or a combination thereof. After storing the biocidal composition or its film at ambient temperature and relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), the biocidal composition or its film exhibits antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing.

[0007] In some instances, the phosphite may be a compound of formula (I):

[0008] ;

[0009] Each R 1 Independently selected from C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl groups, any of which may optionally be substituted with fluorine. In some instances, the phosphine may be a compound of formula (II):

[0010] ;

[0011] Each R 2 Independently selected from C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl groups, any of which may optionally be substituted with a hydroxyl group. In some examples, the support may comprise a polyurethane, a polyurethane precursor, or a combination thereof. In some examples, the support may comprise an epoxy resin, an epoxy resin precursor, or a combination thereof. In some examples, the support may comprise an organic solvent. In some examples, the copper (I) salt may be copper halide (I), copper iodide (triethyl phosphite) (I), or copper tetrakis(acetonitrile) (I). In some examples, the copper (I) salt may be copper bromide (I) or copper iodide (I). In some examples, each R... 1 It can be independently selected from C2-C 13 Alkyl and phenyl. In some instances, each R 3 It can be independently selected from C2-C 13 Alkyl group. In some instances, the copper auxiliary additive may be triethyl phosphite, tributylphosphine, triphenyl phosphite, or any combination thereof. In some instances, the molar ratio of the copper auxiliary additive to the copper (I) salt may be at least 0.5:1. In some instances, the biocidal composition may further comprise a compound of formula (III), a compound of formula (IV), a compound of formula (V), or any combination thereof:

[0012] ;

[0013] ;

[0014] ;

[0015] Each R 3 Independently selected from hydrogen, C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl, provided that all R 3 They are not all hydrogen at the same time; each of the R's is hydrogen. 4 Independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; wherein each R 5 is independently selected from hydrogen, Ci-C 20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 5 are not simultaneously hydrogen. In certain examples, each R 3 may be independently selected from Ci-C 13 alkyl. In certain examples, the biocidal composition can further comprise 2-ethylhexyl phosphoric acid. In certain examples, each R 4 may be independently selected from Ci-C 13 alkyl. In certain examples, the biocidal composition can further comprise tributyl borate. In certain examples, each R 5 may be independently selected from Ci-C 13 alkyl. In certain examples, the biocidal composition can further comprise tributyl citrate. In certain examples, the biocidal composition can exhibit a delta E of less than 6, as calculated according to:

[0016] ; and

[0017] wherein L * , a * , and b * are the CIE values of the biocidal composition after the biocidal composition is prepared and then stored at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L * 对照 , a * 对照 , and b * 对照the biocidal composition or the film thereof exhibits a transmittance of at least 98% when measured at a thickness of 40 pm, as measured at each wavelength from 400 nanometers to 700 nanometers. In certain examples, the transmittance can be within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that is free of the copper (I) salt or the copper-assisting additive, when measured at a thickness of 40 pm. In certain examples, a method of making the biocidal composition can comprise 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.

[0018] In another example, the present disclosure provides a biocidal additive formulation comprising: a copper (I) salt; and a copper-assisting additive. The biocidal composition or the film thereof exhibits an antimicrobial efficacy of at least 3 log kill after storing a biocidal composition comprising the biocidal additive formulation and a carrier or a film of 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), as measured by the EPA test. The carrier comprises a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof. The biocidal composition exhibits a delta E of less than 6, as calculated according to:

[0019] .

[0020] L * , a * and b * are the CIE values of the biocidal composition after making the biocidal composition 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 * 对照 , a * 对照 and b * 对照 are the CIE values of an otherwise identical composition that is free of the copper (I) salt or the copper-assisting additive.

[0021] In some instances, the biocidal additive formulation may further comprise an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof. In some instances, the copper (I) salt may be copper halide (I), copper iodide (triethyl phosphite) (I), or copper tetrakis(acetonitrile) (I). In some instances, the copper (I) salt may be copper bromide (I) or copper iodide (I). In some instances, the copper auxiliary additive may comprise a phosphite, phosphine, or a combination thereof. In some instances, the phosphite may be a compound of formula (I):

[0022] ;

[0023] Each R 1 Independently selected from C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl groups, any of which may optionally be substituted with fluorine. In some instances, the phosphine may be a compound of formula (I):

[0024] ;

[0025] Each R 2 Independently selected from C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl groups, any of which may optionally be substituted with a hydroxyl group. In some instances, each R 1 It can be independently selected from C2-C 13 Alkyl and phenyl. In some instances, each R 2 It can be independently selected from C2-C 13 Alkyl group. In some instances, the copper auxiliary additive may be triethyl phosphite, tributylphosphine, triphenyl phosphite, or any combination thereof. In some instances, the molar ratio of the copper auxiliary additive to the copper (I) salt may be at least 0.5:1. In some instances, the biocidal additive formulation may further comprise a compound of formula (III), a compound of formula (IV), a compound of formula (V), or any combination thereof:

[0026] ;

[0027] ;

[0028] ;

[0029] Each R 3 Independently selected from hydrogen, C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl, provided that all R 3 They are not all hydrogen at the same time; each of the R's is hydrogen. 4 Independently selected from hydrogen, C1-C20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; wherein each R 5 is independently selected from hydrogen, Ci-C 20 alkyl, aryl, and aryl(Ci-C4)alkyl, provided that all R 5 are not simultaneously hydrogen. In certain examples, each R 3 may be independently selected from Ci-C 13 alkyl. In certain examples, the biocidal additive formulation can further comprise 2-ethylhexyl phosphonate. In certain examples, each R 4 may be independently selected from Ci-C 13 alkyl. In certain examples, the biocidal additive formulation can further comprise tributyl borate. In certain examples, each R 5 may be independently selected from Ci-C 13 alkyl. In certain examples, the biocidal additive formulation can further comprise tributyl citrate. The biocidal composition or the film thereof can exhibit a transmittance of at least 98% as measured at each wavelength from 400 nanometers to 700 nanometers when measured at a thickness of 40 pm. In certain examples, the transmittance can be within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assisted additive when measured at a thickness of 40 pm. In certain examples, the biocidal additive formulation can further comprise an antioxidant package. In certain examples, the biocidal additive formulation can further comprise a reducing agent. In certain examples, the formulation can be in a sealed container comprising an inert atmosphere.

[0030] Additional areas of application will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF DRAWINGS

[0031] So that the present disclosure can be well understood, various forms thereof will now be described by way of example with reference to the drawings. The components in the drawings are not necessarily to scale. Furthermore, in the drawings, like reference numerals designate corresponding parts throughout the several views. The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

[0032] Figure 1 Graphs demonstrating the antimicrobial efficacy of various examples of biocidal compositions comprising a two-component polyurethane as a carrier and comprising a copper source such as tetrakis(acetonitrile)copper(I) and copper-containing glass ("CCG") prepared in accordance with the principles of the present disclosure;

[0033] Figure 2 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0034] Figure 3 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0035] Figure 4 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0036] Figure 5 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0037] Figure 6 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0038] Figure 7 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0039] Figure 8 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP");

[0040] Figure 9 FIG. 1 shows plots of the antimicrobial efficacy of examples of biocidal compositions prepared according to the principles of the present disclosure containing a two-part polyurethane as a carrier, a copper source such as copper(I) tetra(acetoni trile) and CCG, triethyl phosphite ("TEP") as a copper co-additive, and further containing 2-ethylhexyl phosphoric acid ("EHP"); and

[0041] Figure 10 FIG. 1 illustrates a plot showing the antimicrobial efficacy of an example of a biocidal composition prepared according to the principles of the present disclosure comprising a bi-component polyurethane as a carrier, copper(I) bromide as a copper source, tributylphosphine (“TBP”) as a copper-assisted additive having a different molar ratio relative to copper, and further comprising EHP; and

[0042] Figure 11 FIG. 4 illustrates a plot showing the % transmittance of a polyurethane film comprising a copper(I) salt and a copper-assisted additive (“doped”) compared to an undoped polyurethane film on glass (“undoped”) and further compared to glass with no coating applied (“control”) at each wavelength from 350 nanometers to 750 nanometers.

[0043] The drawings described herein are for purposes of illustration only and are not intended to limit the scope of the present disclosure in any way. DETAILED DESCRIPTION

[0044] The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.

[0045] In describing the elements of the present disclosure, the terms “1st,” “2nd,” “first,” “second,” “A,” “B,” “(a),” “(b)” etc. can be used herein. These terms are used only to distinguish one element from another, but do not limit the corresponding element in any way.

[0046] Numerical values including range endpoints can be expressed herein as approximations, e.g., by using the terms “about,” “approximately,” etc. In such instances, other instances can carry the indicated precision. Whether or not numerical values are expressed as approximations, the disclosed disclosure is understood to include both the recited precise value and the approximated value. It is further understood that the endpoints of each of the ranges are significant, both in relation to the other endpoint, and independently of the other endpoint.

[0047] As used herein, the term “antimicrobial” refers to a composition, material, or surface of a material, including when such composition or material is in the form of a coating or a dry film, that will kill or inhibit the growth of a microorganism, including but not limited to a bacteria, a virus, a mildew, a mold, an algae, a fungus, or any combination thereof. As used herein, the term “antimicrobial” does not necessarily mean that the material or surface of a material will kill or inhibit the growth of all microorganism species within such family, but rather that the material or surface of a material will kill or inhibit the growth of one or more microorganism species from such family.

[0048] As used herein, the term “complete kill” refers to a log reduction of a given microorganism and / or virus that is equivalent to the log reduction of the same microorganism and / or virus on a copper metal surface.

[0049] As used herein, the term “dry film” refers to a coating that has been applied to a surface and allowed to dry, either actively or passively, such that the coating has a moisture content that has equilibrated with the surrounding environment. In some aspects, moisture content can be used to describe a dry film, such as a moisture content of less than 20 wt. % (e.g., less than 15 wt. %, less than 10 wt. %, less than 5 wt. %, less than 4 wt. %, less than 3 wt. %, less than 2 wt. %, less than 1 wt. %, less than 0.5 wt. %, or less than 0.1 wt. %); alternatively or additionally, a moisture content of greater than 0 wt. %, greater than 0.1 wt. %, greater than 0.5 wt. %, greater than 1 wt. %, greater than 2 wt. %, greater than 3 wt. %, greater than 4 wt. %, greater than 5 wt. %, greater than 10 wt. %, or greater than 15 wt. %; or a range formed by any two of the foregoing weight percentages; including any subranges therebetween.

[0050] As used herein, the term “biocidal” refers to a composition or material having an active substance intended to destroy, repel, render harmless, prevent the activity of, or otherwise exert a controlling effect on an undesirable organism, such as bacteria, viruses, mold, mildew, algae, and / or fungi, and in some aspects, biocidal compositions have antimicrobial properties.

[0051] As used herein, the term “log reduction” refers to the negative value of log (C a C0, where C a refers to the number of colony forming units (“CFU”) on an antimicrobial surface, and C0refers to the CFU on a control surface that is not antimicrobial. As an example, a log reduction of 3 is equivalent to killing 99.9% of microorganisms, and a log reduction of 5 is equivalent to killing 99.999% of microorganisms. Log reduction values can be measured according to one or more of ASTM D2574-16 (2016) “Standard Test Method for Resistance of Emulsion Paints in the Container to Attack by Microorganisms,” a modified JIS Z 2801 test for bacteria, a modified JIS Z 2801 test for viruses, or an EPA test, as described in greater detail elsewhere herein. “Log reduction” can also be referred to herein as “log kill.” Unless otherwise indicated, all log reduction information disclosed herein is in accordance with the EPA test.

[0052] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the disclosure (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of a range of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

[0053] As used herein, the terms “comprise(s)”, “include(s)”, “having”, “has”, “can”, “contain(s)”, and variants thereof, are open-ended transitional phrases, terms, or words that are intended to encompass the possibility that additional actions, structures, elements, or components can be possi ble beyond those that are recited. The specification also contemplates the other examples “comprising,” “consisting of,” and “consisting essentially of,” the examples or elements presented herein, whether or not explicitly set forth or otherwise set forth in the claims.

[0054] As used herein, the term “about,” when used in the context of a recited numerical value or range, means ±15% or less of the recited numerical value. For example, values that differ by ±15%, ±14%, ±10%, or ±5% etc. would meet the definition of “about” unless otherwise indicated in the specific circumstances. As used herein, the term “substantially” means that a value is 90% or more of a recited value, unless otherwise indicated in the specific circumstances.

[0055] The term “alkyl,” by itself or as part of another substituent means, unless otherwise indicated, a straight-chain, branched-chain, or cyclic hydrocarbon (“cycloalkyl”), having the number of carbon atoms designated (in other words, “C1-C 30 ” means one to thirty carbons). Examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, t-butyl, cyclobutyl, methylcyclopropyl, cyclopropylmethyl, pentyl, neopentyl, hexyl, and cyclohexyl. Other examples are -(C1-C 18 )alkyl, -(C1-C 15 )alkyl, -(C1-C 10 )alkyl, -(C1-C8)alkyl, -(C1-C6)alkyl, and -(C2-C6)alkyl. Such alkyl groups and depicted ranges of carbons can apply to any formula, R group, or chemical species disclosed herein. In certain examples of the disclosure, -(C1-C 30) alkyl, whether straight-chain, branched, or cyclic, can not be -C1alkyl, and / or can not be -C2alkyl, and / or can not be -C3alkyl, and / or can not be -C4alkyl, and / or can not be -C5alkyl, and / or can not be -C6alkyl, and / or can not be -C7alkyl, and / or can not be -C8alkyl, and / or can not be -C9alkyl, and / or can not be -C 10 alkyl, and / or can not be -C 11 alkyl, and / or can not be -C 12 alkyl, and / or can not be -C 13 alkyl, and / or can not be -C 14 alkyl, and / or can not be -C 15 alkyl, and / or can not be -C 16 alkyl, and / or can not be -C 17 alkyl, and / or can not be -C 18 alkyl, and / or can not be -C 19 alkyl, and / or can not be -C 20 alkyl, and / or can not be -C 21 alkyl, and / or can not be -C 22 alkyl, and / or can not be -C 23 alkyl, and / or can not be -C 24 alkyl, and / or can not be -C 25 alkyl, and / or can not be -C 26 alkyl, and / or can not be -C 27 alkyl, and / or can not be -C 28 alkyl, and / or can not be -C 29 alkyl, and / or can not be -C 30 alkyl. In certain instances of the disclosure, at least one hydrogen of an alkyl group is replaced with a hydroxyl group represented by -OH.

[0056] The term "aromatic" generally refers to a carbocyclic or heterocyclic ring having one or more polyunsaturated rings having aromatic character (in other words, having (4n+2) delocalized pi electrons, where n is an integer).

[0057] The term "aryl" by itself or in combination with another substituent means a carbocyclic aromatic system containing one or more rings (typically one, two, or three rings), which can be fused together in a cataiicyclic fashion, like naphthyl, or linked in a catenaric fashion, like biphenyl. Examples can include phenyl, anthryl, and naphthyl. Preferred are phenyl and naphthyl, most preferred is phenyl.

[0058] The term “aryl(C1-C4)alkyl” refers to a functional group in which one to four carbon alkylene chains are attached to an aryl group, for example -CH2-CH2-phenyl. Examples can include benzyl.

[0059] The term “fluorine-substituted” refers to an organic compound or moiety that (1) includes both carbon-hydrogen bonds and carbon-fluorine bonds; or (2) is “perfluorinated,” in which case the carbons are bonded to fluorine atoms and no hydrogen atoms.

[0060] Unless otherwise indicated, the term “carrier” can refer to a melamine resin, a polyurethane, a precursor thereof, an epoxy resin, a precursor thereof, or a combination thereof, as described herein.

[0061] As used herein, the term “polyurethane” refers to a class of polymers, such as alternating copolymers, that include organic units connected by urethane (urea) linkages.

[0062]

[0063] Polyurethanes can have highly cross-linked molecular structures. Examples of polyurethanes can be produced by reacting two separate polyurethane precursors together, optionally in the presence of a catalyst or upon exposure to ultraviolet light. In certain examples, the polyurethane precursors can include a diisocyanate species. Examples of diisocyanates can include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, and 4,4’-diphenylmethane diisocyanate:

[0064]

[0065]

[0066]

[0067] In other examples, the polyurethane precursors can include a polyol species. The polyol species can be compatible with examples of copper(I) salts and examples of copper-assisted additives of the present disclosure. Examples of difunctional polyols can include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-butanediol:

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] Examples of commercially available polyurethanes can include Eastwood® 4:1 High Solids Urethane Premium Show Clear.

[0076] As used herein, the term “epoxy resin” refers to a class of copolymers also known as “polyepoxides.” Examples of commercially available epoxy resins can include WiseBond® Bar & Table Top 1:1 Ratio. Examples of epoxy resins can be produced by reacting two separate epoxy resin precursors together. In certain examples, the epoxy resin precursors can include an epoxy functional group. Examples of epoxy resin precursors including an epoxy functional group can include bisphenol A diglycidyl ether:

[0077]

[0078] In other examples, the epoxy resin precursors can include a multifunctional amine, carboxylic acid, phenol, alcohol, thiol, or any combination thereof, which can react with the epoxide containing monomer as a nucleophile to form the epoxy resin, and which can be compatible with examples of copper (I) salts and examples of copper-assisted additives of the present disclosure.

[0079] As used herein, the term “halide” refers to a negative ion of a halogen atom carrying a -1 form of charge (“anion”). Examples of halides include fluoride ion (F -1 ), chloride ion (Cl -1 ), bromide ion (Br -1 ), and iodide ion (I -1 ).

[0080] As used herein, the term "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 the availability of copper (I) at the surface and / or interface of a composition or material, consistent with the following explanation. Without wishing to be bound by theory, it is believed that copper (I) is mostly colorless and more antimicrobial potent, whereas copper (II) is generally energetically favorable, but produces color and has lower antimicrobial potency. Thus, copper (I) is generally more favored for function and color, but copper (II) is generally more stable. To promote the persistence and / or availability of copper (I) in a composition or material, several strategies / mechanisms can be considered, including employing a reducing agent (e.g., to reduce copper (II) to copper (I), or to reduce other oxidizing agents that can be present), an antioxidant (e.g., to scavenge oxidizing agents, either by reduction or by chelation through coordination or binding, such that these oxidizing agents cannot oxidize copper (II) to copper (I)), a ligand with hydrophobic and / or bulky side chains (e.g., to limit access of oxidizing agents to copper (I) in copper complexes), a ligand that favors complexation with copper (I) over copper (II) (e.g., that is energetically favorable to copper (I) to be maintained, that promotes migration of copper (I) to the surface and / or interface, or any combination thereof. Thus, it is generally believed that the copper-assisting additives disclosed herein perform one or more of the above functions to promote the persistence of copper (I), including in some aspects in a composition in liquid form (e.g., at ambient conditions (1 atm (~101.3 kPa) and 20 °C), in a coating (e.g., a dry film), and / or in a bulk material (e.g., a polyurethane or an epoxy resin). In some aspects, the copper-assisting additive is a reducing agent, an antioxidant, a copper coordinating ligand with one or more hydrophobic side chains (e.g., that coordinates with copper (I) and / or copper (II)), a copper coordinating ligand with one or more bulky side chains (e.g., that coordinates with copper (I) and / or copper (II)), a copper coordinating ligand that preferentially complexes with copper (I) over copper (II) (e.g., that coordinates with copper (I) and / or copper (II)), a copper coordinating ligand with two or more copper coordination sites (e.g., that coordinates with copper (I) and / or copper (II)), or any combination thereof.

[0081] As used herein, the term "at. %" refers to atomic weight percent. In some aspects, "at. %" is used relative to the amount of copper in a composition. By way of simple example, a biocidal composition can comprise an amount of copper that is "X at. %" (where X is a number), and this means that the mass of copper atoms (using molecular weight) is added and expressed as a percentage relative to a given basis (e.g., based on the mass of the biocidal composition). In this aspect, when determining the mass of copper, the mass of other species in the copper complex or molecule (e.g., oxygen atoms in Cu20) is excluded, but included as part of the biocidal composition. The amount of copper expressed in at. % can be determined by methods known in the art.

[0082] As used herein, "weight" and "mass" are used interchangeably.

[0083] As used herein, the nomenclature convention for phosphorus-containing functional groups is standardized herein. Generally, the nomenclature convention for a functional group relative to a given phosphorus atom is determined by the number of oxygen atoms that form double bonds with the phosphorus atom ("A"), the total number of carbon and hydrogen atoms that form single bonds with the phosphorus atom ("B"), and the number of oxygen atoms that form single bonds with the phosphorus atom ("C"). In this aspect, the coordinates "(A, B, C)" can be used to identify a phosphorus-containing functional group. In this aspect, a "phosphate" has coordinates (1, 0, 3); a "phosphite" has coordinates (0, 0, 3); a "phosphine" has coordinates (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.

[0084] As used herein, the term "ambient temperature" refers to the temperature of the atmosphere in the immediate surroundings of an object or device.

[0085] As used herein, the term "ambient relative humidity" refers to the amount of water vapor present in the specific volume of the immediate surrounding atmosphere at ambient temperature, expressed as a percentage of the amount of water vapor required to be saturated at the same temperature. In certain examples, the value of ambient relative humidity can be 42%.

[0086] As used herein, the term "percentage point" refers to the unit of an arithmetic difference between two percentages. For example, the difference between transmittance values of 88% and 98% 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). In contrast, a percentage represents a relative or proportional part of a whole; 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).

[0087] In an example, the present disclosure provides a biocidal composition comprising a carrier, a copper(I) salt, and a copper-assist additive that is different from the carrier. In certain examples, the molar ratio of the copper-assist additive to the copper(I) salt is at least 0.5: 1. In other examples, the copper-assist additive can be combined with the copper(I) salt and added to the carrier at a total concentration of the two components of the biocidal composition from 1 gram per liter to 300 grams per liter.

[0088] In an example, the copper(I) salt can comprise a copper(I) halide, copper(I) iodite (triethyl phosphite), or a tetrakis(acetonitrile) copper(I) salt, or any combination thereof. In certain examples, the copper(I) halide can be copper(I) fluoride, copper(I) chloride, copper(I) bromide, copper(I) iodide, or any combination thereof. In certain examples, the tetrakis(acetonitrile) copper(I) salt can be tetrakis(acetonitrile) copper(I) hexafluorophosphate, tetrakis(acetonitrile) copper(I) tetrafluoroborate, tetrakis(acetonitrile) copper(I) perchlorate, tetrakis(acetonitrile) copper(I) triflate, tetrakis(acetonitrile) copper(I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

[0089] In an example, the biocidal composition can comprise a carrier, a copper(I) salt, and a copper-assist additive. In certain examples, the carrier can comprise a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof. In other examples, when the copper(I) salt is combined with the copper-assist additive and the carrier, or then when the copper(I) salt and the copper-assist additive are combined with the carrier, the copper(I) salt can be combined with the copper-assist additive and the carrier while maintaining antimicrobial efficacy (or preventing antimicrobial efficacy from decreasing below a certain level) and / or stabilizing the color of the carrier. Upon combining the copper(I) salt with the copper-assist additive and the carrier, or combining the copper(I) salt and the copper-assist additive with the carrier, examples of the present disclosure can maintain antimicrobial efficacy (or prevent antimicrobial efficacy from decreasing below a certain level) and / or reduce changes in the color of the carrier. Examples of the present disclosure can reduce changes in antimicrobial efficacy and / or reduce changes in the color of the carrier between a time after combining the copper(I) salt with the copper-assist additive and the carrier, or combining the copper(I) salt and the copper-assist additive with the carrier, and the final antimicrobial efficacy and / or the color of the carrier.

[0090] In an example, a material (e.g., a coating, such as a dry film) can exhibit a log reduction 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, over a period of one month or longer or over a period of three months or longer or any other period of time described herein elsewhere. The period of time (e.g., the one-month period or the three-month period) can begin at or after the material is applied as a layer to a surface. In such examples, the layer exhibits a log reduction 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 by reference in their entirety herein.

[0091] In an example, in the biocidal compositions disclosed herein, the antimicrobial efficacy of the composition or coating can be maintained, or at least prevented from decreasing below a certain level, for example by using a copper-assisted additive. The effectiveness of the compositions of the present disclosure (e.g., coatings, such as dry films) as biocidal compositions can be measured as a function of the log reduction of the biocidal composition. The log reduction value of the biocidal composition can be related to the ability of the biocidal composition to kill various biological organisms to which the biocidal composition is exposed, but can also allow the copper (I) salt to act as a preservative for the composition during storage (e.g., a container in a container, such as but not limited to a tank, a can, a drum, a keg, a bottle, or a tube). According to examples of the present disclosure, the log reduction of the biocidal composition can 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. In certain examples, as described elsewhere herein, the log reduction can be maintained (e.g., prevented from falling below) any of the above values or above any of the above values for a given period of time. The biocidal properties of the composition can make it effective to substantially kill various biological organisms, including bacteria, viruses, and fungi. When the coating is configured to have biocidal properties against bacteria, examples of suitable bacteria include Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, E. coli, and mixtures thereof. In certain examples, the copper (I) salt exhibits at least a log reduction, a 4 log reduction, a 5 log reduction, or even a 6 log reduction under EPA testing at a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, and E. coli, or exhibits a 3 log reduction or greater, or a 4 log reduction or greater (e.g., a 5 log reduction or greater) under JIS Z 2801 (2000) test conditions or under a modified JIS Z 2801 test for bacteria. In other examples, the copper (I) salt exhibits a 2 log reduction or more, a 3 log reduction or more, a 4 log reduction or more, or a 5 log reduction or more under a modified JIS Z 2801 for virus testing at a concentration of Murine Novovirus or Severe Acute Respiratory Syndrome (“SARS”) Coronavirus 2 (“SARS-CoV-2”).Procedures for modified JIS Z 2801 tests against bacteria and modified JIS Z 2801 (2000) tests against viruses are provided in International Patent Application Publication No. WO 2021 / 055300 Al, “COLOR STABILIZATION OF BIOCIDAL COATINGS,” which is incorporated herein by reference in its entirety.

[0092] Briefly, as used herein, the modified JIS Z 2801 test against bacteria involves evaluating bacteria under the standard JIS Z 2801 (2000) test with modified conditions that include heating a glass or article to a temperature of 23 to 37 degrees Celsius for 6 hours under 38% to 42% humidity. The modified JIS Z 2801 (2000) test against viruses involves the following procedure. For each material being tested (e.g., biocidal composition, composition comprising a copper (I) salt, composition comprising a copper adjunct additive, control composition), three samples of the material (contained in separate sterile petri dishes) are inoculated with a 20 pL aliquot of the test virus (where antimicrobial activity is measured) or an organic soil-loaded test medium comprising 5% fetal bovine serum with or without the test virus (where cytotoxicity is measured), respectively. The inoculum is then covered with a film, and the film is pressed down so that the test virus and / or test medium spreads on the film but does not spread beyond the edges of the film. The exposure time begins at the time of inoculation of each sample. The inoculated samples are transferred to a controlled room set at a relative humidity of 42% at room temperature or “ambient” temperature (20 °C) for 2 hours. Exposure time for control samples is discussed below. After the 2-hour exposure time, the film is lifted using sterile forceps, and a 2.00 mL aliquot of the test virus and / or test medium is pipetted onto each material sample, and the underside of the film (or the side of the film exposed to the sample) is 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. (At 10 2 Dilutions) The test virus and / or test medium is collected, mixed using a vortex-type mixer, and serial 10-fold dilutions are prepared. The antimicrobial activity and / or cytotoxicity of the dilutions is then determined.

[0093] To prepare a control sample for modified JIS Z 2801 testing against a virus for testing antimicrobial activity (also referred to as a "zero time virus control"), three control samples (contained in separate sterile petri dishes) were each inoculated with a 20 pL aliquot of test virus. Immediately after inoculation, a 2.00 mL aliquot of test virus was pipetted onto each control sample. The surface of each sample was individually swabbed with a sterile plastic cell scraper to collect test virus. (At 10 2 Dilutions) Test virus was collected, mixed using a vortex-type mixer, and serial 10-fold dilutions were prepared. The antimicrobial activity of the dilutions was determined.

[0094] To prepare a control sample for modified JIS Z 2801 testing against a virus with cytotoxicity (also referred to as a "2 hour control virus"), one control sample (contained in a separate sterile petri dish) was inoculated with a 20 pL aliquot of test medium containing organic soil load (5% fetal bovine serum) instead of test virus. The inoculum was covered with a membrane and the membrane was pressed down so that the test medium spread on the membrane but did not spread beyond the edge of the membrane. The exposure time was started from the time of inoculation of each control sample. The control sample was transferred to a controlled room set at room temperature (20°C) with a relative humidity of 42% for a 2 hour exposure time. After this exposure time, the membrane was picked up using sterile forceps and a 2.00 mL aliquot of test medium was pipetted onto each control sample and the underside of the membrane (the side exposed to the sample), respectively. The surface of each sample was individually swabbed with a sterile plastic cell scraper to collect test medium. (At 10 2 Dilutions) Test medium was collected, mixed using a vortex-type mixer, and serial 10-fold dilutions were prepared. The cytotoxicity of the dilutions was determined.

[0095] A representative description of the EPA test is as follows. Copper (I) salt was ground into a powder using a 2-inch jet mill. The jet milled copper (I) salt powder was then added to a carrier (e.g., commercially available Eastwood® two-component urethane) and mixed. Control coupons coated with the carrier without copper (I) salt were prepared simultaneously with coupons coated with copper (I) salt. Films were formed on Lenata scrub plots (P121-10N) using a 7-mil wet film thickness drawdown bar. The films were dried for 2 days at laboratory ambient temperature before antimicrobial testing. The dry film thickness was about 80 pm. A 1-inch x 1-inch square coupon was cut from the center of the painted scrub test panel. The stainless steel carrier used as a reference was cleaned and sterilized by soaking in a 75% ethanol solution followed by rinsing with deionized water. Vials containing a bacterial stock culture of Staphylococcus aureus (ATCC 6538) were stored at -80 °C until use. A 20 pL aliquot of the thawed bacterial culture was added to 10 mL of tryptic soy broth. These bacterial suspensions were incubated in an orbital shaker at 36 °C for 3 consecutive 18-24 hour periods and then for 1 48-hour period in a polypropylene snap-capped tube. The culture was then mixed on a vortex mixer and allowed to settle. The upper two-thirds of the suspension was drawn from each tube and the OD 600 was measured to estimate the bacterial density. The culture was diluted with phosphate buffered saline to bring the bacterial inoculum concentration close to the target value of 1.0 x 10 7 CFU / mL. 0.25 mL of 5% fetal bovine serum and 0.05 mL Triton TM X-100 were added to 4.70 mL of the bacterial suspension to help spread the inoculum. Each test coupon was inoculated with 20 pL of the bacterial test culture. The inoculum volume was spread evenly using a curved, sterile pipette tip to ensure complete and uniform coverage, spreading as close to the edges of the coupon as possible. The coupons were then incubated in a controlled environment set at 42% relative humidity and 23 °C for a period of 120 minutes. After the 120-minute exposure period, the coupons were neutralized in Letheen broth. Ten-fold serial dilutions of the neutralization solution were plated on tryptic soy agar plates using standard spread plate techniques and incubated at 36 °C for 24 hours to yield a countable number of surviving bacterial colonies (approximately 20-200 colonies per plate). The log and percent reduction measurements of the bactericidal efficacy test measured the difference in CFU between the stainless steel and glass-containing coupons. The antimicrobial efficacy measurements expressed as log reduction were repeated and the results averaged to arrive at the average log kill value.

[0096] In one example, a copper (I) salt can be combined with a copper-assist additive to prevent the antimicrobial efficacy from decreasing below a certain threshold (e.g., less than 3 log reduction or any other value disclosed herein) and / or limit the color shift of the biocidal composition relative to the color of a standard carrier (e.g., a carrier that does not contain a copper (I) or copper-assist additive). For example, the CIE L * a * b * ΔE * 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 the range of 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.

[0097] It is understood that the CIE L * a * b * color space is a color scale for determining color. The CIE L * a * b * three coordinates (or dimensions / components) represent lightness (L * = 0 indicates black, and L * = 100 indicates white), a position between red (sometimes also called magenta) and green (negative a * values indicate green, while positive a * values indicate red), and a position between yellow and below (negative b * values indicate blue, and positive b * values indicate yellow). The L * component closely matches human perception of lightness. Related to the CIE L * a * b * color space is the CIE L * C * h * color space, which is a cylindrical representation of the following three perceptual color-related factors: lightness, chroma, and hue. The axial components of CIE L * C * h * are the same lightness attribute L * a * b * as CIE L *, the radial component is chroma, and the angular component is hue. Using CIE L * a * b * and CIE L * C * h * Color spaces can measure the color difference (e.g., ΔΕ * ) between a standard color and an observed color, and can measure the extent to which a desired color of a coating is altered by the ingredients therein.

[0098] In an example, a biocidal composition is disclosed, the biocidal composition comprising: a carrier; a copper (I) salt; and a copper-assisted additive. In certain examples, the carrier can comprise a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, a melamine resin, or any combination thereof. In certain examples, the biocidal composition is in a liquid form at ambient conditions (1 atm (about 101.3 kPa) and 20 °C). In certain examples, the biocidal composition does not contain a polyurethane (e.g., 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.

[0099] In certain examples, a desired level of antimicrobial efficacy (e.g., by any of the tests disclosed herein, such as the EPA test) can be achieved with the copper-assisted additive.

[0100] In certain examples, the carrier and the copper-assisted additive are different. As used herein, “different” means that a given chemical species (e.g., a polyurethane) cannot simultaneously be both a carrier and a copper-assisted additive; rather, if the carrier is, for example, a polyurethane, the copper-assisted additive cannot be a polyurethane, but must be another chemical species (e.g., triethyl phosphite).

[0101] In certain examples, the biocidal composition comprises a polymer, a monomer, a binder, an organic solvent, an inorganic solvent, water, a dispersion of a finely divided solid in a liquid medium that can be applied to a surface to form a film, a pigment, a filler, an extender, a drying agent, a rheology modifier, or any combination thereof. In certain examples, the biocidal composition does not contain (e.g., 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 a finely divided solid in a liquid medium that can 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 drying agent, and / or does not contain a rheology modifier.

[0102] In an example, the copper-assisting additive is or comprises a phosphite, a phosphine, or any combination thereof. In certain examples, the copper-assisting additive can be hydrophobic, hydrophilic, or amphiphilic, and any of the above copper-assisting additives (or any other copper-assisting additive disclosed herein) can be characterized as hydrophobic, hydrophilic, or amphiphilic. For example, the copper-assisting additive can be or can comprise a hydrophobic phosphite, a hydrophobic phosphine, or any combination thereof.

[0103] In certain examples, the biocidal composition does not contain (e.g., 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 amphoteric copper-assisting additive.

[0104] In an example, the copper-assisting additive is a compound of Formula (I), a compound of Formula (II), or any combination thereof.

[0105] In an example, the copper-assisting additive can be a compound of Formula (I):

[0106] ;

[0107] wherein each R 1 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups can be optionally substituted with fluorine.

[0108] In certain examples, each R 1 is independently selected from the group consisting of C2-C 13 alkyl, phenyl, and benzyl.

[0109] In certain examples, each R 1 is independently selected from the group consisting of C1-C8 alkyl.

[0110] In certain examples, each R 1 is independently selected from the group consisting of C1-C5 alkyl.

[0111] In certain examples, at least one R 1 is a secondary or tertiary carbon.

[0112] Certain examples of the compound of Formula (I) can comprise particular combinations of R 1 that complex with copper, interact with copper, or otherwise affect copper (e.g., by affecting the persistence of a given oxidation state, such as copper (I)), but not R 1other combinations of the foregoing as desired or preferred, 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 the particular compound of Formula (I). In certain examples of compounds of Formula (I), each R 1 independently can not be any of C1-C 20 alkyl, and / or can not be aryl, and / or can not be aryl(C1-C4)alkyl. In certain examples, the biocidal composition does not include a compound of Formula (I), and / or the copper- assisted additive is not a compound of Formula (I).

[0113] Examples of compounds of Formula (I) can include trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,2,2-fluoroethyl) phosphite, tris(2- ethylhexyl) phosphite, triisopropyl phosphite, and tris(l, 1, 1,3,3,3-hexafluoro-2- propyl) phosphite. In certain examples, the biocidal composition does not include (e.g., the copper-assisted 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 include tris(l, 1, 1,3,3,3-hexafluoro-2-propyl) phosphite, and / or does not include triphenyl phosphite.

[0114] In certain examples, for a compound of any of Formula (I), Formula (II), Formula (III), Formula (IV), or Formula (V), C1-C 20 alkyl can include C1-C 19 alkyl, C1-C 18 alkyl, C1-C 17 alkyl, C1-C 16 alkyl, C1-C 15 alkyl, C1-C 14 alkyl, C1-C 13 alkyl, C1-C 12 alkyl, C1-C 11 alkyl, C1-C 10 alkyl, C1-C9alkyl, C1-C8alkyl, C1-C7alkyl, C1-C6alkyl, C1-C5alkyl, C1-C4alkyl, C1-C3alkyl, C1-C2alkyl, C2-C 20 alkyl, C2-C 19 alkyl, C2-C 18 alkyl, C2-C 17 alkyl, C2-C 16 alkyl, C2-C 15 alkyl, C2-C 14alkyl, C2-C 13 alkyl, C2-C 12 alkyl, C2-C 11 alkyl, C2-C 10 alkyl, C2-C9alkyl, C2-C8alkyl, C2-C7alkyl, C2-C6alkyl, C2-C5alkyl, C2-C4alkyl, C2-C3alkyl, C3-C 20 alkyl, C3-C 19 alkyl, C3-C 18 alkyl, C3-C 17 alkyl, C3-C 16 alkyl, C3-C 15 alkyl, C3-C 14 alkyl, C3-C 13 alkyl, C3-C 12 alkyl, C3-C 11 alkyl, C3-C 10 alkyl, C3-C9alkyl, C3-C8alkyl, C3-C7alkyl, C3-C6alkyl, C3-C5alkyl, C3-C4alkyl, C4-C 20 alkyl, C4-C 19 alkyl, C4-C 18 alkyl, C4-C 17 alkyl, C4-C 16 alkyl, C4-C 15 alkyl, C4-C 14 alkyl, C4-C 13 alkyl, C4-C 12 alkyl, C4-C 11 alkyl, C4-C 10 alkyl, C4-C9alkyl, C4-C8alkyl, C4-C7alkyl, C4-C6alkyl, C4-C5alkyl, C5-C 20 alkyl, C5-C 19 alkyl, C5-C 18 alkyl, C5-C 17 alkyl, C5-C 16 alkyl, C5-C 15 alkyl, C5-C 14 alkyl, C5-C 13 alkyl, C5-C 12 alkyl, C5-C 11 alkyl, C5-C 10 alkyl, C5-C9alkyl, C5-C8alkyl, C5-C7alkyl, C5-C6alkyl, C6-C 20 alkyl, C6-C 19 alkyl, C6-C 18 alkyl, C6-C 17alkyl, C6-C 16 alkyl, C6-C 15 alkyl, C6-C 14 alkyl, C6-C 13 alkyl, C6-C 12 alkyl, C6-C 11 alkyl, C6-C 10 alkyl, C6-C9alkyl, C6-C8alkyl, C6-C7alkyl, C7-C 20 alkyl, C7-C 19 alkyl, C7-C 18 alkyl, C7-C 17 alkyl, C7-C 16 alkyl, C7-C 15 alkyl, C7-C 14 alkyl, C7-C 13 alkyl, C7-C 12 alkyl, C7-C 11 alkyl, C7-C 10 alkyl, C7-C9alkyl, C7-C8alkyl, C8-C 20 alkyl, C8-C 19 alkyl, C8-C 18 alkyl, C8-C 17 alkyl, C8-C 16 alkyl, C8-C 15 alkyl, C8-C 14 alkyl, C8-C 13 alkyl, C8-C 12 alkyl, C8-C 11 alkyl, C8-C 10 alkyl, C8-C9alkyl, C9-C 20 alkyl, C9-C 19 alkyl, C9-C 18 alkyl, C9-C 17 alkyl, C9-C 16 alkyl, C9-C 15 alkyl, C9-C 14 alkyl, C9-C 13 alkyl, C9-C 12 alkyl, C9-C 11 alkyl, C9-C 10 alkyl, C 10 -C 20 alkyl, C 10 -C 19 alkyl, C 10 -C 18 alkyl, C 10 -C 17 alkyl, C 10 -C16 Alkyl, C 10 -C 15 Alkyl, C 10 -C 14 Alkyl, C 10 -C 13 Alkyl, C 10 -C 12 Alkyl, C 10 -C 11 Alkyl, C 11 -C 20 Alkyl, C 11 -C 19 Alkyl, C 11 -C 18 Alkyl, C 11 -C 17 Alkyl, C 11 -C 16 Alkyl, C 11 -C 15 Alkyl, C 11 -C 14 Alkyl, C 11 -C 13 Alkyl, C 11 -C 12 Alkyl, C 12 -C 20 Alkyl, C 12 -C 19 Alkyl, C 12 -C 18 Alkyl, C 12 -C 17 Alkyl, C 12 -C 16 Alkyl, C 12 -C 15 Alkyl, C 12 -C 14 Alkyl, C 12 -C 13 Alkyl, C 13 -C 20 Alkyl, C 13 -C 19 Alkyl, C 13 -C 18 Alkyl, C 13 -C 17 Alkyl, C 13 -C 16 Alkyl, C 13 -C 15 Alkyl, C 13 -C 14 Alkyl, C 14 -C 20 Alkyl, C 14 -C 19alkyl, C 14 -C 18 alkyl, C 14 -C 17 alkyl, C 14 -C 16 alkyl, C 14 -C 15 alkyl, C 15 -C 20 alkyl, C 15 -C 19 alkyl, C 15 -C 18 alkyl, C 15 -C 17 alkyl, C 15 -C 16 alkyl, C 16 -C 20 alkyl, C 16 -C 19 alkyl, C 16 -C 18 alkyl, C 16 -C 17 alkyl, C 17 -C 20 alkyl, C 17 -C 19 alkyl, C 17 -C 18 alkyl, C 18 -C 20 alkyl, C 18 -C 19 alkyl and C 19 -C 20 alkyl.

[0115] In certain instances of the compound of formula (I), each R 1 may not be C1alkyl, and / or may not be C2alkyl, and / or may not be C3alkyl, and / or may not be C4alkyl, and / or may not be C5alkyl, and / or may not be C6alkyl, and / or may not be C7alkyl, and / or may not be C8alkyl, and / or may not be C9alkyl, and / or may not be C 10 alkyl, and / or may not be C 10alkyl, and / or can not be C 11 alkyl, and / or can not be C 11 alkyl, and / or can not be C 12 alkyl, and / or can not be C 12 alkyl, and / or can not be C 13 alkyl, and / or can not be C 13 alkyl, and / or can not be C 14 alkyl, and / or can not be C 14 alkyl, and / or can not be C 15 alkyl, and / or can not be C 15 alkyl, and / or can not be C 16 alkyl, and / or can not be C 16 alkyl, and / or can not be C 17 alkyl, and / or can not be C 17 alkyl, and / or can not be C 18 alkyl, and / or can not be C 18 alkyl, and / or can not be C 19 alkyl, and / or can not be C 19 alkyl, and / or can not be C 20 alkyl, and / or can not be C 20 alkyl, and / or can not be C

[0116] Without being bound by any particular theory, it is believed that the presence or maintenance of copper (I) is facilitated by the use of a compound of Formula (I) or any salt thereof, and that 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 the antimicrobial efficacy of the biocidal composition, preventing the antimicrobial efficacy of the biocidal composition from decreasing below a certain level (e.g., less than 3 log reduction), minimizing the color shift of the biocidal composition, or any combination thereof. The antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EPA test.

[0117] In one example, the copper co-additive can be a compound of Formula (II) or any salt thereof:

[0118] ;

[0119] wherein each R 2 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with hydroxyl.

[0120] In certain instances, each R 2 is independently selected from C2-C 13 alkyl, any of which groups is optionally substituted with hydroxyl.

[0121] In certain instances, each R 2 is independently selected from C1-C 10 alkyl, any of which groups is optionally substituted with hydroxyl.

[0122] In certain instances, each R 2 is independently selected from C1-C6 alkyl, any of which groups is optionally substituted with hydroxyl.

[0123] In certain instances, at least one R 2 is a secondary or tertiary carbon.

[0124] Certain instances of compounds of Formula (II) can include combinations of R 2 that complex with copper, interact with copper, or otherwise affect copper (e.g., by affecting the persistence of a given oxidation state, such as copper (I)), but are not as desirable or preferred as other specific combinations of R 2 , 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). In certain instances of compounds of Formula (II), each R 2 independently can not be C1 alkyl, and / or can not be C1 alkyl optionally substituted with hydroxyl, and / or can not be C2 alkyl, and / or can not be C2 alkyl optionally substituted with hydroxyl, and / or can not be C3 alkyl, and / or can not be C3 alkyl optionally substituted with hydroxyl, and / or can not be C4 alkyl, and / or can not be C4 alkyl optionally substituted with hydroxyl, and / or can not be C5 alkyl, and / or can not be C5 alkyl optionally substituted with hydroxyl, and / or can not be C6 alkyl, and / or can not be C6 alkyl optionally substituted with hydroxyl, and / or can not be C7 alkyl, and / or can not be C7 alkyl optionally substituted with hydroxyl, and / or can not be C8 alkyl, and / or can not be C8 alkyl optionally substituted with hydroxyl, and / or can not be C9 alkyl, and / or can not be C9 alkyl optionally substituted with hydroxyl, and / or can not be C 10 alkyl, and / or can not be C 10 alkyl, and / or can not be C 11 alkyl, and / or can not be C 11 alkyl, and / or can not be C12 alkyl, and / or can not be C 12 alkyl, and / or can not be C 13 alkyl, and / or can not be C 13 alkyl, and / or can not be C 14 alkyl, and / or can not be C 14 alkyl, and / or can not be C 15 alkyl, and / or can not be C 15 alkyl, and / or can not be C 16 alkyl, and / or can not be C 16 alkyl, and / or can not be C 17 alkyl, and / or can not be C 17 alkyl, and / or can not be C 18 alkyl, and / or can not be C 18 alkyl, and / or can not be C 19 alkyl, and / or can not be C 19 alkyl, and / or can not be C 20 alkyl, and / or can not be C 20 alkyl. In certain examples, the biocidal composition does not include a compound of Formula (II), and / or the copper-assisted additive is not a compound of Formula (II).

[0125] Examples of compounds of Formula (II) can include tris(hydroxypropyl)phosphine and tributylphosphine. In certain examples, the biocidal composition does not include (e.g., the copper-assisted additive is not) one or more of tris(hydroxypropyl)phosphine or tributylphosphine.

[0126] Without being bound by any particular theory, it is believed that the presence or maintenance of copper (I) is facilitated by the use of a compound of Formula (II), and that biocidal compositions containing a compound of Formula (II) exhibit one or more effects when combined with a copper (I) salt, including maintaining the antimicrobial efficacy of the biocidal composition below a certain level (e.g., less than 3 log reduction), minimizing the color shift of the biocidal composition, or any combination thereof.

[0127] In an example, the biocidal composition of the present disclosure can include a compound of Formula (III), a compound of (IV), a compound of (V), or any combination thereof:

[0128] ;

[0129] ;

[0130] ;

[0131] wherein each R 3 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl.

[0132] In certain examples, each R 3 is independently selected from the group consisting of hydrogen, C1-C 13 alkyl, phenyl, and benzyl, provided that all R 3 are not simultaneously hydrogen.

[0133] In certain examples, at least one R 3 is a secondary or tertiary carbon.

[0134] Certain examples of compounds of Formula (III) can include particular combinations of R 3 that are independently selected such that the compound of Formula (III) complexes with copper, interacts with copper, or otherwise affects copper (e.g., by affecting the persistence of a given oxidation state, such as copper (I)), but are not as desirable or preferred as other particular combinations of R 3 due to the combined effects of chemical phenomena understood by one of skill in the art, including but not limited to hydrophobicity, solubility, electronic effects, and / or steric effects resulting from the chemical structure of the particular compound of Formula (III). In certain examples of compounds of Formula (III), each R 3 may independently not be hydrogen, and / or can not be any of C1-C 20 alkyl, and / or can not be aryl, and / or can not be aryl(C1-C4)alkyl. In certain examples, the biocidal composition does not include a compound of Formula (III).

[0135] Examples of compounds of Formula (III) can include 2-ethylhexyl phosphate, bis(2- ethylhexyl) phosphate, tri(2-ethylhexyl) phosphate, methyl phosphate, diethyl phosphate, trimethyl phosphate, butyl phosphate (e.g., n-butyl, sec-butyl, or t-butyl), dibutyl phosphate (e.g., n-butyl, sec-butyl, and / or t-butyl), tributyl phosphate (e.g., n-butyl, sec-butyl, and / or t-butyl), phenyl phosphate, diphenyl phosphate, triphenyl phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, or any combination thereof. In certain examples, the biocidal composition does not include 2-ethylhexyl phosphate, and / or does not include bis(2-ethylhexyl) phosphate, and / or does not include tri(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 (e.g., n-butyl, sec-butyl, or t-butyl), and / or does not include dibutyl phosphate (e.g., n-butyl, sec-butyl, or t-butyl), and / or does not include tributyl phosphate (e.g., n-butyl, sec-butyl, or t-butyl), and / or does not include phenyl phosphate, and / or does not include diphenyl phosphate, and / or does not include triphenyl phosphate, and / or does not include benzyl phosphate, and / or does not include dibenzyl phosphate, and / or does not include tribenzyl phosphate.

[0136] In certain examples of compounds of Formula (III), each R 3 may not be C1alkyl, and / or may not be C2alkyl, and / or may not be C3alkyl, and / or may not be C4alkyl, and / or may not be C5alkyl, and / or may not be C6alkyl, and / or may not be C7alkyl, and / or may not be C8alkyl, and / or may not be C9alkyl, and / or may not be C 10 alkyl, and / or may not be C 11 alkyl, and / or may not be C 12 alkyl, and / or may not be C 13 alkyl, and / or may not be C 14 alkyl, and / or may not be C 15 alkyl, and / or may not be C 16 alkyl, and / or may not be C 17 alkyl, and / or may not be C 18 alkyl, and / or may not be C 19 alkyl, and / or may not be C 20 alkyl.

[0137] In certain examples, each R 4 is independently selected from the group consisting of hydrogen, C1-C 13 alkyl, phenyl, and benzyl, provided that all R 4 are not simultaneously hydrogen.

[0138] In certain examples, at least one R 4 is a secondary carbon or a tertiary carbon.

[0139] Certain examples of compounds of Formula (IV) can include particular combinations of R 4 that result in complexing with copper, interacting with copper, or otherwise affecting copper (e.g., by affecting the persistence of a given oxidation state, such as copper (I)) that are not desired or preferred as other particular combinations of R 4 , due to the combined effects of chemical phenomena understood by those of skill in the art, including but not limited to hydrophobicity, solubility, electronic effects, and / or steric effects arising from the chemical structure of the particular compound of Formula (IV). In certain examples of compounds of Formula (IV), each R 4 may independently be other than hydrogen, and / or can be other than any of C1-C 20 alkyl, and / or can be other than aryl, and / or can be other than aryl(C1-C4)alkyl. In certain examples, the biocidal composition does not include a compound of Formula (IV).

[0140] Examples of compounds of Formula (IV) can include tributyl borate. In certain examples, the biocidal composition does not include tributyl borate.

[0141] In certain examples of compounds of Formula (IV), each R 4 may be other than C1 alkyl, and / or can be other than C2 alkyl, and / or can be other than C3 alkyl, and / or can be other than C4 alkyl, and / or can be other than C5 alkyl, and / or can be other than C6 alkyl, and / or can be other than C7 alkyl, and / or can be other than C8 alkyl, and / or can be other than C9 alkyl, and / or can be other than C 10 alkyl, and / or can be other than C 11 alkyl, and / or can be other than C 12 alkyl, and / or can be other than C 13 alkyl, and / or can be other than C 14 alkyl, and / or can be other than C 15 alkyl, and / or can be other than C 16 alkyl, and / or can be other than C 17 alkyl, and / or can be other than C 18 alkyl, and / or can be other than C 19 alkyl, and / or can be other than C 20 alkyl.

[0142] In certain examples, each R 5 is independently selected from the group consisting of hydrogen, C1-C 13 alkyl, phenyl, and benzyl, provided that all R5 are not both hydrogen at the same time.

[0143] In certain examples, at least one R 5 is a secondary or tertiary carbon.

[0144] Certain examples of compounds of Formula (V) can include particular combinations of R 5 that result in complexing with copper, interacting with copper, or otherwise affecting copper (e.g., by affecting the persistence of a given oxidation state, such as copper (I)), but are not as desirable or preferred as other particular combinations of R 5 , due to the combined effects of chemical phenomena understood by those of skill 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). In certain examples of compounds of Formula (V), each R 5 may independently be other than hydrogen, and / or can be other than any of C1-C4 20 alkyl, and / or can be other than aryl, and / or can be other than aryl(C1-C4)alkyl. In certain examples, the biocidal composition does not include a compound of Formula (V).

[0145] Examples of compounds of Formula (V) can include tributyl citrate. In certain examples, the biocidal composition does not include tributyl citrate.

[0146] In one example, the biocidal composition comprises copper in an amount of at least 0.01 at.%, based on 100 percent by weight of the biocidal composition. In certain examples, the biocidal composition comprises copper in an amount of less than 10 at.%, based on the total 100 percent by weight of the biocidal composition. In certain examples, the biocidal composition comprises copper in an amount (at.%, based on 100 percent by weight 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 - 2, 0.02 - 1, 0.02 - 0.9, 0.02 - 0.8, 0.02 - 0.7, 0.02 - 0.6, 0.02 - 0.5, 0.02 - 0.4, 0.02 - 0.3, 0.02 - 0.2, 0.02 - 0.1, 0.02 - 0.05, 0.05 - 10, 0.05 - 9, 0.05 - 8, 0.05 - 7, 0.05 - 6, 0.05 - 5, 0.05 - 4, 0.05 - 3, 0.05 - 2, 0.05 - 1, 0.05 - 0.9, 0.05 - 0.8, 0.05 - 0.7, 0.05 - 0.6, 0.05 - 0.5, 0.05 - 0.4, 0.05 - 0.3, 0.05 - 0.2, 0.05 - 0.1, 0.1 - 10, 0.1 - 9, 0.1 - 8, 0.1 - 7, 0.1 - 6, 0.1 - 5, 0.1 - 4, 0.1 - 3, 0.1 - 2, 0.1 - 1, 0.1 - 0.9, 0.1 - 0.8, 0.1 - 0.7, 0.1 - 0.6, 0.1 - 0.5, 0.1 - 0.4, 0.1 - 0.3, 0.1 - 0.2, 0.2 - 10, 0.2 - 9, 0.2 - 8, 0.2 - 7, 0.2 - 6, 0.2 - 5, 0.2 - 4, 0.2 - 3, 0.2 - 2, 0.2 - 1, 0.2 - 0.9, 0.2 - 0.8, 0.2 - 0.7, 0.2 - 0.6、0.2 - 0.5、0.2 -0.4、0.2 - 0.3、0.3 -10、0.3 - 9、0.3 - 8、0.3 - 7、0.3 - 6、0.3 - 5、0.3 - 4、0.3 -3、0.3 - 2、0.3 - 1、0.3 - 0.9、0.3 - 0.8、0.3 - 0.7、0.3 - 0.6、0.3 - 0.5、0.3 -0.4、0.4 - 10、0.4 - 9、0.4 - 8、0.4 - 7、0.4 - 6、0.4 - 5、0.4 - 4、0.4 - 3、0.4 - 2、0.4 - 1、0.4 - 0.9、0.4 - 0.8、0.4 - 0.7、0.4 - 0.6、0.4 - 0.5、0.5 - 10、0.5 -9、0.5- 8、0.5 - 7、0.5 - 6、0.5 - 5、0.5 - 4、0.5 - 3、0.5 - 2、0.5 - 1、0.5 - 0.9、0.5 -0.8、0.5 - 0.7、0.5 - 0.6、0.6 -10、0.6 - 9、0.6 - 8、0.6 - 7、0.6 - 6、0.6 - 5、0.6 -4、0.6 - 3、0.6 - 2、0.6 - 1、0.6 - 0.9、0.6 - 0.8、0.6 - 0.7、0.7 - 10、0.7 - 9、0.7- 8、0.7 - 7、0.7 - 6、0.7 - 5、0.7 - 4、0.7 - 3、0.7 - 2、0.7 - 1、0.7 - 0.9、0.7 -0.8、0.8 - 10、0.8 - 9、0.8 - 8、0.8 - 7、0.8 - 6、0.8 - 5、0.8 - 4、0.8 - 3、0.8 - 2、0.8 - 1、0.8 - 0.9、0.9 - 10、0.9 - 9、0.9 - 8、0.9 - 7、0.9 - 6、0.9 - 5、0.9 - 4、0.9 - 3、0.9 - 2、0.9 - 1, 1 - 10, 1 - 9, 1 - 8, 1 - 7, 1 - 6, 1 - 5, 1 - 4, 1 - 3, 1 - 2, 2 - 10, 2 - 9, 2 - 8, 2 - 7, 2 - 6, 2 - 5, 2 - 4, 2 - 3, 3 - 10, 3 - 9, 3 - 8, 3 - 7, 3 - 6, 3 - 5, 3 - 4, 4 - 10, 4 - 9, 4 - 8, 4 - 7, 4 - 6, 4 - 5, 5 - 10, 5 - 9, 5 - 8, 5 - 7, 5 - 6, 6 - 10, 6 - 9, 6 - 8, 6 - 7, 7 - 10, 7 - 9, 7 - 8, 8 - 10, 8 - 9, 9 - 10, 0.06 - 0.5, 0.07 - 0.4, 0.08 - 0.3, 0.09 - 0.2, 0.02 - 1.9, 0.03 - 1.8, 0.03 - 1.7, 0.04 - 1.7, 0.05 - 1.8, 0.06 - 1.7, 0.07 - 1.6, 0.08 - 1.5, 0.09 - 1.4, 0.1 - 1.3, 0.2 - 1.2, 0.3 - 1.1; or any combination thereof; or any range formed by any two of the foregoing at.% values; including any subranges therebetween.

[0147] In an example, the total of the individual copper (I) salt, the individual copper- assisted additive, or both the copper (I) salt and the copper-assisted additive can be described by any of the following values and ranges: 0.01 wt.% to 20 wt.% based on the weight of the carrier or the biocidal composition, such as the following amounts (wt.% based on 100 wt.% of the carrier or biocidal composition): 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 - 2.3, 0.01 - 2.2, 0.01 - 2.1, 0.01 - 2, 0.01 - 1.9, 0.01 - 1.8, 0.01 - 1.7, 0.01 - 1.6, 0.01 - 1.5, 0.01 - 1.4, 0.01 - 1.3, 0.01 - 1.2, 0.01 - 1.1, 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, 0.02 - 5, 0.03 - 5, 0.04 - 5, 0.05 - 5, 0.06 - 5, 0.07 - 5, 0.08 - 5, 0.09 - 5, 0.1 - 5, 0.2 - 5, 0.3 - 5, 0.4 - 5, 0.5 - 5, 0.6 - 5, 0.7 - 5, 0.8 - 5, 0.9 - 5, 1 - 5, 1 - 4, 1 - 3, 1 - 2, 2 - 5, 2 - 4, 2 - 3, 3 - 5, 4 - 5, 0.1 - 3, 0.1 - 2, 0.1 - 1, 0.1 - 1.9, 0.1 - 1.8, 0.1 - 1.7, 0.1 - 1.6, 0.1 - 1.5, 0.1 - 1.4, 0.1 - 1.3, 0.1 - 1.2, 0.1 - 1.1, 0.1 - 1, 0.1 - 0.9, 0.1 - 0.8, 0.1 - 0.7, 0.1 - 0.6, 0.1 - 0.5, 0.1 - 0.4, 0.1 - 0.3, 0.1 - 0.2, 0.1 - 5, 0.2 - 4.5, 0.3 - 4, 0.4 - 3.5, 0.5 - 3, 0.6 - 2.5, 0.7 - 2, 0.8 - 1.5, 0.9 - 1, 0.15 - 1.8, 0.2 - 1.6, 0.25 - 1.4, 0.3 - 1.2, 0.35 - 1, 0.4 - 0.95, 0.45 - 0.9, 0.5 - 0.85, 6 - 20, 7 - 20, 8 - 20, 9 - 20, 10 - 20, 11 - 20, 12 - 20, 13 - 20, 14 - 20, 15 - 20, 16 - 20, 17 - 20, 18 - 20, 19 - 20, 0.1 - 15, 0.5 - 14, 1 - 13, 1.5 - 12, 2 - 10, or any combination thereof. Such numerical values can refer to the absolute amount present, or the amount added to the composition. Basis weight can be of the carrier or biocidal composition, which will become clear from the context, as in certain instances the carrier is the primary component of the biocidal composition. Thus, in certain instances, the amount of one or more given components relative to the carrier or biocidal composition will be similar values.

[0148] In one or more instances, the copper (I) salt and copper-assisting additive can be present in a 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).

[0149] In one example, the copper (I) salt and copper-assisting additive can be present in a total amount (grams per liter of carrier or biocidal composition) of 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 - 10, 3 - 5, 4 - 50, 4 - 45, 4 - 40, 4 - 35, 4 - 30, 4 - 25, 4 - 20, 4 - 15, 4 - 10, 4 - 5, 5 - 50, 5 - 45, 5 - 40, 5 - 35, 5 - 30, 5 - 25, 5 - 20, 5 - 15, 5 - 10, 10 - 50, 10 - 45, 10 - 40, 10 - 35, 10 -30, 10 - 25, 10 - 20, 10 - 15, 15 - 50, 15 - 45, 15 - 40, 15 - 35, 15 - 30, 15 - 25, 15- 20, 20 - 50, 20 - 45, 20 - 40, 20 - 35, 20 - 30, 20 - 25, 25 - 50, 25 - 45, 25 - 40, 25 - 35, 25 - 30, 30 - 50, 30 - 45, 30 - 40, 30 - 35, 35 - 50, 35 - 45, 35 - 40, 40 -50, 40 - 45, 45 - 50, 6 - 50, 6 - 45, 6 - 40, 6 - 35, 6 - 30, 6 - 25, 6 - 20, 6 - 15, 6- 10, 7 - 50, 7 - 45, 7 - 40, 7 - 35, 7 - 30, 7 - 25, 7 - 20, 7 - 15, 7 - 10, 8 - 50, 8- 45, 8 - 40, 8 - 35, 8 - 30, 8 - 25, 8 - 20, 8 - 15, 8 - 10, 9 - 50, 9 - 45, 9 - 40, 9- 35, 9 - 30, 9 - 25, 9 - 20, 9 - 15 or 9 - 10. As disclosed elsewhere herein, the base can be expressed as a carrier or biocidal composition.

[0150] In one example, the copper (I) salt can be present in the biocidal composition in an amount of at least 1 gram per liter of the biocidal composition or carrier. In certain examples, the copper (I) salt can be present in the biocidal composition or carrier in an amount of less than 135 grams per liter of the biocidal composition or carrier. In certain examples, the copper (I) salt can be present in the biocidal composition or carrier in an amount (grams per liter of the 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, 1 - 35, 1 - 30, 1 - 25, 1 - 20, 1 - 15, 1 - 10, 1 - 5, 2 - 135, 2 - 130, 2 - 125, 2 - 120, 2 - 115, 2 - 110, 2 - 105, 2 - 100, 2 - 95, 2 - 90, 2 - 85, 2 - 80, 2 - 75, 2 - 70, 2 - 65, 2 - 60, 2 - 55, 2 - 50, 2 - 45, 2 - 40, 2 - 35, 2 - 30, 2 - 25, 2 - 20, 2 - 15, 2 - 10, 2 - 5, 5 -135, 5 - 130, 5 - 125, 5 - 120, 5 - 115, 5 -110, 5 - 105, 5 - 100, 5 - 95, 5 - 90, 5 - 85, 5 - 80, 5 - 75, 5 - 70, 5 - 65, 5 - 60, 5- 55, 5 - 50, 5 - 45, 5 - 40, 5 - 35, 5 - 30, 5 - 25, 5 - 20, 5 - 15, 5 - 10, 10 - 135, 10 - 130, 10 - 125, 10 - 120, 10 - 115, 10 - 110, 10 - 105, 10 - 100, 10 - 95, 10 -90, 10 - 85, 10 - 80, 10 - 75, 10 - 70, 10 - 65, 10 - 60, 10 - 55, 10 - 50, 10 - 45, 10- 40, 10 - 35, 10 -30, 10 - 25, 10 - 20, 10 - 15, 15 - 135, 15 - 130, 15 - 125, 15 -120, 15 - 115, 15 - 110, 15 - 105, 15 - 100, 15 - 95, 15- 90、15 - 85、15 - 80、15 -75、15 - 70、15 - 65、15 - 60、15 - 55、15 - 50、15 - 45、15 - 40、15 - 35、15 - 30、15- 25、15 - 20、20 -135、20 - 130、20 - 125、20 - 120、20 - 115、20 - 110、20 - 105、20- 100、20 - 95、20 - 90、20 - 85、20 - 80、20 - 75、20 - 70、20 - 65、20 - 60、20 -55、20 - 50、20 - 45、20 - 40、20 - 35、20 - 30、20 - 25、25 - 135、25 - 130、25 -125、25 - 120、25 - 115、25 - 110、25 - 105、25 - 100、25 - 95、25 - 90、25 - 85、25 -80、25 - 75、25 - 70、25 - 65、25 - 60、25 - 55、25 - 50、25 - 45、25 - 40、25 - 35、25- 30、30 - 135、30 - 130、30 - 125、30 - 120、30 - 115、30 - 110、30 - 105、30 - 100、30 - 95、30 - 90、30 - 85、30 - 80、30 - 75、30 - 70、30 - 65、30 - 60、30 - 55、30 -50、30 - 45、30 - 40、30 - 35、35 - 135、35 - 130、35 - 125、35 - 120、35 - 115、35 -110、35 - 105、35 - 100、35 - 95、35 - 90、35 - 85、35 - 80、35 - 75、35 - 70、35 -65、35 - 60、35 - 55、35 - 50、35 - 45、35 - 40、40 - 135、40 - 130、40 - 125、40 -120、40 - 115、40 - 110、40 - 105、40 - 100、40 - 95、40 - 90、40 - 85、40 - 80、40 -75、40 - 70、40 - 65、40 - 60、40 - 55、40 - 50、40 - 45、45 - 135、45 -130、45 -125、45 - 120、45 - 115、45 - 110、45 - 105、45 - 100、45 - 95、45 - 90、45 - 85、45 -80、45 - 75、45 - 70、45 - 65、45 - 60、45 - 55、45 - 50、50 - 135、50 - 130、50 -125、50 - 120、50 - 115、50 - 110、50 - 105、50 -100、50 - 95、50 - 90、50 - 85、50 -80、50 - 75、50 - 70、50 - 65、50 - 60、50 - 55、55 - 135、55 - 130、55 - 125、55 -120、55 - 115、55 - 110、55 - 105、55 - 100、55 - 95、55 - 90、55 - 85、55 - 80、55 -75、55 - 70、55 - 65、55 - 60、60 - 135、60 - 130、60 - 125、60 - 120、60 - 115、60 -110、60 - 105、60 - 100、60 - 95、60 - 90、60 - 85、60 - 80、60 - 75、60 - 70、60 -65、65 - 135、65 - 130、65 - 125、65 - 120、65 - 115、65 - 110、65 - 105、65 - 100、65- 95、65 - 90、65 - 85、65 - 80、65 - 75、65 - 70、70 - 135、70 - 130、70 - 125、70 -120、70 - 115、70 - 110、70 - 105、70 - 100、70 - 95、70 - 90、70 - 85、70 - 80、70 -75、75 - 135、75 - 130、75 - 125、75 - 120、75 - 115、75 - 110、75 - 105、75 - 100、75- 95、75 - 90、75 - 85、75 - 80、80 - 135、80 - 130、80 - 125、80 - 120、80 - 115、80- 110、80 - 105、80 - 100、80 - 95、80 - 90、80 - 85、85 - 135、85 - 130、85 - 125、85-120, 85 - 115, 85 - 110, 85 - 105, 85 - 100, 85 - 95, 85 - 90, 90 - 135, 90 - 130, 90 - 125, 90 - 120, 90 - 115, 90 - 110, 90 - 105, 90 - 100, 90 - 95, 95 - 135, 95 - 130, 95 - 125, 95 - 120, 95 - 115, 95 - 110, 95 - 105, 95 - 100, 100 - 135, 100 - 130, 100 - 125, 100 - 120, 100 - 115, 100 - 110, 100 - 105, 105 - 135, 105 - 130, 105 - 125, 105 - 120, 105 - 115, 105 - 110, 110 - 135, 110 - 130, 110 - 125, 110 - 120, 110 - 115, 115 - 135, 115 - 130, 115 - 125, 115 - 120, 120 - 135, 120 - 130, 120 - 125, 125 - 135, 125 - 130, 130 - 135; any combination thereof; or any range formed by any two of the foregoing amounts in grams per liter; including any subranges therebetween.

[0151] In one example, the molar ratio of copper auxiliary additive to copper (I) salt in the biocidal composition can be 0.1 : 1 to 50: 1, including for example, 0.1 : 1 to 49: 1, 0.1 : 1 to 48: 1, 0.1 : 1 to 47: 1, 0.1 : 1 to 46: 1, 0.1 : 1 to 45: 1, 0.1 : 1 to 44: 1, 0.1 : 1 to 43: 1, 0.1 : 1 to 42: 1, 0.1 : 1 to 41 : 1, 0.1 : 1 to 40: 1, 0.1 : 1 to 39: 1, 0.1 : 1 to 38: 1, 0.1 : 1 to 37: 1, 0.1 : 1 to 36: 1, 0.1 : 1 to 35: 1, 0.1 : 1 to 34: 1, 0.1 : 1 to 33: 1, 0.1 : 1 to 32: 1, 0.1 : 1 to 31 : 1, 0.1 : 1 to 30: 1, 0.1 : 1 to 29: 1, 0.1 : 1 to 28: 1, 0.1 : 1 to 27: 1, 0.1 : 1 to 26: 1, 0.1 : 1 to 25: 1, 0.1 : 1 to 24: 1, 0.1 : 1 to 23: 1, 0.1 : 1 to 22: 1, 0.1 : 1 to 21 : 1, 0.1 : 1 to 20: 1, 0.1 : 1 to 19: 1, 0.1 : 1 to 18: 1, 0.1 : 1 to 17: 1, 0.1 : 1 to 16: 1, 0.1 : 1 to 15: 1, 0.1 : 1 to 14.9: 1, 0.1 : 1 to 14.8: 1, 0.1 : 1 to 14.7: 1, 0.1 : 1 to 14.6: 1, 0.1 : 1 to 14.5: 1, 0.1 : 1 to 14.4: 1, 0.1 : 1 to 14.3: 1, 0.1 : 1 to 14.2: 1, 0.1 : 1 to 14.1 : 1, 0.1 : 1 to 14: 1, 0.1 : 1 to 13.9: 1, 0.1 : 1 to 13.8: 1, 0.1 : 1 to 13.7: 1, 0.1 : 1 to 13.6: 1, 0.1 : 1 to 13.5: 1, 0.1 : 1 to 13.4: 1, 0.1 : 1 to 13.3: 1, 0.1 : 1 to 13.2: 1, 0.1 : 1 to 13.1 : 1, 0.1 : 1 to 13: 1, 0.1 : 1 to 12.9: 1, 0.1 : 1 to 12.8: 1, 0.1 : 1 to 12.7: 1, 0.1 : 1 to 12.6: 1, 0.1 : 1 to 12.5: 1, 0.1 : 1 to 12.4: 1, 0.1 : 1 to 12.3: 1, 0.1 : 1 to 12.2: 1, 0.1 : 1 to 12.1 : 1, 0.1 : 1 to 12: 1, 0.1 : 1 to 11.9: 1, 0.1 : 1 to 11.8: 1, 0.1 : 1 to 11.7: 1, 0.1 : 1 to 11.6: 1, 0.1 : 1 to 11.5: 1, 0.1 : 1 to 11.4: 1, 0.1 : 1 to 11.3: 1, 0.1 : 1 to 11.2: 1, 0.1 : 1 to 11.1 : 1, 0.1 : 1 to 11 : 1, 0.1 : 1 to 10.9: 1, 0.1 : 1 to 10.8: 1, 0.1 : 1 to 10.7: 1, 0.1 : 1 to 10.6: 1, 0.1:1 to 10.5:1, 0.1:1 to 10.4:1, 0.1:1 to 10.3:1, 0.1:1 to 10.2:1, 0.1:1 to 10.1:1, 0.1:1 to 10:1, 0.1:1 to 9.9:1, 0.1:1 to 9.8:1, 0.1:1 to 9.7:1, 0.1:1 to 9.6:1, 0. 1:1 to 9.5:1, 0.1:1 to 9.4:1, 0.1:1 to 9.3:1, 0.1:1 to 9.2:1, 0.1:1 to 9.1:1, 0.1:1 to 9:1, 0.1:1 to 8.9:1, 0.1:1 to 8.8:1, 0.1:1 to 8.7:1, 0.1:1 to 8.6:1, 0.1:1 to 8.5 :1, 0.1:1 to 8.4:1, 0.1:1 to 8.3:1, 0.1:1 to 8.2:1, 0.1:1 to 8.1:1, 0.1:1 to 8:1, 0.1:1 to 7.9:1, 0.1:1 to 7.8:1, 0.1:1 to 7.7:1, 0.1:1 to 7.6:1, 0.1:1 to 7.5:1, 0.1: 1 to 7.4:1, 0.1:1 to 7.3:1, 0.1:1 to 7.2:1, 0.1:1 to 7.1:1, 0.1:1 to 7:1, 0.1:1 to 6.9:1, 0.1:1 to 6.8:1, 0.1:1 to 6.7:1, 0.1:1 to 6.6:1, 0.1:1 to 6.5:1, 0.1:1 to 6.4:1 0.1:1 to 6.3:1, 0.1:1 to 6.2:1, 0.1:1 to 6.1:1, 0.1:1 to 6:1, 0.1:1 to 5.9:1, 0.1:1 to 5.8:1, 0.1:1 to 5.7:1, 0.1:1 to 5.6:1, 0.1:1 to 5.5:1, 0.1:1 to 5.4:1, 0.1:1 0.1:1 to 5.2:1, 0.1:1 to 5.1:1, 0.1:1 to 5:1, 0.1:1 to 4.9:1, 0.1:1 to 4.8:1, 0.1:1 to 4.7:1, 0.1:1 to 4.6:1, 0.1:1 to 4.5:1, 0.1:1 to 4.4:1, 0.1:1 to 4.3:1, 0.1:1 to 4.2:1, 0.1:1 to 4.1:1, 0.1:1 to 4:1, 0.1:1 to 3.9:1, 0.1:1 to 3.8:1, 0.1:1 to 3.7:1, 0.1:1 to 3.6:1, 0.1:1 to 3.5:1, 0.1:1 to 3.4:1, 0.1:1 to 3.3:1, 0.1:1 to 3 0.2:1, 0.1:1 to 3.1:1, 0.1:1 to 3:1, 0.1:1 to 2.9:1, 0.1:1 to 2.8:1, 0.1:1 to 2.7:1, 0.1:1 to 2.6:1, 0.1:1 to 2.5:1, 0.1:1 to 2.4:1, 0.1:1 to 2.3:1, 0.1:1 to 2.2:1, 0.1 : 1 to 2.1 : 1, 0.1 : 1 to 2: 1, 0.1 : 1 to 1.9: 1, 0.1 : 1 to 1.8: 1, 0.1 : 1 to 1.7: 1, 0.1 : 1 to 1.6: 1, 0.1 : 1 to 1.5: 1, 0.1 : 1 to 1.4: 1, 0.1 : 1 to 1.3: 1, 0.1 : 1 to 1.2: 1, 0.1 : 1 to 1.1 : 1, 0.1 : 1 to 1 : 1, 0.2: 1 to 50: 1, 0.3: 1 to 50: 1, 0.4: 1 to 50: 1, 0.5: 1 to 50: 1, 0.6: 1 to 50: 1, 0.7: 1 to 50: 1, 0.8: 1 to 50: 1, 0.9: 1 to 50: 1, 1 : 1 to 50: 1, 1.1 : 1 to 50: 1, 1.2: 1 to 50: 1, 1.3: 1 to 50: 1, 1.4: 1 to 50: 1, 1.5: 1 to 50: 1, 1.6: 1 to 50: 1, 1.7: 1 to 50: 1, 1.8: 1 to 50: 1, 1.9: 1 to 50: 1, 2: 1 to 50: 1, 2.1 : 1 to 50: 1, 2.2: 1 to 50: 1, 2.3: 1 to 50: 1, 2.4: 1 to 50: 1, 2.5: 1 to 50: 1, 2.6: 1 to 50: 1, 2.7: 1 to 50: 1, 2.8: 1 to 50: 1, 2.9: 1 to 50: 1, 3: 1 to 50: 1, 3.1 : 1 to 50: 1, 3.2: 1 to 50: 1, 3.3: 1 to 50: 1, 3.4: 1 to 50: 1, 3.5: 1 to 50: 1, 3.6: 1 to 50: 1, 3.7: 1 to 50: 1, 3.8: 1 to 50: 1, 3.9: 1 to 50: 1, 4: 1 to 50: 1, 4.1 : 1 to 50: 1, 4.2: 1 to 50: 1, 4.3: 1 to 50: 1, 4.4: 1 to 50: 1, 4.5: 1 to 50: 1, 4.6: 1 to 50: 1, 4.7: 1 to 50: 1, 4.8: 1 to 50: 1, 4.9: 1 to 50: 1, 5: 1 to 50: 1, 5.1 : 1 to 50: 1, 5.2: 1 to 50: 1, 5.3: 1 to 50: 1, 5.4: 1 to 50: 1, 5.5: 1 to 50: 1, 5.6: 1 to 50: 1, 5.7: 1 to 50: 1, 5.8: 1 to 50: 1, 5.9: 1 to 50: 1, 6: 1 to 50: 1, 6.1 : 1 to 50: 1, 6.2: 1 to 50: 1, 6.3: 1 to 50: 1, 6.4: 1 to 50: 1, 6.5: 1 to 50: 1, 6.6: 1 to 50: 1, 6.7: 1 to 50: 1, 6.8: 1 to 50: 1, 6.9: 1 to 50: 1, 7: 1 to 50: 1, 7.1 : 1 to 50: 1, 7.2: 1 to 50: 1, 7.3: 1 to 50: 1, 7.4: 1 to 50: 1, 7.5: 1 to 50: 1, 7.6: 1 to 50: 1, 7.7: 1 to 50: 1, 7.8: 1 to 50: 1, 7.9: 1 to 50: 1, 8: 1 to 50: 1, 8.1 : 1 to 50: 1, 8.2: 1 to 50: 1, 8.3: 1 to 50: 1, 8.4: 1 to 50: 1, 8.5: 1 to 50: 1, 8.6: 1 to 50: 1, 8.7: 1 to 50: 1, 8.8: 1 to 50: 1, 8.9: 1 to 50: 1, 9: 1 to 50: 1, 9.1 : 1 to 50: 1, 9.2: 1 to 50: 1, 9.3: 1 to 50: 1, 9.4: 1 to 50: 1, 9.5: 1 to 50: 1, 9.6: 1 to 50: 1, 9.7: 1 to 50: 1, 9.8: 1 to 50: 1, 9.9: 1 to 50: 1, 10: 1 to 50: 1, 10.1 : 1 to 50: 1, 10.2: 1 to 50: 1, 10.3: 1 to 50: 1, 10.4: 1 to 50: 1, 10.5: 1 to 50: 1, 10.6: 1 to 50: 1, 10.7: 1 to 50: 1, 10.8: 1 to 50: 1, 10.9: 1 to 50: 1, 11 : 1 to 50: 1, 11.1 : 1 to 50: 1, 11.2: 1 to 50: 1, 11.3: 1 to 50: 1, 11.4: 1 to 50: 1, 11.5: 1 to 50: 1, 11.6: 1 to 50: 1, 11.7: 1 to 50: 1, 11.8: 1 to 50: 1, 11.9: 1 to 50: 1, 12: 1 to 50: 1, 12.1 : 1 to 50: 1, 12.2: 1 to 50: 1, 12.3: 1 to 50: 1, 12.4: 1 to 50: 1, 12.5: 1 to 50: 1, 12.6: 1 to 50: 1, 12.7: 1 to 50: 1, 12.8: 1 to 50: 1, 12.9: 1 to 50: 1, 13: 1 to 50: 1, 13.1 : 1 to 50: 1, 13.2: 1 to 50: 1, 13.3: 1 to 50: 1, 13.4: 1 to 50: 1, 13.5: 1 to 50: 1, 13.6: 1 to 50: 1, 13.7: 1 to 50: 1, 13.8: 1 to 50: 1, 13.9: 1 to 50: 1, 14: 1 to 50: 1, 14.1 : 1 to 50: 1, 14.2: 1 to 50: 1, 14.3: 1 to 50: 1, 14.4: 1 to 50: 1, 14.5: 1 to 50: 1, 14.6: 1 to 50: 1, 14.7: 1 to 50: 1, 14.8: 1 to 50: 1, 14.9:1 to 50:1, 15:1 to 50:1, 16:1 to 50:1, 17:1 to 50:1, 18:1 to 50:1, 19:1 to 50:1, 20:1 to 50:1, 21:1 to 50:1, 22:1 to 50:1, 23:1 to 50:1, 24:1 to 50:1, 25:1 to 50:1, 26:1 to 50:1, 27:1 to 50:1, 28:1 to 50:1, 29:1 to 50:1, 30:1 to 50:1, 31:1 to 50:1, 32:1 to 50:1, 33:1 to 50:1, 34:1 to 50:1, 35:1 to 50:1, 36:1 to 50:1, 37:1 to 50:1, 38:1 to 50:1, 39:1 to 50:1, 40:1 to 50:1, 41:1 to 50:1, 42:1 to 50:1, 43:1 to 50:1, 44:1 to 50:1, 45:1 to 50:1, 46:1 to 50:1, 47:1 to 50:1, 48:1 to 50:1, 49:1 to 50:1; or any range formed by any two of the foregoing ratios, including any sub-ratios therein. The foregoing ratios generally refer to the number of moles of copper auxiliary additive relative to the number of moles of copper (I) salt, but such ratios can also be used to represent the number of moles of copper auxiliary additive relative to the number of moles of copper (calculated on an atomic basis).

[0152] After the copper (I) salt and copper-assisting additive are combined with the carrier, as described herein, the composition (e.g., biocidal composition) or resulting material can be shaped into a desired article or can be applied to a surface. In cases where 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, such a composition can be applied to a surface as a layer. Examples of surfaces to which the biocidal composition can be applied include wood, polymers, metals, glass, ceramics, stone, concrete, cement, minerals, drywall, asphalt, or any combination thereof. Examples of articles that can be formed using the compositions described herein include housings or enclosures for electronic devices (e.g., mobile phones, smartphones, tablets, video players, information terminal devices, laptop computers), architectural structures (e.g., countertops, walls, trim, ceilings, floors, facades, and trim), appliances (e.g., stovetops, refrigerator doors, and dishwasher doors), information displays (e.g., whiteboards), automotive parts (e.g., dashboards, windshields, window parts), and high-touch surfaces (e.g., computer mice, computer keyboards, railings, doors, door handles, door push plates, telephones, telephone buttons, or elevator buttons). The articles can be shaped by any method known in the art, such as by molding (e.g., injection molding), or otherwise shaping the article into a desired shape. In certain examples, the entire article can include the biocidal composition (e.g., the entire article is formed from the biocidal composition). In certain examples, a method of forming an article is disclosed, 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 (e.g., injection molding). In certain examples, a method of preparing a masterbatch is disclosed, the method including mixing the biocidal composition in concentrated form.

[0153] The compositions described herein can include pigments to impart color. Thus, a coating or layer made from such a composition can exhibit a variety of colors, depending on the carrier color, carrier mixture, and particle loading. Furthermore, it is contemplated that the compositions and / or coatings described herein will not show an adverse effect on paint adhesion, as measured by ASTM D4541. In certain examples, the adhesion of the composition or coating to the 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 fails before the coating separates from the surface of the substrate.

[0154] In some aspects, the biocidal composition can be in the form of an article, a layer, a coating, a dry film, or as a liquid composition including a suspension and a solution, which can be applied to a surface or stored in a container (e.g., prior to use). In some aspects, the biocidal composition is not in the form of a molded article, such as an injection molded article or an extruded article.

[0155] One or more examples of the biocidal composition of the present disclosure can include a copper (I) salt (which can be optionally pre-treated with a pre-treatment solution), a copper-assisted additive, and a carrier having a loading level of the copper (I) salt, such that the composition can exhibit resistance or preservation against the presence or growth of a contaminant (e.g., a microorganism). Contaminants include fungi, bacteria, viruses, molds, mildews, algae, and combinations thereof. In certain examples, the presence of a contaminant in a material (such as a polyurethane, an epoxy resin) can cause a change in color of the composition, can reduce the integrity of the composition, and can negatively impact various properties of the composition. By including a minimum loading amount of a copper (I) salt (e.g., 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less; alternatively or additionally, the following amounts: 0 wt% or more, e.g., greater than 0 wt%, 0.01 wt% or more, 0.05 wt% or more, 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 2 wt% or more, 3 wt% or more, or 4 wt% or more, based on the weight of the carrier or the composition) and a copper-assisted additive in the carrier, the contaminant can be eliminated or reduced. In certain examples, the composition can or can not include certain components when the contaminant is eliminated or reduced. Thus, the formulation used in one or more examples of the compositions described herein can have greater flexibility and variation than previously possible when used in known compositions that do not include a copper (I) salt.

[0156] In an example, the biocidal composition can exhibit one or more of the following effects: (1) a concentration of a microorganism selected from Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-Cov-2, and mixtures thereof, is greater than a 3-log reduction; (2) a change in color of 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-assisted additive or the carrier and the copper-assisted additive without the copper (I) salt; or (3) any combination thereof. The antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EPA test.

[0157] In an example, a biocidal composition comprising a support, a copper (I) salt, and a copper-assisting additive has better antimicrobial efficacy over time (e.g., 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 at least 90 days) compared to an otherwise identical composition that does not include a copper-assisting additive or does not include a copper (I) salt (e.g., copper in a specified amount, such as an amount of 0.01 at.% to 10 at.% or 0.01 at.% to 2 at.%; a copper (I) salt in an amount of 0.01 wt.% to 15 wt.% in the composition; and / or a molar ratio of the amount of copper-assisting additive to the amount of copper is 0.1 : 1 to 50: 1). Similarly, in certain examples, such a biocidal composition also has minimal color change (e.g., color shift and / or color shift) compared to an otherwise identical composition, as disclosed elsewhere herein.

[0158] In one example, when the biocidal composition forms a coating (e.g., a dry film) within one day of making the biocidal composition and the coating is stored at ambient conditions for 7 days or at least 7 days (e.g., 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 365 days, less than 180 days, less than 150 days, less than 120 days, less than 100 days, less than 90 days, less than 75 days, less than 60 days, less than 50 days, less than 40 days, less than 30 days, less than 25 days, less than 20 days, less than 15 days, or less than 10 days) to form a stored coating or stored article, the stored coating or article exhibits a concentration of microorganisms selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-Cov-2, and mixtures thereof that is greater than a 1 log reduction (e.g., greater than a 2.5 log reduction, greater than a 3 log reduction, greater than a 3.5 log reduction, greater than a 4 log reduction, greater than a 4.5 log reduction, or greater than a 5 log reduction; alternatively or additionally, less than a 6 log reduction, less than a 5.5 log reduction, less than a 5 log reduction, less than a 4.5 log reduction, less than a 4 log reduction, less than a 3.5 log reduction, less than a 3 log reduction, less than a 2.5 log reduction, less than a 2 log reduction, or less than a 1.5 log reduction). Generally and without wishing to be bound by theory, it is believed that the above feature demonstrates an extension of the antimicrobial efficacy of a coating (e.g., a dry film) or article comprising the biocidal composition over time. The antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EPA test.

[0159] As used herein, the term “for X days” or “for X years” (where X is a number) means that the extension of the specified property lasts for a minimum of X days (or for X years). The extension of the specified property can continue for a longer period of time, and after such longer period of time, the specified property (e.g., log reduction or color value) can begin to decrease; however, if the specified property is present for X days (or X years), then the “for X days” (or “for X years”) is satisfied. In this regard, the term “for X days” and the term “for at least X days” are intended to be synonymous terms.

[0160] In an example, when the biocidal composition is stored as a liquid composition, mixture, or suspension under ambient conditions for a period of 7 days or at least 7 days (e.g., 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 days, less than 120 days, less than 100 days, less than 90 days, less than 75 days, less than 60 days, less than 50 days, less than 40 days, less than 30 days, less than 25 days, less than 20 days, less than 15 days, or less than 10 days) to form the stored liquid composition, mixture, or suspension in one day, exhibits a concentration of microorganisms selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-Cov-2, and mixtures thereof that is greater than 1 log reduction (e.g., greater than 2.5 log reduction, greater than 3 log reduction, greater than 3.5 log reduction, greater than 4 log reduction, greater than 4.5 log reduction, or greater than 5 log reduction; alternatively or additionally, less than 6 log reduction, less than 5.5 log reduction, less than 5 log reduction, less than 4.5 log reduction, less than 4 log reduction, less than 3.5 log reduction, less than 3 log reduction, less than 2.5 log reduction, less than 2 log reduction, or less than 1.5 log reduction). Generally, without wishing to be bound by theory, it is believed that the above feature demonstrates antimicrobial efficacy of a coating (e.g., a dry film) or article after the biocidal composition is stored in liquid form (e.g., a can of polyurethane or epoxy precursor) for a certain period of time. The antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EPA test.

[0161] In an example, minimizing the color change corresponds to a CIE Delta E * value 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):

[0162] (VI)

[0163] where L * , a * , and b* CIE L * , a * and b * values for a biocidal composition * 对照 , a * 对照 and b * 对照 CIE L * , a * and b * values for an otherwise identical composition without a copper (I) salt or copper-assisted additive.

[0164] In one example, the biocidal composition or film prepared from the biocidal composition exhibits (1) a transmittance as measured at each wavelength from 400 nm to 700 nm, and / or (2) an average transmittance as measured over the wavelength range from 400 nm 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 55%, or at least 56%, or at least 57%, or at least 58%, or at least 59%, or at least 60%, or at least 61%, or at least 62%, or at least 63%, or at least 64%, or at least 65%, or at least 66%, or at least 67%, or at least 68%, or at least 69%, or at least 70%, or at least 71%, or at least 72%, or at least 73%, or at least 74%, or at least 75%, or at least 76%, or at least 77%, or at least 78%, or at least 79%, or at least 80%, or at least 81%, or at least 82%, or at least 83%, or at least 84%, or at least 85%, or at least 86%, or at least 87%, or at least 88%, or at least 89%, or at least 90%, or at least 90.5%, or at least 91.0%, or at least 91.5%, or at least 92.0%, or at least 92.5%, or at least 93.0%, or at least 93.5%, or at least 94.0%, or at least 94.5%, or at least 95.0%, or at least 95.1%, or at least 95.2%, or at least 95.3%, or at least 95.4%, or at least 95.5%, or at least 95.6%, or at least 95.7%, or at least 95.8%, or at least 95.9%, or at least 96.0%, or at least 96.1%, or at least 96.2%, or at least 96.3%, or at least 96.4%, or at least 96.5%, or at least 96.6%, or at least 96.7%, or at least 96.8%, or at least 96.9%, or at least 97.0%, or at least 97.1%, or at least 97.2%, or at least 97.3%, or at least 97.4%, or at least 97.5%, or at least 97.6%, or at least 97.7%, or at least 97.8%, or at least 97.9%, or at least 98.0%, or at least 98.1%, or at least 98.2%, or at least 98.3%, or at least 98.4%, or at least 98.5%, or at least 98.6%, or at least 98.7%, or at least 98.8%, or at least 98.9%, or at least 99.0%, or at least 99.1%, or at least 99.2%, or at least 99.3%, or at least 99.4%, or at least 99.5%, or at least 99.6%, or at least 99.7%, or at least 99.8%, or at least 99.9%, or at least > 99.9%; when measured at a thickness of 40 pm. The average transmittance is calculated by adding the transmittance at each wavelength between 400 nm and 700 nm and dividing by the total number of such wavelengths.

[0165] In an example, the biocidal composition or film thereof exhibits a transmittance as measured at each wavelength from 400 nanometers to 700 nanometers that can be within 20 percent points of a second transmittance of an otherwise identical composition or film thereof that does not contain a copper (I) salt or a copper-assisted additive; including, for example, within 19.5 percent points, or within 19.0 percent points, or within 18.5 percent points, or within 18.0 percent points, or within 17.5 percent points, or within 17.0 percent points, or within 16.5 percent points, or within 16.0 percent points, or within 15.5 percent points, or within 15.0 percent points, or within 14.5 percent points, or within 14.0 percent points, or within 13.5 percent points, or within 13.0 percent points, or within 12.5 percent points, or within 12.0 percent points, or within 11.5 percent points, or within 11.0 percent points, or within 10.5 percent points, or within 10.0 percent points, or within 9.9 percent points, or within 9.8 percent points, or within 9.7 percent points, or within 9.6 percent points, or within 9.5 percent points, or within 9.4 percent points, or within 9.3 percent points, or within 9.2 percent points, or within 9.1 percent points, or within 9.0 percent points, or within 8.9 percent points, or within 8.8 percent points, or within 8.7 percent points, or within 8.6 percent points, or within 8.5 percent points, or within 8.4 percent points, or within 8.3 percent points, or within 8.2 percent points, or within 8.1 percent points, or within 8.0 percent points, or within 7.9 percent points, or within 7.8 percent points, or within 7.7 percent points, or within 7.6 percent points, or within 7.5 percent points, or within 7.4 percent points, or within 7.3 percent points, or within 7.2 percent points, or within 7.1 percent points, or within 7.0 percent points, or within 6.9 percent points, or within 6.8 percent points, or within 6.7 percent points, or within 6.6 percent points, or within 6.5 percent points, or within 6.4 percent points, or within 6.3 percent points, or within 6.2 percent points, or within 6.1 percent points, or within 6.0 percent points, or within 5.9 percent points, or within 5.8 percent points, or within 5.7 percent points, or within 5.6 percent points, or within 5.5 percent points, or within 5.4 percent points, or within 5.3 percent points, or within 5.2 percent points, or within 5.1 percent points, or within 5.0 percent points, or within 4.9 percent points, or within 4.8 percent points, or within 4.7 percent points, or within 4.6 percent points, or within 4.5 percent points, or within 4.4 percent points, or within 4.3 percent points, or within 4.2 percent points, or within 4.1 percent points, or within 4.0 percent points, or within 3.9 percent points, or within 3.8 percent points, or within 3.7 percent points, or within 3.6 percent points, or within 3.5 percent points, or within 3.4 percent points, or within 3.3 percent points, or within 3.2 percent points, or within 3.1 percent points, or within 3.0 percent points, or within 2.9 percent points, or within 2.8 percent points, or within 2.7 percent points, or within 2.6 percent points, or within 2.5 percent points, or within 2.4 percent points, or within 2.3 percent points, or within 2.2 percent points, or within 2.1 percent points, or within 2.0 percent points, or within 1.9 percent points, or within 1.8 percent points, or within 1.7 percent points, or within 1.6 percent points, or within 1.5 percent points, or within 1.4 percent points, or within 1.3 percent points, or within 1.2 percent points, or within 1.1 percent points, or within 1.0 percent points, or within 0.9 percent points, or within 0.8 percent points, or within 0.7 percent points, or within 0.6 percent points, or within 0.5 percent points, or within 0.4 percent points, or within 0.3 percent points, or within 0.2 percent points, or within 0.1 percent points, or within 0.0 percent points, when measured at a thickness of 40 µm.3 percentage points, or within 3.2 percentage points, or within 3.1 percentage points, or within 3.0 percentage points, or within 2.9 percentage points, or within 2.8 percentage points, or within 2.7 percentage points, or within 2.6 percentage points, or within 2.5 percentage points, or within 2.4 percentage points, or within 2.3 percentage points, or within 2.2 percentage points, or within 2.1 percentage points, or within 2.0 percentage points, or within 1.9 percentage points, or within 1.8 percentage points, or within 1.7 percentage points, or within 1.6 percentage points, or within 1.5 percentage points, or within 1.4 percentage points, or within 1.3 percentage points, or within 1.2 percentage points, or within 1.1 percentage points, or within 1.0 percentage points, or within 0.9 percentage points, or within 0.8 percentage points, or within 0.7 percentage points, or within 0.6 percentage points, or within 0.5 percentage points, or within 0.4 percentage points, or within 0.3 percentage points, or within 0.2 percentage points, or within 0.1 percentage points.

[0166] In an example, the film of the biocidal composition can have a thickness of 30 pm to 3000 pm, including for example, 40 pm, or 50 pm, or 60 pm, or 70 pm, or 80 pm, or 90 pm, or 100 pm, or 110 pm, or 120 pm, or 130 pm, or 140 pm, or 150 pm, or 160 pm, or 170 pm, or 180 pm, or 190 pm, or 200 pm, or 210 pm, or 220 pm, or 230 pm, or 240 pm, or 250 pm, or 260 pm, or 270 pm, or 280 pm, or 290 pm, or 300 pm, or 310 pm, or 320 pm, or 330 pm, or 340 pm, or 350 pm, or 360 pm, or 370 pm, or 380 pm, or 390 pm, or 400 pm, or 410 pm, or 420 pm, or 430 pm, or 440 pm, or 450 pm, or 460 pm, or 470 pm, or 480 pm, or 490 pm, or 500 pm, or 510 pm, or 520 pm, or 530 pm, or 540 pm, or 550 pm, or 560 pm, or 570 pm, or 580 pm, or 590 pm, or 600 pm, or 610 pm, or 620 pm, or 630 pm, or 640 pm, or 650 pm, or 660 pm, or 670 pm, or 680 pm, or 690 pm, or 700 pm, or 710 pm, or 720 pm, or 730 pm, or 740 pm, or 750 pm, or 760 pm, or 770 pm, or 780 pm, or 790 pm, or 800 pm, or 810 pm, or 820 pm, or 830 pm, or 840 pm, or 850 pm, or 860 pm, or 870 pm, or 880 pm, or 890 pm, or 900 pm, or 910 pm, or 920 pm, or 930 pm, or 940 pm, or 950 pm, or 960 pm, or 970 pm, or 980 pm, or 990 pm, or 1000 pm, or 1050 pm, or 1100 pm, or 1150 pm, or 1200 pm, or 1250 pm, or 1300 pm, or 1350 pm, or 1400 pm, or 1450 pm, or 1500 pm, or 1550 pm, or 1600 pm, or 1650 pm, or 1700 pm, or 1750 pm, or 1800 pm, or 1850 pm, or 1900 pm, or 1950 pm, or 2000 pm, or 2050 pm, or 2100 pm, or 2150 pm, or 2200 pm, or 2250 pm, or 2300 pm, or 2350 pm, or 2400 pm, or 2450 pm, or 2500 pm, or 2550 pm, or 2600 pm, or 2650 pm, or 2700 pm, or 2750 pm, or 2800 pm, or 2850 pm, or 2900 pm, or 2950 pm, or 3000 pm.30 µm to 40 µm, or to 50 µm, or to 60 µm, or to 70 µm, or to 80 µm, or to 90 µm, or to 100 µm, or to 110 µm, or to 120 µm, or to 130 µm, or to 140 µm, or to 150 µm, or to 160 µm, or to 170 µm, or to 180 µm, or to 190 µm, or to 200 µm, or to 210 µm, or to 220 µm, or to 230 µm, or to 240 µm, or to 250 µm, or to 260 µm, or to 270 µm, or to 280 µm, or to 290 µm, or to 300 µm, or to 310 µm, or to 320 µm, or to 330 µm, or to 340 µm, or to 350 µm, or to 360 µm, or to 370 µm, or to 380 µm, or to 390 µm, or to 400 µm, or to 410 µm, or to 420 µm, or to 430 µm, or to 440 µm, or to 450 µm, or to 460 µm, or to 470 µm, or to 480 µm, or to 490 µm, or to 500 µm, or to 510 µm, or to 520 µm, or to 530 µm, or to 540 µm, or to 550 µm, or to 560 µm, or to 570 µm, or to 580 µm, or to 590 µm, or to 600 µm, or to 610 µm, or to 620 µm, or to 630 µm, or to 640 µm, or to 650 µm, or to 660 µm, or to 670 µm, or to 680 µm, or to 690 µm, or to 700 µm, or to 710 µm, or to 720 µm, or to 730 µm, or to 740 µm, or to 750 µm, or to 760 µm, or to 770 µm, or to 780 µm, or to 790 µm, or to 800 µm, or to 810 µm, or to 820 µm, or to 830 µm, or to 840 µm, or to 850 µm, or to 860 µm, or to 870 µm, or to 880 µm, or to 890 µm, or to 900 µm, or to 910 µm, or to 920 µm, or to 930 µm, or to 940 µm, or to 950 µm, or to 960 µm, or to 970from 980 pm, or from 990 pm, or from 1000 pm, or from 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 2800 pm, or from 2850 pm, or from 2900 pm, or from 2950 pm, or a range formed by any two of the foregoing thicknesses; including any sub-ranges therein.

[0167] In an example, a method of making a biocidal composition is disclosed, the method comprising adding a biocidal additive formulation to a carrier. When the carrier is a polyurethane or an epoxy resin, the biocidal additive formulation can comprise a copper (I) salt and a copper-assisting additive. When the carrier is a second polyurethane precursor, the biocidal additive formulation can comprise a first polyurethane precursor, a copper (I) salt, and a copper-assisting additive. When the carrier is a second epoxy resin precursor, the biocidal additive formulation can comprise a first epoxy resin precursor, a copper (I) salt, and a copper-assisting additive.

[0168] In an example, a method is disclosed that includes applying a biocidal composition to a surface. The biocidal composition can include any of the components described elsewhere herein. In an example, the surface is or includes wood, a polymer (e.g., plastic or rubber), a metal (e.g., steel, iron, copper, gold, silver, aluminum, tin, platinum, alloys thereof, or any combination thereof), glass (e.g., lithium aluminosilicate glass, borosilicate glass, chemically strengthened glass, or ion-exchanged glass), ceramic, glass-ceramic, stone, concrete, cement, mineral, drywall, asphalt, or any combination thereof. In an example, the method of applying to the surface can be any suitable method, including spraying, spin coating, dipping, and the like, or any combination thereof. For example, the composition can be sprayed onto the surface. In some aspects of applying to the surface, such as in spraying the composition, the copper(I) species (e.g., ion or salt) can at least partially exist in a solubilized form (e.g., facilitated by complexation with a copper co-additive), although such copper(I) species can alternatively or additionally exist in a suspended form.

[0169] In an example, a method of improving or maintaining the antimicrobial efficacy of a biocidal composition (any of the biocidal compositions disclosed herein) is disclosed, the method comprising: combining a carrier, a copper(I) salt, and a copper-assisting additive, wherein the biocidal composition comprises copper in an amount of 0.01 at.% to 10 at.%, and the carrier and the copper-assisting additive are different. In certain examples, the molar ratio of the amount of the copper-assisting additive to the amount of copper is 0.1:1 to 50:1. In certain examples, the copper(I) salt is first combined with the copper-assisting additive to form a mixture, and then the mixture is combined with the carrier to form the biocidal composition. In other examples, the color change of the biocidal composition is minimized relative to the color change of an otherwise identical composition in the absence of the copper-assisting additive, or an otherwise identical composition free of the copper(I) salt, or an otherwise identical composition free of both the copper-assisting additive and the copper(I) salt. In still other examples, a method of minimizing the color change of a biocidal composition is provided, wherein the copper-assisting additive is any of the compounds disclosed herein or a formula (e.g., a compound of Formula (I), a compound of Formula (II), or any combination thereof), alone or with a compound of Formula (III), a compound of Formula (IV), a compound of Formula (V), or any combination thereof. In still other examples, a method of minimizing the color change of a biocidal composition is provided, wherein the copper-assisting additive is any of the compounds 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(hydroxypropyl) phosphine, tributyl phosphine, or any combination thereof, alone or with a compound such as 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, tris(2-ethylhexyl) phosphate, methyl phosphate, dimethyl phosphate, trimethyl phosphate, butyl phosphate (e.g., n-butyl, sec-butyl, or t-butyl), dibutyl phosphate (e.g., n-butyl, sec-butyl, or t-butyl), tributyl phosphate (e.g., n-butyl, sec-butyl, or t-butyl), phenyl phosphate, diphenyl phosphate, triphenyl phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, tributyl borate, tributyl citrate, or any combination thereof. In still other examples, a method of minimizing the color change of a biocidal composition is provided, wherein the composition exhibits a concentration of microorganisms greater than a 3-log reduction of microorganisms selected from the group consisting of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-Cov-2, and mixtures thereof. The antimicrobial efficacy can be measured as described elsewhere herein, such as by using the EPA test. In still other examples, a method of minimizing the color change of a biocidal composition is provided, wherein the CIE DE *a value less than 10, as measured according to equation (VI):

[0170] (VI)

[0171] where L * , a * and b * are the CIE L * , a * and b * values of the biocidal material, and L * 对照 , a * 对照 and b * 对照 are the CIE L * , a * and b * values of the otherwise identical composition without the copper (I) salt or copper- assisted additive.

[0172] In one example, the biocidal composition can exhibit a delta E that can be 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 equation (VI):

[0173] (VI)

[0174] where L * , a * and b * are the CIE values of the biocidal composition after preparation, and then the biocidal composition is stored at ambient temperature and ambient relative humidity for 7 days (e.g., 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) within one day of preparation, and L * 对照 , a * 对照 and b * 对照 are the CIE values of the otherwise identical composition without the copper (I) salt or copper-assisted additive.

[0175] In an example, the present disclosure provides a biocidal additive formulation comprising a copper(I) salt and a copper-assist additive. In some aspects, the biocidal additive formulation can be a relatively concentrated formulation to be added to a carrier to provide a biocidal composition. In this aspect, in some aspects, the biocidal additive formulation can be in the form of a packet that can be added by an end user to, for example, a polyurethane, a polyurethane precursor, an epoxy resin, an epoxy resin precursor, or a melamine resin, in order to render the polyurethane, polyurethane precursor, epoxy resin, epoxy resin precursor, or melamine resin antimicrobial without substantially affecting color and / or clarity. Such biocidal additive formulations can also be added by a manufacturer during or after production of a large quantity of polyurethane precursor or epoxy resin precursor, in order to impart, for example, desired antimicrobial properties. Examples of biocidal additive formulations can include powders, slurries, gels, liquids, concentrates, and solutions. In certain examples, the biocidal additive formulation is in a liquid form at ambient conditions (1 atm (about 101.3 kPa) and 20 °C). In some aspects, the biocidal additive formulation includes a dissolved copper(I) salt in the form of a copper complex, where the copper(I) salt is coordinated or otherwise associated with a copper-assist additive that promotes solubility of the copper(I) salt. Without wishing to be bound by theory, it is believed that in some aspects, it is desirable to first prepare 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-assist additive separately to a composition. For example, it is believed that in some cases, adding a copper salt alone or adding a copper salt and an additive separately to the same composition (without premixing) can not allow the copper-assist additive to sufficiently promote availability and / or persistence of copper(I) ions. For example, separate addition can not allow the copper-assist additive to find and associate with the copper salt. However, in certain aspects, separate addition of the copper salt and copper-assist additive can be sufficient, for example, when the additive is present in a sufficiently high concentration and / or the medium of the composition otherwise does not inhibit the ability of the additive and copper salt to come together, such as due to viscosity, diffusion, or some other reason. In certain examples, the biocidal additive formulation can include an antioxidant package. The antioxidant package can include a single component or a ternary mixture. Examples of antioxidant packages can include a primary antioxidant; a phenolic, such as BHT; a secondary antioxidant, such as Ultranox TM 626、Weston TM430 ZP; sulfur ester-based antioxidant (thiosynergist), such as distearyl-3,3'- thiodipropionate; ascorbate ester, such as ascorbyl palmitate; or any combination thereof. In certain examples, the biocidal additive formulation can include a reducing agent. Examples of reducing agents can include ascorbic acid, hydroxylamine hydrochloride, various phosphines, sulfite compounds, oxalic acid, sodium thiosulfate, or any combination thereof. Examples of biocidal additive formulation forms can include a powder, a slurry, a gel, a liquid, a concentrate, and a solution. In certain examples, the biocidal additive formulation can include an antioxidant package. The antioxidant package can include a single component or a ternary mixture. Examples of antioxidant packages can include a primary antioxidant; a phenolic, such as BHT; a secondary antioxidant, such as Ultranox TM 626、Weston TM 430 ZP; sulfur ester-based antioxidant (thiosynergist), such as distearyl-3,3'- thiodipropionate; ascorbate ester, such as ascorbyl palmitate; or any combination thereof. In certain examples, the biocidal additive formulation can include a reducing agent. Examples of reducing agents can include ascorbic acid, hydroxylamine hydrochloride, various phosphines, sulfite compounds, oxalic acid, sodium thiosulfate, or any combination thereof. In certain examples, the biocidal additive formulation can be in a sealed container that includes an inert atmosphere.

[0176] In an example, the molar concentration of the copper(I) salt in solution in the biocidal additive formulation is from 20 mM to 200 mM, including, for example, 25 mM, or 30 mM, or 35 mM, or 40 mM, or 45 mM, or 50 mM, or 55 mM, or 60 mM, or 65 mM, or 70 mM, or 75 mM, or 80 mM, or 85 mM, or 90 mM, or 95 mM, or 100 mM, or 105 mM, or 110 mM, or 115 mM, or 120 mM, or 125 mM, or 130 mM, or 135 mM, or 140 mM, or 145 mM, or 150 mM, or 155 mM, or 160 mM, or 165 mM, or 170 mM, or 175 mM, or 180 mM, or 185 mM, or 190 mM, or 195 mM to 200 mM; or from 20 mM to 25 mM, or to 30 mM, or to 35 mM, or to 40 mM, or to 45 mM, or to 50 mM, or to 55 mM, or to 60 mM, or to 65 mM, or to 70 mM, or to 75 mM, or to 80 mM, or to 85 mM, or to 90 mM, or to 95 mM, or to 100 mM, or to 105 mM, or to 110 mM, or to 115 mM, or to 120 mM, or to 125 mM, or to 130 mM, or to 135 mM, or to 140 mM, or to 145 mM, or to 150 mM, or to 155 mM, or to 160 mM, or to 165 mM, or to 170 mM, or to 175 mM, or to 180 mM, or to 185 mM, or to 190 mM, or to 195 mM; or a range formed by any two of the foregoing molar concentrations; including any subranges therebetween.

[0177] In certain examples, the biocidal additive formulation can comprise a copper- assisted additive at a molar concentration in the biocidal additive formulation of 0.06 mM to 0.6 mM; including, for example, 0.065 mM, or 0.07 mM, or 0.075 mM, or 0.08 mM, or 0.085 mM, or 0.09 mM, or 0.095 mM, or 0.1 mM, or 0.105 mM, or 0.110 mM, or 0.115 mM, or 0.120 mM, or 0.125 mM, or 0.130 mM, or 0.135 mM, or 0.140 mM, or 0.145 mM, or 0.150 mM, or 0.155 mM, or 0.160 mM, or 0.165 mM, or 0.170 mM, or 0.175 mM, or 0.180 mM, or 0.185 mM, or 0.190 mM, or 0.195 mM, or 0.200 mM, or 0.205 mM, or 0.210 mM, or 0.215 mM, or 0.220 mM, or 0.225 mM, or 0.230 mM, or 0.235 mM, or 0.240 mM, or 0.245 mM, or 0.250 mM, or 0.255 mM, or 0.260 mM, or 0.265 mM, or 0.270 mM, or 0.275 mM, or 0.280 mM, or 0.285 mM, or 0.290 mM, or 0.295 mM, or 0.300 mM, or 0.305 mM, or 0.310 mM, or 0.315 mM, or 0.320 mM, or 0.325 mM, or 0.330 mM, or 0.335 mM, or 0.340 mM, or 0.345 mM, or 0.350 mM, or 0.355 mM, or 0.360 mM, or 0.365 mM, or 0.370 mM, or 0.375 mM, or 0.380 mM, or 0.385 mM, or 0.390 mM, or 0.395 mM, or 0.400 mM, or 0.405 mM, or 0.410 mM, or 0.415 mM, or 0.420 mM, or 0.425 mM, or 0.430 mM, or 0.435 mM, or 0.440 mM, or 0.445 mM, or 0.450 mM, or 0.455 mM, or 0.460 mM, or 0.465 mM, or 0.470 mM, or 0.475 mM, or 0.480 mM, or 0.485 mM, or 0.490 mM, or 0.495 mM, or 0.500 mM, or 0.505 mM, or 0.510 mM, or 0.515 mM, or 0.520 mM, or 0.525 mM, or 0.530 mM, or 0.535 mM, or 0.540 mM, or 0.545 mM, or 0.550 mM, or 0.555 mM, or 0.560 mM, or 0.565 mM, or 0.570 mM, or 0.575 mM, or 0.580 mM, or 0.585 mM, or 0.590 mM, or 0.595 mM to 0.600 mM; or 0.06 mM to 0.065 mM, or to 0.07 mM, or to 0.075 mM, or to 0.08 mM, or to 0.085 mM, or to 0.09 mM, or to 0.095 mM, or to 0.100 mM, or to 0.105 mM, or to 0.110 mM, or to 0.115 mM, or to 0.120 mM, or to 0.125 mM, or to 0.130 mM, or to 0.135 mM, or to 0.140 mM, or to 0.145 mM, or to 0.150 mM, or to 0.155 mM, or to 0.160 mM, or to 0.165 mM, or to 0.170 mM, or to 0.175 mM, or to 0.180 mM, or to 0.185 mM, or to 0.190 mM, or to 0.195 mM, or to 0.200 mM, or to 0.205 mM, or to 0.210 mM, or to 0.215 mM, or to 0.220 mM, or to 0.225 mM, or to 0.230 mM, or to 0.235 mM, or to 0.240 mM, or to 0.245 mM, or to 0.250 mM, or to 0.255 mM, or to 0.260 mM, or to 0.265 mM, or to 0.270 mM, or to 0.275 mM, or to 0.280 mM, or to 0.285 mM, or to 0.290 mM, or to 0.295 mM, or to 0.300 mM, or to 0.305 mM, or to 0.310 mM, or to 0.315 mM, or to 0.320 mM, or to 0.325 mM, or to 0.330 mM, or to 0.335 mM, or to 0.340 mM, or to 0.345 mM, or to 0.350 mM, or to 0.355 mM, or to 0.360 mM, or to 0.365 mM, or to 0.370 mM, or to 0.375 mM, or to 0.380 mM, or to 0.385 mM, or to 0.390 mM, or to 0.395 mM, or to 0.400 mM, or to 0.405 mM, or to 0.410 mM, or to 0.415 mM, or to 0.420 mM, or to 0.425 mM, or to 0.430 mM, or to 0.435 mM, or to 0.440 mM, or to 0.445 mM, or to 0.450 mM, or to 0.455 mM, or to 0.460 mM, or to 0.465 mM, or to 0.470 mM, or to 0.475 mM, or to 0.480 mM, or to 0.485 mM, or to 0.490 mM, or to 0.495 mM, or to 0.500 mM, or to 0.505 mM, or to 0.510 mM, or to 0.515 mM, or to 0.520 mM, or to 0.525 mM, or to 0.530 mM, or to 0.535 mM, or to 0.540 mM, or to 0.545 mM, or to 0.550 mM, or to 0.555 mM, or to 0.560 mM, or to 0.565 mM, or to 0.570 mM, or to 0.575 mM, or to 0.580 mM, or to 0.585 mM, or to 0.590 mM, or to 0.595 mM; or a range formed by any two of the foregoing molar concentrations; including any subranges therebetween.

[0178] In some examples, the biocidal additive formulation can include a copper (I) salt and a copper-assisting additive in any of the ratios disclosed elsewhere herein.

[0179] In certain examples, the biocidal additive formulation can comprise a solvent at a molar concentration in the biocidal additive formulation of 0.8 mM to 8.00 mM, including for example 0.85 mM, or 0.90 mM, or 0.95 mM, or 1.00 mM, or 1.05 mM, or 1.10 mM, or 1.15 mM, or 1.20 mM, or 1.25 mM, or 1.30 mM, or 1.35 mM, or 1.40 mM, or 1.45 mM, or 1.50 mM, or 1.55 mM, or 1.60 mM, or 1.65 mM, or 1.70 mM, or 1.75 mM, or 1.80 mM, or 1.85 mM, or 1.90 mM, or 1.95 mM, or 2.00 mM, or 2.05 mM, or 2.10 mM, or 2.15 mM, or 2.20 mM, or 2.25 mM, or 2.30 mM, or 2.35 mM, or 2.40 mM, or 2.45 mM, or 2.50 mM, or 2.55 mM, or 2.60 mM, or 2.65 mM, or 2.70 mM, or 2.75 mM, or 2.80 mM, or 2.85 mM, or 2.90 mM, or 2.95 mM, or 3.00 mM, or 3.05 mM, or 3.10 mM, or 3.15 mM, or 3.20 mM, or 3.25 mM, or 3.30 mM, or 3.35 mM, or 3.40 mM, or 3.45 mM, or 3.50 mM, or 3.55 mM, or 3.60 mM, or 3.65 mM, or 3.70 mM, or 3.75 mM, or 3.80 mM, or 3.85 mM, or 3.90 mM, or 3.95 mM, or 4.00 mM, or 4.05 mM, or 4.10 mM, or 4.15 mM, or 4.20 mM, or 4.25 mM, or 4.30 mM, or 4.35 mM, or 4.40 mM, or 4.45 mM, or 4.50 mM, or 4.55 mM, or 4.60 mM, or 4.65 mM, or 4.70 mM, or 4.75 mM, or 4.80 mM, or 4.85 mM, or 4.90 mM, or 4.95 mM, or 5.00 mM, or 5.05 mM, or 5.10 mM, or 5.15 mM, or 5.20 mM, or 5.25 mM, or 5.30 mM, or 5.35 mM, or 5.40 mM, or 5.45 mM, or 5.50 mM, or 5.55 mM, or 5.60 mM, or 5.65 mM, or 5.70 mM, or 5.75 mM, or 5.80 mM, or 5.85 mM, or 5.90 mM, or 5.95 mM, or 6.00 mM, or 6.05 mM, or 6.10 mM, or 6.15 mM, or 6.20 mM, or 6.25 mM, or 6.30 mM, or 6.35 mM, or 6.40 mM, or 6.45 mM, or 6.50 mM, or 6.55 mM, or 6.60 mM, or 6.65 mM, or 6.70 mM, or 6.75 mM, or 6.80 mM, or 6.85 mM, or 6.90 mM, or 6.95 mM, or 7.00 mM, or 7.05 mM, or 7.10 mM, or 7.15 mM, or 7.20 mM, or 7.25 mM, or 7.30 mM, or 7.35 mM, or 7.40 mM, or 7.45 mM, or 7.50 mM, or 7.55 mM, or 7.60 mM, or 7.65 mM, or 7.70 mM, or 7.75 mM, or 7.80 mM, or 7.85 mM, or 7.90 mM, or 7.95 mM to 8.00 mM; or 0.80 mM to 0.85 mM, or to 0.90 mM, or to 0.95 mM, or to 1.00 mM, or to 1.05 mM, or to 1.10 mM, or to 1.15 mM, or to 1.20 mM, or to 1.25 mM, or to 1.30 mM, or to 1.35 mM, or to 1.40 mM, or to 1.45 mM, or to 1.50 mM, or to 1.55 mM, or to 1.60 mM, or to 1.65 mM, or to 1.70 mM, or to 1.75 mM, or to 1.80 mM, or to 1.85 mM, or to 1.90 mM, or to 1.95 mM, or to 2.00 mM, or to 2.05 mM, or to 2.10 mM, or to 2.15 mM, or to 2.20 mM, or to 2.25 mM, or to 2.30 mM, or to 2.35 mM, or to 2.40 mM, or to 2.45 mM, or to 2.50 mM, or to 2.55 mM, or to 2.60 mM, or to 2.65 mM, or to 2.70 mM, or to 2.75 mM, or to 2.80 mM, or to 2.85 mM, or to 2.90 mM, or to 2.95 mM, or to 3.00 mM, or to 3.05 mM, or to 3.10 mM, or to 3.15 mM, or to 3.20 mM, or to 3.25 mM, or to 3.30 mM, or to 3.35 mM, or to 3.40 mM, or to 3.45 mM, or to 3.50 mM, or to 3.55 mM, or to 3.60 mM, or to 3.65 mM, or to 3.70 mM, or to 3.75 mM, or to 3.80 mM, or to 3.85 mM, or to 3.90 mM, or to 3.95 mM, or to 4.00 mM, or to 4.05 mM, or to 4.10 mM, or to 4.15 mM, or to 4.20 mM, or to 4.25 mM, or to 4.30 mM, or to 4.35 mM, or to 4.40 mM, or to 4.45 mM, or to 4.50 mM, or to 4.55 mM, or to 4.60 mM, or to 4.65 mM, or to 4.70 mM, or to 4.75 mM, or to 4.80 mM, or to 4.85 mM, or to 4.90 mM, or to 4.95 mM, or to 5.00 mM, or to 5.05 mM, or to 5.10 mM, or to 5.15 mM, or to 5.20 mM, or to 5.25 mM, or to 5.30 mM, or to 5.35 mM, or to 5.40 mM, or to 5.45 mM, or to 5.50 mM, or to 5.55 mM, or to 5.60 mM, or to 5.65 mM, or to 5.70 mM, or to 5.75 mM, or to 5.80 mM, or to 5.85 mM, or to 5.90 mM, or to 5.95 mM, or to 6.00 mM, or to 6.05 mM, or to 6.10 mM, or to 6.15 mM, or to 6.20 mM, or to 6.25 mM, or to 6.30 mM, or to 6.35 mM, or to 6.40 mM, or to 6.45 mM, or to 6.50 mM, or to 6.55 mM, or to 6.60 mM, or to 6.65 mM, or to 6.70 mM, or to 6.75 mM, or to 6.80 mM, or to 6.85 mM, or to 6.90 mM, or to 6.95 mM, or to 7.00 mM, or to 7.05 mM, or to 7.10 mM, or to 7.15 mM, or to 7.20 mM, or to 7.25 mM, or to 7.30 mM, or to 7.35 mM, or to 7.40 mM, or to 7.45 mM, or to 7.50 mM, or to 7.55 mM, or to 7.60 mM, or to 7.65 mM, or to 7.70 mM, or to 7.75 mM, or to 7.80 mM, or to 7.85 mM, or to 7.90 mM, or to 7.95 mM; or a range formed by any two of the foregoing molar concentrations; including any subranges therebetween. Examples of organic solvents in biocidal compositions and biocidal additive formulations can include acetonitrile and ethyl acetate.

[0180] In an example, the present disclosure provides 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-assist additive different from the carrier; wherein the copper-assist 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 after storage of the biocidal composition or film thereof at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), as measured by the EPA test.

[0181] In certain examples, the phosphite can be a compound of Formula (I):

[0182] ;

[0183] wherein each R 1 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups are optionally substituted with fluorine.

[0184] In certain examples, the phosphine can be a compound of Formula (II):

[0185] ;

[0186] wherein each R 2 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups are optionally substituted with fluorine.

[0187] In certain examples, the carrier can comprise a polyurethane, a polyurethane precursor, or a combination thereof.

[0188] In certain examples, the carrier can comprise an epoxy resin, an epoxy resin precursor, or a combination thereof.

[0189] In certain examples, the carrier can comprise an organic solvent.

[0190] In certain examples, the copper (I) salt can be a copper (I) halide, copper (I) iodide (triethyl phosphite), or a tetrakis(acetonitrile) copper (I) salt.

[0191] In certain examples, the copper (I) salt can be copper (I) bromide or copper (I) iodide.

[0192] In certain examples, each R 1 may be independently selected from the group consisting of C2-C 13alkyl, C1-C8alkyl, C1-C6alkyl, C2-C5alkyl, C2-C4alkyl, or phenyl.

[0193] In certain examples, each R 2 may be independently selected from C2-C 13 alkyl, C1-C8alkyl, C1-C6alkyl, C2-C5alkyl, or C2-C4alkyl.

[0194] In certain examples, the copper co-additive can be triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.

[0195] In certain examples, the molar ratio of the copper co-additive to the copper (I) salt can be at least 0.5: 1.

[0196] In certain examples, the biocidal composition can further comprise a compound of Formula (III), a compound of Formula (IV), a compound of Formula (V), or any combination thereof:

[0197] ;

[0198] ;

[0199] ;

[0200] wherein each R 3 may be independently selected from hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 may be independently selected from hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 may be independently selected from hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.

[0201] In certain examples, each R 3 may be independently selected from C1-C 13 alkyl, C1-C8alkyl, C1-C6alkyl, C2-C5alkyl, or C2-C4alkyl.

[0202] In certain examples, the biocidal composition can further comprise 2- ethylhexyl phosphate.

[0203] In certain examples, each R 4 may be independently selected from C1-C13 alkyl, Ci-C8alkyl, Ci-C6alkyl, C2-C5alkyl, or C2-C4alkyl.

[0204] In certain examples, the biocidal composition can further comprise tributyl borate.

[0205] In certain examples, each R 5 may be independently selected from Ci-C 13 alkyl, Ci-C8alkyl, Ci-C6alkyl, C2-C5alkyl, or C2-C4alkyl.

[0206] In certain examples, the biocidal composition can further comprise tributyl citrate.

[0207] In certain examples, the biocidal composition can exhibit a delta E of less than 6, as calculated according to:

[0208] ; and

[0209] where L * , a * , and b * are the CIE values of the biocidal composition after the biocidal composition is prepared and then stored at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L * 对照 , a * 对照 , and b * 对照 are the CIE values of an otherwise identical composition that does not contain the copper (I) salt or the copper-assisted additive.

[0210] In certain examples, the biocidal composition or the film thereof can exhibit a transmittance of at least 98% when measured at a thickness of 40 pm, as measured at each wavelength from 400 nanometers to 700 nanometers.

[0211] In certain examples, the transmittance can be within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assisted additive, when measured at a thickness of 40 pm.

[0212] In certain examples, a method of making the biocidal composition can comprise: adding a biocidal additive formulation to a carrier; wherein when the carrier is a polyurethane or an epoxy resin, the biocidal additive formulation can comprise the copper(I) salt and the copper-assist additive; wherein when the carrier is a second polyurethane precursor, the biocidal additive formulation can comprise a first polyurethane precursor, the copper(I) salt, and the copper-assist additive; and wherein when the carrier is a second epoxy resin precursor, the biocidal additive formulation can comprise a first epoxy resin precursor, the copper(I) salt, and the copper-assist additive.

[0213] In an example, a biocidal additive formulation, the biocidal additive formulation comprising: a copper(I) salt; and a copper-assist additive; wherein a biocidal composition or a film of the biocidal composition comprising the biocidal additive formulation and a carrier exhibits an antimicrobial efficacy of at least 3 log kill after the biocidal composition or the film of the biocidal composition is stored at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), as measured by the EPA test; 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 delta E of less than 6, as calculated according to:

[0214] ; and

[0215] wherein L * , a * , and b * are the CIE values of the biocidal composition after the biocidal composition is made and then stored at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L * 对照 , a * 对照 , and b * 对照 are the CIE values of an otherwise identical composition without the copper(I) salt or the copper-assist additive.

[0216] In certain examples, a biocidal additive formulation can comprise an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof.

[0217] In certain examples, the copper(I) salt can be a copper(I) halide, copper(I) iodite, or a copper(I) tetra(acetonitrile) salt.

[0218] In certain examples, the copper(I) salt can be copper(I) bromide or copper(I) iodide.

[0219] In certain examples, the copper-assisting additive can include a phosphite, a phosphine, or a combination thereof.

[0220] In certain examples, the phosphite can be a compound of Formula (I):

[0221] ;

[0222] wherein each R 1 may be independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups are optionally substituted with fluorine, provided that all R 1 are not simultaneously hydrogen.

[0223] In certain examples, the phosphine can be a compound of Formula (II):

[0224] ;

[0225] wherein each R 2 may be independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups are optionally substituted with fluorine, provided that all R 2 are not simultaneously hydrogen.

[0226] In certain examples, each R 1 may be independently selected from the group consisting of C2-C 13 alkyl, C1-C8 alkyl, C1-C6 alkyl, C2-C5 alkyl, or C2-C4 alkyl, or phenyl.

[0227] In certain examples, each R 2 may be independently selected from the group consisting of C2-C 13 alkyl, C1-C8 alkyl, C1-C6 alkyl, C2-C5 alkyl, or C2-C4 alkyl.

[0228] In certain examples, the copper-assisting additive can be triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.

[0229] In certain examples, the molar ratio of the copper-assisting additive to the copper (I) salt can be at least 0.5: 1.

[0230] In certain examples, the biocidal additive formulation can further include a compound of Formula (III), a compound of Formula (IV), a compound of Formula (V), or any combination thereof:

[0231] ;

[0232] ;

[0233] ;

[0234] wherein each R 3 may be independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 may be independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 may be independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.

[0235] In certain examples, each R 3 may be independently selected from the group consisting of C1-C 13 alkyl, C1-C8 alkyl, C1-C6 alkyl, C2-C5 alkyl, or C2-C4 alkyl.

[0236] In certain examples, the biocidal additive formulation can further comprise 2- ethylhexyl phosphate.

[0237] In certain examples, each R 4 may be independently selected from the group consisting of C1-C 13 alkyl, C1-C8 alkyl, C1-C6 alkyl, C2-C5 alkyl, or C2-C4 alkyl.

[0238] In certain examples, the biocidal additive formulation can further comprise tributyl borate.

[0239] In certain examples, each R 5 may be independently selected from the group consisting of C1-C 13 alkyl, C1-C8 alkyl, C1-C6 alkyl, C2-C5 alkyl, or C2-C4 alkyl.

[0240] In certain examples, the biocidal additive formulation can further comprise tributyl citrate.

[0241] In certain examples, the biocidal composition or the film thereof can exhibit a transmittance of at least 98% as measured at each wavelength from 400 nanometers to 700 nanometers when measured at a thickness of 40 µm.

[0242] In certain examples, the transmittance can be within 10 percent points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assisting additive, when measured at a thickness of 40 pm.

[0243] In certain examples, the biocidal additive formulation can further comprise an antioxidant.

[0244] In certain examples, the biocidal additive formulation can further comprise a reducing agent.

[0245] In certain examples, the formulation can be in a sealed container comprising an inert atmosphere.

[0246] While the disclosure has been described with reference to examples and drawings and tables, the disclosure is not limited thereto, but can be modified and changed by those skilled in the art to which the disclosure pertains without departing from the spirit and scope of the disclosure.

[0247] Various aspects are contemplated herein, with several aspects set forth in the following paragraphs. Any aspect or portion thereof can be combined as expressly contemplated. In certain examples, the biocidal composition can further comprise an antioxidant.

[0248] A first aspect is directed 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 after storage of the biocidal composition or film thereof at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), as measured by the EPA test.

[0249] A second aspect is directed to the biocidal composition of aspect 1 or any of the preceding aspects, wherein the phosphite is a compound of formula (I):

[0250] ;

[0251] wherein each R 1 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups are optionally substituted with fluorine.

[0252] A third aspect is directed to the biocidal composition of any of the preceding aspects, wherein the phosphine is a compound of formula (II):

[0253] ;

[0254] wherein each R 2 is independently selected from C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with hydroxyl.

[0255] A fourth aspect relates to the biocidal composition of any of the preceding aspects, wherein the carrier comprises a polyurethane, a polyurethane precursor, or a combination thereof.

[0256] A fifth aspect relates to the biocidal composition of aspects 1-3 or any of the preceding aspects, wherein the carrier comprises an epoxy resin, an epoxy resin precursor, or a combination thereof.

[0257] A sixth aspect relates to the biocidal composition of any of the preceding aspects, wherein the carrier comprises an organic solvent.

[0258] A seventh aspect relates to the biocidal composition of any of the preceding aspects, wherein the copper(I) salt is a copper(I) halide, copper(I) iodite, or a copper(I) tetra(acetonitrile) salt.

[0259] An eighth aspect relates to the biocidal composition of any of the preceding aspects, wherein the copper(I) salt is copper(I) bromide or copper(I) iodide.

[0260] A ninth aspect relates to the biocidal composition of aspects 2-8 or any of the preceding aspects, wherein each R 1 is independently selected from C2-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, C2-C4 alkyl) or phenyl.

[0261] A tenth aspect relates to the biocidal composition of aspects 3-9 or any of the preceding aspects, wherein each R 2 is independently selected from C2-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0262] An eleventh aspect relates to the biocidal composition of any of the preceding aspects, wherein the copper co-additive is triethyl phosphite, triphenyl phosphite, tributyl phosphine, or any combination thereof.

[0263] A twelfth aspect relates to the biocidal composition of any of the preceding aspects, wherein the molar ratio of the copper co-additive to the copper(I) salt is at least 0.5:1.

[0264] A thirteenth aspect is directed to the biocidal composition of any of the preceding aspects, further comprising a compound of Formula (III), a compound of Formula (IV), a compound of Formula (V), or any combination thereof:

[0265] ;

[0266] ;

[0267] ;

[0268] wherein each R 3 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.

[0269] A fourteenth aspect is directed to the biocidal composition of aspect 13 or any of the preceding aspects, wherein each R 3 is independently selected from the group consisting of C1-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0270] A fifteenth aspect is directed to the biocidal composition of any of the preceding aspects, further comprising 2-ethylhexyl phosphoric acid ester.

[0271] A sixteenth aspect is directed to the biocidal composition of aspect 13 or any of the preceding aspects, wherein each R 4 is independently selected from the group consisting of C1-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0272] A seventeenth aspect is directed to the biocidal composition of any of the preceding aspects, further comprising tributyl borate.

[0273] An eighteenth aspect is directed to the biocidal composition of aspect 13 or any of the preceding aspects, wherein each R 5 is independently selected from the group consisting of C1-C 13alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0274] The nineteenth aspect relates to the biocidal composition of any of the preceding aspects, further comprising tributyl citrate.

[0275] The twentieth aspect relates to the biocidal composition of any of the preceding aspects, wherein the biocidal composition exhibits a Delta E of less than 6, as calculated according to:

[0276] ; and

[0277] where L * , a * , and b * are the CIE values of the biocidal composition after the biocidal composition is prepared and then stored at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), and L * 对照 , a * 对照 , and b * 对照 are the CIE values of an otherwise identical composition that does not contain the copper (I) salt or the copper-assisting additive.

[0278] The twenty-first aspect relates to the biocidal composition of any of the preceding aspects, wherein the biocidal composition or the film thereof exhibits a transmittance of at least 98% as measured at each wavelength from 400 nanometers to 700 nanometers when measured at a thickness of 40 µm.

[0279] The twenty-second aspect relates to the biocidal composition of aspect 21 or any of the preceding aspects, wherein the transmittance is within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assisting additive when measured at a thickness of 40 µm.

[0280] The twenty-third aspect relates to a method of making the biocidal composition of any of the preceding aspects, the method 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.

[0281] A twenty-fourth aspect is directed to a biocidal additive formulation comprising: a copper(I) salt; and a copper-assisted additive; wherein the biocidal composition or a film of the biocidal composition comprising the biocidal additive formulation and a carrier exhibits an antimicrobial efficacy of at least 3 log kill after storage of the biocidal composition or the film of 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); 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 delta E of less than 6, as calculated according to:

[0282] ; and

[0283] wherein L * , a * , and b * are the CIE values of the biocidal composition after preparation of the biocidal composition and then storage of 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 * 对照 , a * 对照 , and b * 对照 are the CIE values of an otherwise identical composition without the copper(I) salt or the copper-assisted additive.

[0284] A twenty-fifth aspect is directed to the biocidal additive formulation according to aspect 24 or any of the preceding aspects, further comprising an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof.

[0285] A twenty-sixth aspect is directed to the biocidal additive formulation according to aspect 24 or 25 or any of the preceding aspects, wherein the copper(I) salt is a copper(I) halide, copper(I) iodite (triethyl phosphite), or a copper(I) tetrakis(acetonitrile) salt.

[0286] A twenty-seventh aspect is directed to the biocidal additive formulation according to aspect 24 to 26 or any of the preceding aspects, wherein the copper(I) salt is copper(I) bromide or copper(I) iodide.

[0287] A twenty-eighth aspect is directed to the biocidal additive formulation according to aspect 24 to 27 or any of the preceding aspects, wherein the copper-assisted additive comprises a phosphite, a phosphine, or a combination thereof.

[0288] A twenty-ninth aspect relates to the biocidal additive formulation of aspect 28, or any of the preceding aspects, wherein the phosphite is a compound of formula (I):

[0289] ;

[0290] wherein each R 1 is independently selected from C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with fluorine.

[0291] A thirtieth aspect relates to the biocidal additive formulation of aspect 28, or any of the preceding aspects, wherein the phosphine is a compound of formula (II):

[0292] ;

[0293] wherein each R 2 is independently selected from C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with hydroxyl.

[0294] A thirty-first aspect relates to the biocidal additive formulation of aspect 29, or any of the preceding aspects, wherein each R 1 is independently selected from C2-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0295] A thirty-second aspect relates to the biocidal additive formulation of aspect 30, or any of the preceding aspects, wherein each R 2 is independently selected from C2-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0296] A thirty-third aspect relates to the biocidal additive formulation of any of aspects 24-32, or any of the preceding aspects, wherein the copper-assist additive is triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.

[0297] A thirty-fourth aspect relates to the biocidal additive formulation of any of aspects 24-33, or any of the preceding aspects, wherein the molar ratio of the copper-assist additive to the copper(I) salt is at least 0.5: 1.

[0298] A thirty-fifth aspect relates to the biocidal additive formulation of any of aspects 24-34, or any of the preceding aspects, further comprising a compound of formula (III), a compound of formula (IV), a compound of formula (V), or any combination thereof:

[0299] ;

[0300] ;

[0301] ;

[0302] wherein each R 3 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.

[0303] A thirty-sixth aspect relates to the biocidal additive formulation of aspect 35, or any of the preceding aspects, wherein each R 3 is independently selected from the group consisting of C1-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0304] A thirty-seventh aspect relates to the biocidal additive formulation of aspects 24-34, or any of the preceding aspects, further comprising 2-ethylhexyl phosphonate.

[0305] A thirty-eighth aspect relates to the biocidal additive formulation of aspect 35, or any of the preceding aspects, wherein each R 4 is independently selected from the group consisting of C1-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0306] A thirty-ninth aspect relates to the biocidal additive formulation of aspects 24-34, or any of the preceding aspects, further comprising tributyl borate.

[0307] A fortieth aspect relates to the biocidal additive formulation of aspect 35, or any of the preceding aspects, wherein each R 5 is independently selected from the group consisting of C1-C 13 alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl).

[0308] A forty-first aspect relates to the biocidal additive formulation of aspects 24-34 or any of the preceding aspects, further comprising tributyl citrate.

[0309] A forty-second aspect relates to the biocidal additive formulation of aspects 24-41 or any of the preceding aspects, wherein the biocidal composition or the film thereof exhibits a transmittance of at least 98% as measured at each wavelength from 400 nanometers to 700 nanometers when measured at a thickness of 40 pm.

[0310] A forty-third aspect relates to the biocidal additive formulation of aspect 42 or any of the preceding aspects, wherein the transmittance is within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assisted additive when measured at a thickness of 40 pm.

[0311] A forty-fourth aspect relates to the biocidal additive formulation of aspects 24-43 or any of the preceding aspects, further comprising an antioxidant package.

[0312] A forty-fifth aspect relates to the biocidal additive formulation of aspects 24-43 or any of the preceding aspects, further comprising a reducing agent.

[0313] A forty-sixth aspect relates to the biocidal additive formulation of aspects 24-45 or any of the preceding aspects, wherein the formulation is in a sealed container comprising an inert atmosphere.

[0314] A forty-seventh aspect relates to a combination of any two or more of the preceding aspects, or any portion thereof.

[0315] The compositions and methods described above can be better understood in connection with the following examples, which are provided as non-limiting examples of the concepts disclosed herein. The procedures described as general methods describe methods believed to be generally effective for preparing the compositions. However, one skilled in the art will appreciate that it can be necessary to alter the procedures of any given example of the disclosure, for example, altering the order or steps and / or chemical reagents used.

[0316] Example

[0317] Comparison of complexes with copper (I) salts with mixtures comprising copper containing glass ("CCG").

[0318] In the examples herein, complexes having copper(I) salts can be compared to mixtures comprising copper-containing materials comprising a plurality of copper-containing glass or glass-ceramic particles. As used herein, the term "copper-containing glass" is intended to include "copper-containing glass-ceramic" unless the context clearly dictates otherwise. In this regard, the "ceramic" portion of the copper-containing glass-ceramic can in some aspects comprise chalcocite crystals.

[0319] In certain examples, the copper-containing material can comprise copper-containing glass or copper-containing glass-ceramic particles. The copper-containing glass or glass-ceramic particles can be biocidal inorganic glass or glass-ceramic powders comprising copper particles. While individual particles of copper-containing glass particles can be effective for use as biocides, such copper-containing glasses can have potential drawbacks related to the color and stability of copper(I) of the resulting compositions.

[0320] The copper-containing glass or glass-ceramic particles can independently comprise Cu metal, Cu 1+ , Cu 2+ , or a combination of Cu 1+ and Cu 2+ . The total amount of the combination of Cu species can be 10 wt% 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 can be substantially free of Cu 2+ . The copper can be uncomplexed or can have ligands bonded thereto to form a complex. The Cu 1+ ions can be present on or in the surface and / or bulk of the copper-containing glass or glass-ceramic particles. The copper-containing glass or glass-ceramic particles can comprise copper-containing glass or glass-ceramic, copper metal, copper(I) oxide, copper(II) oxide, or a combination thereof. In certain examples, the copper-containing glass or glass-ceramic particles can comprise only one of copper-containing glass or glass-ceramic, copper metal, copper(I) oxide, or copper(II) oxide. In certain examples, the Cu 1+ ions can be present in the glass or glass-ceramic network and / or glass or glass-ceramic matrix of the copper-containing glass or glass-ceramic particles. When the Cu 1+ ions are present in the glass or glass-ceramic network, the Cu 1+ ions and are atomically bonded to the atoms in the glass or glass-ceramic mixture. When the Cu 1+ ions are present in the glass or glass-ceramic matrix, the Cu 1+ ions can be present in the form of Cu 1+ crystals dispersed in the glass or glass-ceramic matrix. In certain examples, the Cu 1+ crystals can comprise chalcocite (Cu20). In the presence of Cu 1+In certain examples of the crystals, the material can be referred to as a glass-ceramic or ceramic, which is intended to refer to a particular type of glass or glass-ceramic having crystals that can or can not be subjected to a traditional ceramming process by which one or more crystalline phases are introduced and / or created in the glass or glass-ceramic. When Cu 1+ ions exist in a non-crystalline form, the material can be referred to as a copper-containing glass. In certain examples, Cu 1+ crystals and Cu 1+ ions not associated with the crystals can both be present in the copper-containing glass or glass-ceramic described herein.

[0321] The copper-containing glass or glass-ceramic can include copper-containing oxide in an amount in the range of 10 to 50, 10 to 49, 10 to 48, 10 to 47, 10 to 46, 10 to 45, 10 to 44, 10 to 43, 10 to 42, 10 to 41, 10 to 40, 10 to 39, 10 to 38, 10 to 37, 10 to 36, 10 to 35, 10 to 34, 10 to 33, 10 to 32, 10 to 31, 10 to 30, 10 to 29, 10 to 28, 10 to 27, 10 to 26, 10 to 25, 10 to 24, 10 to 23, 10 to 22, 10 to 21, 10 to 20, 11 to 50, 12 to 50, 13 to 50, 14 to 50, 15 to 50, 16 to 50, 17 to 50, 18 to 50, 19 to 50, 20 to 50, 10 to 30, 11 to 29, 12 to 28, 13 to 27, 14 to 26, 15 to 25, 16 to 24, 17 to 23, 18 to 22, 19 to 21; or a range formed by any two of the foregoing mole %; and all sub-ranges therebetween. The copper-containing oxide can be present in the copper-containing glass or glass-ceramic in an amount of 20 mole %, 25 mole %, 30 mole %, or 35 mole %. The copper-containing oxide can include CuO, Cu2O, and / or combinations thereof. The copper-containing glass or glass-ceramic particles can include cuprous oxide in an amount of 29.0 wt % to 36.0 wt % of the copper-containing glass or glass-ceramic particles. The copper-containing oxide in the copper-containing glass or glass-ceramic forms Cu 1+ ions present in the resulting glass or glass-ceramic. Copper can exist in the glass or glass-ceramic or composition thereof in various forms, including Cu 0 , Cu 1+ , and Cu 2+ .

[0322] The copper-containing glass or glass-ceramic portion of the individual particles of the copper-containing glass or glass-ceramic particles can be formed from a glass composition that can include, but is not limited to, in mol%: Si02 in a range from 30 to 70, AI2O3 in a range from 0 to 20, copper-containing oxide in a range from 10 to 50, CaO in a range from 0 to 15, MgO in a range from 0 to 15, P2O5 in a range from 0 to 25, B2O3 in a range from 0 to 25, K2O in a range from 0 to 20, ZnO in a range from 0 to 5, Na20 in a range from 0 to 20, and / or Fe203 in a range from 0 to 5, nanoparticles thereof, and / or mixtures thereof. In such examples, the amount of copper-containing oxide is greater than the amount of AI2O3. In certain examples, the glass composition can include a content of R2O, where R can include K, Na, Li, Rb, Cs, and combinations thereof.

[0323] In certain examples, the glass composition can include one or more divalent cation oxides, such as alkaline earth metal oxides and / or ZnO. In certain examples, the glass composition can include NiO, Ti02, Fe203, Cr203, or Co304 in an amount in a range up to 10 mol% or 0.01 mol% to 10 mol%, 1 mol% to 10 mol%, 2 mol% to 10 mol%, 5 mol% to 10 mol%, 0.01 mol% to 0.8 mol%, or 0.01 mol% to 5 mol%.

[0324] The copper-containing glass or glass-ceramic formed from the glass composition can 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 dispersed in the glass matrix are Cu 1+ crystals. The Cu 1+ may exist in the form of cuprite. The cuprite present in the copper-containing glass-ceramic can form a phase distinct from the glass matrix or glass phase. In other examples, the cuprite can form part of one or more glass phases, or can be associated with one or more glass phases.

[0325] The copper-containing glass can be produced by any suitable method. For example, the copper-containing glass can be carried out using a melting tank typically used for melting glass compositions such as soda-lime silicate. In certain examples, the copper-containing glass can be shaped into a sheet using a shaping process known in the art. The shaping method can include a float glass process and a down-draw process such as fusion draw and slot draw. After shaping, the copper-containing glass can be shaped into a sheet and can be formed, polished, or otherwise processed to achieve a desired end use. In certain examples, the copper-containing glass can be ground into a powder or particulate form. In certain examples, the particulate copper-containing glass can be combined with other materials or carriers.

[0326] The EPA test was used to test the antimicrobial efficacy of all examples herein.

[0327] Example 1

[0328] The following example illustrates the determination of baseline antimicrobial efficacy of a two-component polyurethane with a copper source (copper (I) salt).

[0329] The antimicrobial efficacy resulting from the addition of a copper source in a two-component polyurethane was negligible with or without the addition of 2-ethylhexyl phosphate (“EHP”). Thin samples as well as down-draws of thick samples were prepared with the ingredient amounts provided in Table 1 below to ensure that there was sufficient copper in the bulk to have sufficient antimicrobial efficacy. Copper-containing glass was used with copper (I) tetra(acetonitrile) together as a comparator, but neither achieved close to 3-log kill as Figure 1 shown.

[0330] A commercially available two-component polyurethane (Eastwood® 4:1 High Solids Urethane Premium Show Clear) was used according to the manufacturer’s instructions using a 4:1 weight:weight ratio of Component A and Component B. Component A and Component B were first mixed together and allowed to sit for 45 minutes before adding the copper source and copper-assisted additives. The copper (I) salt and copper-containing glass were first prepared, during which the copper source was dissolved or dispersed in acetonitrile (“ACN”) (with EHP if used), allowed to sit for 1 hour before adding triethyl phosphite (“TEP”), and the mixture was added to the polyurethane mixture. The resulting material was mixed thoroughly and a film was cast on a PVC sheet and allowed to cure for 24 hours. Antimicrobial testing was performed on 1” x 1” cuts of the resulting film.

[0331] Table 1

[0332]

[0333] An equivalent procedure was performed using an epoxy resin, except that the ratio of epoxy Component A to epoxy Component B was 1:1.

[0334] In subsequent experiments, the procedure for two-part polyurethanes and two-part epoxy resins was as follows: the solvent and copper-assisted additives were mixed together to form a homogeneous solution and added to the 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 adding 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 sit under exposure to air and occasional stirring to allow the polyurethane mixture to begin reacting. If necessary, after the solids were filtered, the copper species and additive mixture was added to the polyurethane mixture and the entire mixture was then stirred until homogeneous. The mixture was applied to a substrate using conventional coating techniques including spraying, spin coating, dip coating, and curtain coating. In the case of curtain coating, a syringe was used to apply the doped two-part polyurethane solution to the front of the curtain coater and the film was drawn down on the substrate with a target wet film thickness between 2 and 10 mils. The film was then allowed to cure under ambient conditions or elevated temperature according to the product specification. Additional coatings could be applied if necessary.

[0335] Example 2

[0336] The following examples illustrate experiments to determine the antimicrobial efficacy of copper(I) salts and copper-assisted additives in commercial two-part polyurethanes and two-part epoxy resins prepared according to the procedure of Example 1.

[0337] Additional copper-assisted additives (TEP) were used in combination with EHP in an attempt to prevent the copper extracted by EHP from oxidizing. However, in both two-part polyurethanes according to the amounts of Table 2 and two-part epoxy resins according to the amounts of Table 3, as shown in Tables 4 and 5, respectively, the copper-containing glass achieved at least 3 log kill antimicrobial efficacy. The antimicrobial efficacy was lower when using copper(I) salts as the copper source, with log kill of about 1-2. The same stoichiometry of the same additives in the same order of addition were used for both the CCG samples and the copper(I) salt samples. Figure 2 and 3 The copper-containing glass achieved at least 3 log kill antimicrobial efficacy. The antimicrobial efficacy was lower when using copper(I) salts as the copper source, with log kill of about 1-2. The same stoichiometry of the same additives in the same order of addition were used for both the CCG samples and the copper(I) salt samples.

[0338] Table 2

[0339]

[0340] Note: 5% CCG means 5 wt% CCG in solution, 0.45% Cu(ACN)4 means 0.45 wt% copper in solution (5% CCG is equivalent to about 0.45% available copper).

[0341] Table 3

[0342]

[0343]

[0344] Example 3

[0345] The following example illustrates experiments to demonstrate the antimicrobial efficacy of copper(I)-additive complexes in a two-component polyurethane prepared according to the procedure of Example 1, where copper(I) iodide (triethylphosphite) ("CuI (TEP)") is the copper(I) salt.

[0346] CuI (TEP) resulted in complete kill whether or not EHP was added. While EHP does not appear to have an impact on antimicrobial efficacy, the addition of EHP according to the amounts in Table 4 below advantageously provides a more neutral color tone in the resulting film. Further addition of TEP surprisingly and unexpectedly results in a decrease in antimicrobial activity for at least 90 days, as Figure 4 shown, indicating that there is a narrow range of stoichiometry of TEP to Cu(I) that is antimicrobially effective, and that excess TEP (molar ratio of TEP to Cu(I) greater than 2: 1) results in a significant decrease in antimicrobial efficacy.

[0347] Table 4

[0348]

[0349] "0.45%" means 0.45 wt% copper in solution.

[0350] Example 4

[0351] The following example illustrates experiments to determine the antimicrobial efficacy of copper(I)-additive complexes in an epoxy resin prepared according to the procedure of Example 1, where copper(I) iodide (triethylphosphite) is the copper(I) salt.

[0352] The use of copper(I) iodide (triethylphosphite) complex did not result in complete kill in the epoxy resin, and did not change the antimicrobial efficacy on the base epoxy resin, as Figure 5 and 6 shown. The addition of TEP to copper(I) tetra(acetonitrile) (3: 1 molar ratio) or copper(I) iodide (3: 1 molar ratio) illustrates that, for epoxy resins, more TEP is needed to obtain antimicrobial efficacy compared to polyurethanes. The addition of more TEP (0.5: 1 to 9: 1 molar relative to copper(I) according to Table 5) does result in higher antimicrobial efficacy with higher amounts of TEP. While TEP can be a strong copper-assisted additive, there are more amine groups in epoxy resins relative to the binding group in TEP.

[0353] Table 5

[0354]

[0355] Even strong binding ligands such as TEP cannot outcompete the amines present in the epoxy resin in reasonable amounts, so it is of interest to reduce the effectiveness of the amines as ligands to allow the TEP to bind to the copper (I). The use of monobasic potassium dihydrogen phosphate in the amounts according to Table 6 below is only partially effective because the salt form is less soluble in the epoxy resin. The acid form of the soluble glass component (phosphoric acid or boric acid) can catalyze the epoxy ring opening and the protonation of the amines can limit the effectiveness of the amine ligands, but the epoxy reaction is not negatively affected.

[0356] Table 6

[0357]

[0358] Example 5

[0359] The following example demonstrates the antimicrobial effectiveness of the copper-ligand complex produced in situ in the two-component polyurethane coating prepared according to the procedure of Example 1.

[0360] Iodine- or bromo(triethyl phosphite) copper (I) complexes can be produced in situ without the need to first synthesize the complex. In acetonitrile, copper (I) bromide can be completely dissolved by the addition of three molar equivalents of EHP in addition to one equivalent of TEP, resulting in the amounts of antimicrobial effectiveness (complete kill) according to Table 7 below, as shown. Figure 7 Without the addition of TEP, copper (I) bromide does not dissolve in solution, resulting in no antimicrobial effectiveness being produced. The solution of copper (I) salt and copper adjunct is pre-filtered before being added to the two-component polyurethane because particulates in the coating would result in a non-level coating. Incorporation of undissolved copper (I) salt can eventually produce antimicrobial effectiveness.

[0361] Table 7

[0362]

[0363] "0.45%" refers to 0.45 wt% copper in the solution, and the values of EHP and TEP refer to molar equivalents relative to the amount of copper in the solution.

[0364] In situ formation using ethyl acetate instead of acetonitrile as the solvent was also demonstrated. Copper (I) bromide and TEP were added together to ethyl acetate and stirred for 2 hours in the amounts according to Table 8 below, then EHP was added to the mixture and stirred for an additional hour before being added to the mixture of components A and B of the polyurethane. The mixture produced essentially no effectiveness. Doubling the amount of solvent increased the solubility, and the effectiveness increased to about 4 log kill, as shown. Figure 8The amount of EHP was doubled to further increase the efficacy of complete kill. Even adding EHP at the beginning of the procedure to make the mixture rather than after 2 hours slightly enhanced the antimicrobial efficacy (log 2 rather than 0.5). Adding sodium phosphate dibasic (“SPDB”) or iodine (“I2”) did not improve solubility or antimicrobial efficacy.

[0365] Table 8

[0366]

[0367]

[0368] “0.45%” refers to 0.45 wt% copper in solution, and the “equiv” values for EtOAc, EHP, TEP, I2, and SPDB are molar equivalents relative to the amount of copper in solution.

[0369] EHP can replace another solubilizing agent according to the amounts in Table 9 below, such as tributyl citrate (“TBC”) or tributyl borate (“TBB”), both of which have been shown to produce higher antimicrobial efficacy (complete kill for tributyl citrate, > 4 log kill for tributyl borate), as shown in Table 10 below. Figure 9

[0370] Table 9

[0371]

[0372]

[0373] “0.45%” refers to 0.45 wt% copper in solution, and the “equiv” values for ACN, TEP, TBC, and TBB are molar equivalents relative to the amount of copper in solution.

[0374] Tributylphosphine (“TBP”) was also shown to be effective as a copper co-additive in a two-component polyurethane with copper(I) bromide and EHP in the amounts provided in Table 10 below. TBP exhibited complete kill antimicrobial efficacy when TBP was slightly in excess relative to copper, but did not exhibit antimicrobial efficacy when TBP was in greater molar excess relative to copper, as shown in Table 11 below. Figure 10

[0375] Table 10

[0376]

[0377] “0.45%” refers to 0.45 wt% copper in solution, and the “equiv” values for ACN, EHP, and TBP are molar equivalents relative to the amount of copper in solution.

[0378] ​​Spin-coated coatings (approximately 40 µm) with and without copper (I) onto glass resulted in minimal color change and only slight transmission loss for the copper-doped glass, with the undoped polyurethane ("undoped") exhibiting a smaller ΔE value relative to the uncoated glass ("glass (control)"). * The value is 0.1, and the ΔE* of the copper-doped polyurethane coating is 0.6. The copper-doped polyurethane coating (“doped”) uses an exemplary composition of ACN + EHP (0.45%) containing iodine (TEP)Cu(I), comprising the amounts described in Table 4 above. It exhibits minimal transmission loss and low absorbance at approximately 350 nm, such as... Figure 11 As shown in Table 11 below, the CIE values ​​for glass, undoped polyurethane, and copper-doped polyurethane are provided.

[0379] Table 11

[0380]

[0381] It should be understood that various disclosed aspects or examples may relate to specific features, elements, or steps described in conjunction with a particular aspect or example. It should also be understood that although a particular aspect or example is described, specific features, elements, or steps may be interchanged or combined with alternative aspects or examples in various combinations or arrangements not shown.

[0382] While the transitional phrase "comprising" may be used to disclose various features, elements, or steps of a particular aspect or instance, it should be understood that implicit alternative aspects or instances include aspects or instances that may be described using the transitional phrases "comprising" or "substantially composed of." Thus, for example, an implicit alternative aspect or instance of a device comprising A+B+C includes aspects or instances where the device is composed of A+B+C and aspects or instances where the device is substantially composed of A+B+C.

[0383] It will be apparent to those skilled in the art that various modifications and variations can be made to this disclosure without departing from its spirit and scope. Since modifications, combinations, sub-combinations, and variations of the disclosed examples incorporating the spirit and substance of this disclosure will be readily apparent to those skilled in the art, this disclosure should be construed as encompassing all contents within the scope of the appended claims and their equivalents.

Claims

1. 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-assisted additive different from the carrier; wherein the copper-assisted 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 after the biocidal composition or the film thereof is stored at ambient temperature and ambient relative humidity for 90 days, as measured by EPA Test.

2. The biocidal composition of claim 1, wherein the phosphite is a compound of Formula (I): ； wherein each R 1 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with fluorine.

3. The biocidal composition of any one of the preceding claims, wherein the phosphine is a compound of Formula (II): ； wherein each R is independently selected from the group consisting of hydrogen, C1-C4alkyl, C1-C4alkoxy, and halogen; 2 independently selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, and halogen; 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with hydroxy.

4. The biocidal composition of any one of the preceding claims, wherein the carrier comprises a polyurethane, a polyurethane precursor, or a combination thereof.

5. The biocidal composition of claims 1-3, wherein the carrier comprises an epoxy resin, an epoxy resin precursor, or a combination thereof.

6. The biocidal composition of any one of the preceding claims, wherein the carrier comprises an organic solvent.

7. The biocidal composition of any one of the preceding claims, wherein the copper (I) salt is a copper (I) halide, copper (I) iodide (triethyl phosphite), or a copper (I) tetrakis(acetonitrile) salt.

8. The biocidal composition of any one of the preceding claims, wherein the copper (I) salt is copper (I) bromide or copper (I) iodide.

9. The biocidal composition of claims 2-8, wherein each R 1 is independently selected from C2-C 13 alkyl and phenyl.

10. The biocidal composition of claims 3-9, wherein each R 2 is independently selected from C2-C 13 alkyl.

11. The biocidal composition of any one of the preceding claims, wherein the copper-assisted additive is triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.

12. The biocidal composition of any one of the preceding claims, wherein the molar ratio of the copper-assisted additive to the copper (I) salt is at least 0.5:

1.

13. The biocidal composition of any one of the preceding claims, further comprising a compound of Formula (III), a compound of Formula (IV), a compound of Formula (V), or any combination thereof: ； ； ； wherein each R 3 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl and aryl(C1-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.

14. The biocidal composition of claim 13, wherein each R 3 is independently selected from C1-C 13 alkyl.

15. The biocidal composition of any one of the preceding claims, further comprising 2- ethylhexyl phosphonate.

16. The biocidal composition of claim 13, wherein each R 4 is independently selected from the group consisting of C1-C 13 alkyl.

17. The biocidal composition of any one of the preceding claims, further comprising tributyl borate.

18. The biocidal composition of claim 13, wherein each R 5 is independently selected from the group consisting of C1-C 13 alkyl.

19. The biocidal composition of any one of the preceding claims, further comprising tributyl citrate.

20. The biocidal composition of any one of the preceding claims, wherein the biocidal composition exhibits a delta E of less than 6, as calculated according to: ; and wherein L * , a * , and b * are the CIE values of the biocidal composition after the biocidal composition is prepared and then stored at ambient temperature and ambient relative humidity for 90 days, and L * 对照 , a * 对照 , and b * 对照 are the CIE values of the otherwise identical composition without the copper (I) salt or the copper-assisted additive.

21. The biocidal composition of any one of the preceding claims, wherein the biocidal composition or the film thereof exhibits a transmittance of at least 98% as measured at each wavelength from 400 nanometers to 700 nanometers when measured at a thickness of 40 pm.

22. The biocidal composition of claim 21, wherein the transmittance is within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assist additive when measured at a thickness of 40 pm.

23. A method of making the biocidal composition of any of the preceding claims, the method 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-assist 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-assist 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-assist additive.

24. A biocidal additive formulation, comprising: a copper (I) salt; and a copper-assist additive; wherein the biocidal composition or a film of the biocidal composition comprising the biocidal additive formulation and a carrier exhibits an antimicrobial efficacy of at least 3 log kill after the biocidal composition or the film of the biocidal composition is stored at ambient temperature and ambient relative humidity for 90 days as measured by the EPA test; 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 delta E of less than 6 as calculated according to: ; and wherein L * , a * , and b * are the CIE values of the biocidal composition after the biocidal composition is prepared and then stored at ambient temperature and ambient relative humidity for 90 days, and L * 对照 , a * 对照 , and b * 对照 are the CIE values of the otherwise identical composition without the copper (I) salt or the copper-assisted additive.

25. The biocidal additive formulation of claim 24, further comprising an organic solvent, a first polyurethane precursor, a first epoxy resin precursor, or any combination thereof.

26. The biocidal additive formulation of claim 24 or 25, wherein the copper (I) salt is a copper (I) halide, copper (I) iodite, or a copper (I) tetrakis(acetonitrile) salt.

27. The biocidal additive formulation of claims 24 to 26, wherein the copper (I) salt is copper (I) bromide or copper (I) iodide.

28. The biocidal additive formulation of claims 24 to 27, wherein the copper-assist additive comprises a phosphite, a phosphine, or a combination thereof.

29. The biocidal additive formulation of claim 28, wherein the phosphite is a compound of Formula (I): ； wherein each R 1 is independently selected from the group consisting of C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with fluorine.

30. The biocidal additive formulation of claim 28, wherein the phosphine is a compound of Formula (II): ； wherein each R is independently selected from the group consisting of hydrogen, C1-C4alkyl, C1-C4alkoxy, and halogen; 2 independently selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, and halogen; 20 alkyl, aryl, and aryl(C1-C4)alkyl, any of which groups is optionally substituted with hydroxy.

31. The biocidal additive formulation of claim 29, wherein each R 1 is independently selected from C2-C 13 alkyl and phenyl.

32. The biocidal additive formulation of claim 30, wherein each R 2 is independently selected from C2-C 13 alkyl.

33. The biocidal additive formulation of claims 24 to 32, wherein the copper-assist additive is triethyl phosphite, tributyl phosphine, triphenyl phosphite, or any combination thereof.

34. The biocidal additive formulation of claims 24 to 33, wherein a molar ratio of the copper-assist additive to the copper (I) salt is at least 0.5:

1.

35. The biocidal additive formulation of claims 24-34, further comprising a compound of Formula (III), a compound of Formula (IV), a compound of Formula (V), or any combination thereof: ； ； ； wherein each R 3 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl and aryl(C1-C4)alkyl, provided that all R 3 are not simultaneously hydrogen; wherein each R 4 is independently selected from hydrogen, C1-C 20 alkyl, aryl, and aryl(C1-C4)alkyl, provided that all R 4 are not simultaneously hydrogen; and wherein each R 5 is independently selected from the group consisting of hydrogen, C1-C 20 alkyl, aryl and aryl(C1-C4)alkyl, provided that all R 5 are not simultaneously hydrogen.

36. The biocidal additive formulation of claim 35, wherein each R 3 is independently selected from the group consisting of C1-C 13 alkyl.

37. The biocidal additive formulation of claims 24-34, further comprising 2- ethylhexyl phosphonate.

38. The biocidal additive formulation of claim 35, wherein each R 4 is independently selected from the group consisting of C1-C 13 alkyl.

39. The biocidal additive formulation of claims 24-34, further comprising tributyl borate.

40. The biocidal additive formulation of claim 35, wherein each R 5 is independently selected from the group consisting of C1-C 13 alkyl.

41. The biocidal additive formulation of claims 24-34, further comprising tributyl citrate.

42. The biocidal additive formulation of claims 24-41, 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.

43. The biocidal additive formulation of claim 42, wherein the transmittance is within 10 percentage points of a second transmittance of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper-assisted additive when measured at a thickness of 40 pm.

44. The biocidal additive formulation of claims 24-43, further comprising an antioxidant package.

45. The biocidal additive formulation of claims 24-43, further comprising a reducing agent.

46. The biocidal additive formulation of claims 24-45, wherein the formulation is in a sealed container comprising an inert atmosphere.

Images