Antimicrobial compositions comprising copper (i) salts and additives

Abstract

Biocidal compositions are provided comprising a carrier, a copper (I) salt, and a copper auxiliary additive different from the carrier, which biocidal compositions have improved antimicrobial efficacy and / or total chromatic aberration in some aspects. Also provided are biocidal compositions or UV curable films thereof that exhibit a high transmittance similar to that of an otherwise identical composition or film thereof that does not contain the copper (I) salt or the copper auxiliary additive. Also provided are biocidal additive formulations wherein the molar concentration of the copper (I) salt is at least 20 mM.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Patent Application No. 18 / 224,348, 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 a copper (I) salt and a copper auxiliary additive. Background Technology

[0004] The composition may be present in the form of an article, a layer, or a coating, or in the form of a liquid composition comprising suspensions and solutions. Liquid compositions may be applied to surfaces or stored in containers (e.g., prior to 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) may be a challenge.

[0005] Therefore, there is a need for copper-containing compositions that improve the availability of copper (such as copper(I)). Summary of the Invention

[0006] In one example, this disclosure provides a biocidal composition comprising a carrier; a copper (I) salt; and a copper auxiliary additive different from the carrier. The copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof.

[0007] ;

[0008] ;

[0009] ;

[0010] ;

[0011] Each R 1 Independently selected from hydrogen, C1-C 20 Alkyl, aryl and aryl (C1-C4) alkyl; wherein each R2 Independently selected from C1-C cells optionally substituted with fluorine. 20 Alkyl groups, and aryl groups (e.g., phenyl groups); wherein each R 3 Independently selected from C1-C cells optionally substituted with hydroxyl groups. 20 Alkyl; wherein each R 4 Independently selected from C1-C 20 Alkyl group; wherein X is an anti-counterionic group; and wherein after storing the biocidal composition or its film or article at ambient temperature and relative humidity for 50 days, the biocidal composition, its film or article exhibits an antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing.

[0012] In some instances, the copper (I) salt may be copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) tetrafluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof. In some instances, the copper auxiliary additive may be 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof. In some instances, the biocidal composition may be in the form of paint, coating, elastomer coating, caulking compound, sealant, floor polish, fabric treatment, dye, varnish, primer, UV-curable composition, UV-curable composition, or plastic. In some instances, the carrier may comprise acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof. In some instances, the copper(I) salt may be copper(I) bromide; the copper auxiliary additive may be trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after 60 days of storage may be at least 3 logarithmic. In some instances, the copper auxiliary additive may be triethyl phosphite; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after 150 days of storage may be at least 3 logarithmic. In some instances, the copper(I) salt may be tetra(acetonitrile)copper(I)hexafluorophosphate; the copper auxiliary additive may be 2-ethylhexyl phosphate; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after one year of storage may be at least 3 logarithmic. In some instances, the copper(I) salt may be copper(I) bromide, copper(I) iodide, or both; the copper auxiliary additive may be trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and the ΔE exhibited by the biocidal composition may be less than 6, as calculated according to the following:

[0013] ;and

[0014] L * a * and b *The CIE value of the biocidal composition can be determined after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It can be the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive. In some instances, each R 1 It can be selected from hydrogen, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl; each R 2 It may be selected from C1-C5 alkyl groups optionally substituted with fluorine; each R 3 It may be selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) optionally substituted with hydroxyl groups; and each R 4 It can be selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl).

[0015] In another example, this disclosure provides a biocidal composition comprising a carrier; a copper (II) salt; and a copper auxiliary additive different from the carrier; wherein, after the biocidal composition or its membrane has been stored at ambient temperature and relative humidity for 90 days, the biocidal composition or its membrane exhibits antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing; and wherein, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the biocidal composition or its membrane or article exhibits a transmittance of at least 98%.

[0016] In some instances, the film thickness of the biocidal composition can be from 30 µm to 1000 µm. In some instances, the copper auxiliary additive can be a compound of formula (II), a compound of formula (III), or any combination thereof:

[0017] ;

[0018] ;

[0019] Each R 2 It can be independently selected from C1-C5 alkyl groups optionally substituted with fluorine, and phenyl groups; and wherein each R 3The copper(I) salt can be independently selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups. In some examples, the copper(I) salt can be copper chloride(I), copper bromide(I), copper iodide(I), tetra(acetonitrile)copper(I) hexafluorophosphate, tetra(acetonitrile)copper(I) tetrafluoroborate, tetra(acetonitrile)copper(I) perchlorate, tetra(acetonitrile)copper(I) trifluoromethanesulfonate, tetra(acetonitrile)copper(I) hydrogen oxalate-oxalate-acetonitrile, copper acetate(I), or any combination thereof. In some examples, the copper auxiliary additive can be triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tris(3-hydroxypropyl)phosphine, or any combination thereof. In some instances, the copper(I) salt may be copper(I) bromide; and the copper auxiliary additive may be triethyl phosphite, trimethyl phosphite, tris(2,2,2-trifluoroethyl) phosphite, or any combination thereof. In some instances, the biocidal composition may exhibit a ΔE of less than 6, as calculated according to the following:

[0020] ;

[0021] L * a * and b * The CIE value of the biocidal composition can be determined after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 The CIE value can be that of a composition otherwise identical without the copper(I) salt or the copper auxiliary additive; and the antimicrobial efficacy exhibited by the biocidal composition or its membrane after 150 days of storage can be at least 3 logarithmic. In some instances, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the transmittance exhibited by the biocidal composition or its membrane can be within 10 percentage points of the second transmittance of a composition or its membrane otherwise identical without the copper(I) salt or the copper auxiliary additive.

[0022] In yet another example, this disclosure provides a biocidal composition comprising a carrier, a copper (I) salt, and a copper auxiliary additive different from the carrier. The copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof:

[0023] ;

[0024] ;

[0025] ;

[0026] ;

[0027] Each R 1 Independently selected from hydrogen, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl; wherein each R 2 Independently selected from C1-C5 alkyl (or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) and phenyl, optionally substituted with fluorine; wherein each R 3 Independently selected from C1-C6 alkyl groups (or C2-C5 alkyl groups, or C2-C4 alkyl groups, or C1-C4 alkyl groups) optionally substituted with hydroxyl groups; wherein each R 4 Independently selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl); wherein X is an anti-counterion; wherein the copper (I) salt is copper halide (I), tetra(acetonitrile) copper (I) salt or any combination thereof; and wherein after storing the biocidal composition or its film or article at ambient temperature and ambient relative humidity for 50 days (or any other time period disclosed herein), the biocidal composition, the film or article thereof exhibits antimicrobial efficacy of at least 3 logarithmic killing, as measured by EPA testing.

[0028] In some instances, the copper (I) salt may be copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof. In some instances, the copper auxiliary additive may be 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof. In some instances, the biocidal composition may be in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV-curable composition, UV-curable composition, or plastic. In some instances, the carrier may comprise acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof. In some instances, the copper(I) salt may be copper(I) bromide; the copper auxiliary additive may be trimethyl phosphite, triethyl phosphite, tris(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and the biocidal composition or its film or article exhibits at least 3 logarithmic antimicrobial efficacy after 60 days of storage.

[0029] In yet another example, this disclosure provides a biocidal additive formulation comprising a copper (I) salt and a copper auxiliary additive. After storing a biocidal composition comprising the biocidal additive formulation and a carrier, a film or article thereof comprising the biocidal composition, at ambient temperature and relative humidity for one year, the biocidal composition, the film thereof, or the article thereof exhibits an antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing. The biocidal composition exhibits a ΔE less than 6, as calculated according to the following:

[0030] ;and

[0031] L * a * and b * The CIE value of the biocidal composition is the value obtained after the biocidal composition has been prepared and then stored at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照It is the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

[0032] In some instances, the copper auxiliary additive may be a compound of formula (I), a compound of formula (II), a compound of formula (III), or any combination thereof:

[0033] ;

[0034] ;

[0035] ;

[0036] Each R 1 It can be independently selected from hydrogen, C1-C 20 Alkyl, aryl, and benzyl; wherein each R 2 It can be independently selected from C1-C cells that are optionally substituted with hydroxyl groups or fluorine groups. 20 Alkyl groups, and aryl groups (e.g., phenyl groups); and wherein each R 3 It can be independently selected from C1-C 20 Alkyl group. In some examples, the copper (I) salt may be copper (I) bromide, tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof. In some examples, the copper auxiliary additive may be 2-ethylhexyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof. In some examples, the molar concentration of the copper (I) salt dissolved in the biocidal additive formulation may be at least 20 mM. In some examples, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the transmittance of the membrane of the biocidal composition may be at least 98%.

[0037] Further applications will become apparent from the description provided herein. It should be understood that the description and specific examples are for illustrative purposes only and are not intended to limit the scope of this disclosure. Attached Figure Description

[0038] To facilitate a good understanding of this disclosure, various forms of the disclosure, given by way of example, will now be described with reference to the accompanying drawings. The components in the drawings are not necessarily to scale. Furthermore, throughout the drawings, the same reference numerals denote corresponding parts. The drawings described herein are for illustrative purposes only and are not intended to limit the scope of this disclosure in any way.

[0039] Figure 1 The diagram shows the antimicrobial efficacy of various paint samples at initial pull-down (0 days in can, 7 days dry) and (50 days in can, 7 days dry) and (0 days in can, 50 days dry), including control paint samples and various examples of biocidal compositions according to this disclosure.

[0040] Figure 2 A graph showing the antimicrobial efficacy of a UV-curable film prepared from an example of a biocidal composition comprising copper(I) bromide and triethyl phosphite according to the present disclosure;

[0041] Figure 3 The graphs show the antimicrobial efficacy of various examples of biocidal compositions according to this disclosure at initial application, after 150 days in a can, and after 150 days as a dry film, compared to control paint samples and compositions containing copper-containing glass.

[0042] Figure 4 A graph showing the antimicrobial efficacy of various examples of biocidal compositions comprising tetra(acetonitrile)copper(I) hexafluorophosphate and 2-ethylhexyl phosphate in different molar ratios, according to this disclosure, after storage at ambient temperature for 13 months;

[0043] Figure 5 A graph showing the antimicrobial efficacy of an example of a biocidal composition comprising PVC plastisol, tetra(acetonitrile)copper(I)hexafluorophosphate and 2-ethylhexyl phosphate according to this disclosure, both of which were initially prepared and stored at ambient temperature for 4 months.

[0044] Figure 6 A graph showing the antimicrobial efficacy of an example of a biocidal composition comprising PVC plastisol, tetra(acetonitrile)copper(I)hexafluorophosphate and 2-ethylhexyl phosphate according to this disclosure, as after storage at ambient temperature and after storage for 7 days under accelerated aging conditions at 65°C and 65% relative humidity.

[0045] Figure 7 The diagram shows the antimicrobial efficacy of various examples of biocidal compositions comprising copper bromide (I), various copper auxiliary additives, and acetonitrile / water as a solvent according to this disclosure, at concentrations of 0.264 g / L, 2.642 g / L, and 26.42 g / L in paints;

[0046] Figure 8 A graph showing the transmittance % of a UV-curable film containing a biocidal composition of copper bromide (I) and triethyl phosphite at each wavelength from 375 nm to 750 nm is shown, where the glass substrate to which the UV curability has been applied has been subtracted.

[0047] Figure 9The UV-Vis absorption spectrum of an example of a biocidal composition precursor solution is shown. The absorption spectrum provides an indication of the oxidation state of copper ions in the precursor solution.

[0048] Figure 10 The diagram illustrates the antimicrobial efficacy of UV-curable films prepared from examples of biocidal compositions comprising 0.2 wt% or 0.6 wt% copper bromide (I) in ethanol and 3 molar equivalents of triethyl phosphite at 7, 30, and 91 days; and

[0049] Figure 11 A graph showing the antimicrobial efficacy of a UV-curable film prepared from an example of a biocidal composition comprising 20% ​​by weight of iodine (triethyl phosphite) copper (I) in propylene glycol methyl ether acetate (PGMEA) according to the present disclosure and mixed with an example of a UV-curable film.

[0050] Figure 12 The graph shows the antimicrobial efficacy of latex paint dry films containing 0.1 wt.% or 0.2 wt.% CuBr-TPP complexes.

[0051] The accompanying drawings described herein are for illustrative purposes only and are not intended to limit the scope of this disclosure in any way. Detailed Implementation

[0052] The following description is exemplary in nature and is not intended to limit this disclosure, application, or use.

[0053] In describing the elements of this disclosure, the terms “first,” “second,” “first,” “second,” “A,” “B,” “(a),” “(b),” etc. are used herein. These terms are used only to distinguish one element from another, but do not limit the corresponding elements, regardless of their nature or order.

[0054] Numerical values ​​that include the endpoints of a range may be represented herein as approximations preceded by terms such as "about," "approximately," etc. In such cases, other instances contain specific numerical values. Regardless of whether a numerical value is represented as an approximation, this disclosure includes two instances: one instance represented as an approximation, and another instance not represented as an approximation. It should be further understood that each endpoint of a range is significant relative to and independent of the other endpoint.

[0055] As used herein, the term "antimicrobial" means a composition, material, or surface of a material that, when in the form of a coating or dry film, kills or inhibits the growth of microorganisms (including, but not limited to, bacteria, viruses, molds, mildews, algae, fungi, or any combination thereof). As used herein, the term "antimicrobial" does not necessarily mean that a material or surface of a material will kill or inhibit the growth of all microbial species within such a family, but rather that a material or surface of a material will kill or inhibit the growth of one or more microbial species from such a family.

[0056] As used herein, the term "dry film" refers to a coating that has been applied to a surface and is allowed to dry actively or passively, such that the coating has a moisture content that has reached equilibrium 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; or any subranges thereof.

[0057] As used herein, the term “biocidal” refers to a composition or material having an active substance intended to destroy, inhibit, render harmless, prevent the activity of undesirable organisms (such as bacteria, viruses, molds, mildews, algae, and / or fungi) or otherwise exert control over them, and in some respects, the biocidal composition has antimicrobial properties.

[0058] As used in this article, the term "logarithmic decrease" refers to log(C) a The negative value of / C0), where C aThe logarithmic reduction refers to the number of colony-forming units (“CFU”) on the antimicrobial surface, where C0 refers to the CFU of the control surface (non-antimicrobial surface). For example, a logarithmic reduction of 3 equals the elimination of 99.9% of microorganisms, and a logarithmic reduction of 5 equals the elimination of 99.999% of microorganisms. The logarithmic reduction value 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 the EPA test, as described in more detail elsewhere herein. “Logarithmic reduction” may also be referred to herein as “logarithmic kill.”

[0059] Unless otherwise indicated herein or clearly contradicted by the context, the terms “a / an” and “the,” and similar references, used in the context of describing this disclosure (particularly in the context of the following claims), should be interpreted as encompassing both the singular and plural. Unless otherwise indicated herein, the description of ranges of values ​​herein is intended only as a shorthand method of individually referring to each individual value falling within the range, and each individual value is incorporated into this specification as if it were individually described herein. Unless otherwise indicated herein or clearly contradicted by the context, all methods described herein may be performed in any suitable order.

[0060] As used herein, the terms “comprise(s)”, “include(s)”, “having”, “has”, “can”, “contain(s)”, and variations thereof are intended as open-ended transitional phrases, terms, or words that do not exclude the possibility of additional actions, structures, elements, or components. Whether explicitly stated or not, this specification also covers other instances of “comprise”, “consisting of”, and “substantially consisting of” the examples or elements presented herein.

[0061] As used herein, when used in the context of the numerical value or range described, the term “about” refers to a change of ±15% or less in said numerical value. For example, values ​​differing by ±15%, ±14%, ±10%, or ±5% would satisfy the definition of “about”, unless defined more narrowly in a particular case.

[0062] Unless otherwise stated, the term "alkyl" on its own or as part of another substituent refers to having a specified number of carbon atoms (in other words, "C1-C2"). 30 "Cycloalkyl" refers to a straight-chain, branched, or cyclic hydrocarbon chain ("cycloalkyl") with one to thirty carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, methylcyclopropyl, cyclopropylmethyl, pentyl, neopentyl, hexyl, and cyclohexyl. Other examples are -(C1-C2) 18 )alkyl, -(C1-C 15 )alkyl, -(C1-C 10 -(C1-C8)alkyl, -(C1-C6)alkyl, and -(C2-C6)alkyl. Such alkyl groups and the depicted carbon count ranges can be applied to any formula, R group, or chemical species disclosed herein. In some examples of this disclosure, -(C1-C6)alkyl... 30 Alkyl groups, whether straight-chain, branched, or cyclic, may not be -C1 alkyl, and / or may not be -C2 alkyl, and / or may not be -C3 alkyl, and / or may not be -C4 alkyl, and / or may not be -C5 alkyl, and / or may not be -C6 alkyl, and / or may not be -C7 alkyl, and / or may not be -C8 alkyl, and / or may not be -C9 alkyl, 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, and / or may not be -C 21 Alkyl, and / or may not be -C 22 Alkyl, and / or may not be -C 23 Alkyl, and / or may not be -C 24 Alkyl, and / or may not be -C 25 Alkyl, and / or may not be -C 26 Alkyl, and / or may not be -C 27 Alkyl, and / or may not be -C 28 Alkyl, and / or may not be -C 29 Alkyl, and / or may not be -C 30Alkyl group. In some examples of this disclosure, at least one hydrogen atom of the alkyl group is replaced by a hydroxyl group represented by -OH.

[0063] The term "aromatic" generally refers to a carbon ring or heterocycle having one or more polyunsaturated rings with aromatic properties (in other words, having (4n+2) delocalized π (pi) electrons, where n is an integer).

[0064] Unless otherwise stated, the term "aryl" on its own, or in combination with another substituent, refers to a carbocyclic aromatic system containing one or more rings (typically one, two, or three rings), wherein these rings may be linked together as side chains, as in biphenyl, or may be fused, as in naphthalene. Examples may include phenyl, anthracene, and naphthyl. Phenyl and naphthyl are preferred, with phenyl being the most preferred.

[0065] The term "aryl (C1-C4)alkyl" refers to a functional group in which one to four carbonyl chains are attached to an aryl group, such as -CH2-CH2-phenyl. Examples may include benzyl.

[0066] The term “fluorine-substituted” refers to an organic compound or part that (1) contains both carbon-hydrogen bonds and carbon-fluorine bonds; or (2) is “perfluorinated”, in which case the carbon is bonded to fluorine atoms and there are no hydrogen atoms.

[0067] The term "counter ion" refers to an ion that accompanies another ion species in order to maintain or at least contribute to neutrality of total charge. Counter ions can be positively charged and referred to as "cations," or they can be negatively charged and referred to as "anions." As an example, in the compound NaCl, Na... + (Sodium ions) are Cl- - The chloride anion is a counter ion of the sodium cation. The chloride anion is also a counter ion of the sodium cation.

[0068] As used herein, unless otherwise specified, the term "carrier" can refer to a polymer, monomer, adhesive, solvent, or combination thereof, as described herein. In specific examples, a carrier is a paint intended for application to a surface (which may include an inner or outer surface). The paint can be a dispersion of subdivided solids in a liquid medium (e.g., water, organic solvents, and / or inorganic solvents) that can be applied to a surface to form a film adhered to the surface. Examples of solids used in the paint may include polymers, pigments, fillers, extenders, drying agents, and rheology modifiers. In some examples, the paint can be a latex paint or a coating. In some examples, the paint can be a direct-to-metal ("DTM") paint or coating. In some aspects, the paint can be a liquid (e.g., aqueous solution, organic solvent, and / or oil) composition or can be in the form of a coating (e.g., a dry film). Examples of solvents may include water and organic solvents such as acetonitrile and methyl ethyl ketone. Examples of polymers may include acrylic acid, polyvinyl acetate, polyvinyl chloride, polyurethane (e.g., polyurethane dispersions (“PUD”), epoxy resins, alkyd resins (e.g., aqueous alkyd resins), fluoropolymers, polyesters, any copolymers thereof, or any combination thereof. Examples of acrylic polymers may include polyacrylic acid, poly(meth)methacrylate (PMMA), polymethacrylate, styrene-acrylic acid, any copolymers thereof, or any combination thereof. In some aspects, the polymer is an emulsion polymer (e.g., latex, aqueous acrylic acid, PUD, aqueous alkyd resin, or any combination thereof). In some aspects, the biocidal composition comprises an emulsion polymer dispersed in a solvent (e.g., water, organic solvents, and / or oils). In some aspects, the biocidal composition is a paint comprising an emulsion polymer dispersed in a solvent (e.g., water, organic solvents, and / or oils). In some aspects, the biocidal composition comprises a paint containing titanium dioxide, benzophenone, kaolin, and a binder comprising a polymer (e.g., an acrylic polymer). In some aspects, the biocidal composition comprises a paint containing titanium dioxide, 2-(2-butoxyethoxy)ethanol, and propoxylated propane-1,2-diol (MW < 2000). In some aspects, the composition is a polymer of a plastic article (e.g., a plastic article or film). In some aspects, the plastic comprises a polymer that may be nylon, polyvinyl chloride (PVC), polyester, polycarbonate (PC), polybutylene terephthalate, polypropylene, polyethylene, polyethyleneimine, aromatic polyamide precursor polymers, polyetherimide, polyamide-imide, polystyrene, poly(meth)methacrylate (PMMA), polyimide, melamine resin, urea-formaldehyde, polyacrylonitrile, copolyimide, amine-containing polymers, amide-containing polymers, imide-containing polymers, pyrrole-containing polymers, indole-containing polymers, any copolymers thereof, or any combination thereof.

[0069] As used herein, a “direct contact metal” or “DTM” composition (e.g., paint or coating) is a composition that can be applied directly to a metal surface without first applying a primer coat to the metal surface. DTM compositions are commonly used in industrial, marine, construction, and automotive applications.

[0070] As used herein, the term "secondary carbon" refers to a carbon in a compound or its substituent group that is covalently bonded to two other carbon atoms.

[0071] As used herein, the term "tertiary carbon" refers to a carbon atom in a compound or its substituent group that is covalently bonded to three other carbon atoms.

[0072] As used herein, the term "α (alpha) carbon" refers to a carbon atom in a compound that is covalently bonded to a functional group or an atom other than a hydrogen or carbon atom.

[0073] As used herein, with respect to a chemical formula or other chemical species, the term "any salt thereof" (and its grammatical variations) refers to (1) the protonated version of the chemical formula or chemical species mentioned; (2) a chemical formula or chemical species in which any C(O)OH, P(O)OH, S(O)OH or α,β-unsaturated carboxylic acid can be respectively converted to C(O)OM 1 P(O)OM 2 S(O)OM 3 Or α,β-unsaturated M 4 Carboxylate substitution, where M 1 M 2 M 3 and M 4 Independently any alkali metal cation (e.g., Li) + Na + K + 、Rb + or Cs + (2) or (3) any combination thereof. For example, a protonated version of a chemical formula or other chemical species (e.g., by protonating the nitrogen atom of an amino group) may be its HX salt, where H is a proton and X is a counter ion optionally selected from fluoride, chloride, bromide, iodide, hexafluorophosphate, sulfate, alkyl sulfonate, and aryl sulfonate. Furthermore, by way of interpretation, in any chemical formula or chemical species, C(O)OH may be replaced by C(O)Ona or any other alkali metal salt.

[0074] As used herein, the term "alkali metal" is interchangeable with "alkali metal cation" and refers to Li + Na + K + 、Rb + or Cs + .

[0075] As used herein, the term "copper auxiliary 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 the composition or material, as interpreted below. Without wishing to be bound by theory, it is considered that copper(I) is mostly colorless and has greater antimicrobial potency, while copper(II) is generally energy-advantageous but produces color and has lower antimicrobial potency. Therefore, copper(I) is generally preferred in terms of function and color, but copper(II) is generally more stable. To promote the durability and / or availability of copper(I) in a composition or material, several strategies / mechanisms may be considered, including the use of reducing agents (e.g., reducing copper(II) to copper(I), or reducing other oxidizing agents that may be present), antioxidants (e.g., scavenging oxidizing agents by reduction or by coordination or binding to prevent these oxidizing agents from oxidizing copper(II) to copper(I)), ligands with hydrophobic and / or bulky side chains (e.g., to restrict oxidizing agents to copper(I) in the copper complex), ligands with hydrophilic side chains and / or sterically empty side chains, ligands that favor complexation with copper(I) relative to copper(II) (e.g., energy-favorable to the copper(I) to be maintained), ligands that promote the migration of copper(I) to surfaces and / or interfaces, or any combination thereof. Therefore, the methods disclosed herein are generally considered to be... Copper-enhancing additives perform one or more of the functions described above to promote the durability of copper (I), and are in some aspects contained in compositions in liquid (e.g., aqueous solutions), in coatings (e.g., dry films), and / or in bulk materials (e.g., plastic articles). In some aspects, copper-enhancing additives are reducing agents, antioxidants, copper coordination ligands having one or more hydrophobic side chains (e.g., coordinated with copper (I) and / or copper (II)), copper coordination ligands having one or more bulky side chains (e.g., coordinated with copper (I) and / or copper (II)), copper coordination ligands that complex with copper (I) preferentially over copper (II) (e.g., coordinated with copper (I) and / or copper (II)), copper coordination ligands having two or more copper coordination sites (e.g., coordinated with copper (I) and / or copper (II)), or any combination thereof.

[0076] As used herein, the term "at.%" refers to an atomic weight percentage. In some respects, "at.%" is used relative to the amount of copper in the composition. Simply by way of example, a biocidal composition may contain an amount of copper of "X at.%" (where X is a number), and this means that the masses of copper atoms (using molecular weight) are added together and expressed as a percentage relative to a given basis (e.g., based on the mass of the biocidal composition). In this respect, when determining the mass of copper, the mass of copper complexes or other species in the molecule (e.g., oxygen atoms in Cu₂O) 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.

[0077] As used in this article, “weight” and “mass” are used interchangeably.

[0078] As used herein, the naming conventions for phosphorus-containing functional groups are standardized. Generally, the naming conventions for functional groups relative to a given phosphorus atom are determined by the number of oxygen atoms forming double bonds with the phosphorus atom (“A”), the total number of carbon and hydrogen atoms forming single bonds with the phosphorus atom (“B”), and the number of oxygen atoms forming single bonds with the phosphorus atom (“C”). In this regard, coordinates “(A,B,C)” can be used to identify phosphorus-containing functional groups. In this regard, “phosphate ester” has coordinates (1,0,3); “phosphite” has coordinates (0,0,3); and “phosphine” has coordinates (0,3,0). Formula (I) is an example of a phosphate ester. Formula (II) is an example of a phosphite. Formula (III) is an example of a phosphine.

[0079] As used in this article, the term "ambient temperature" refers to the atmospheric temperature in the immediate surrounding environment of an object or device.

[0080] As used herein, the term "ambient relative humidity" refers to the amount of water vapor present in a specific volume of the immediate surrounding atmosphere at ambient temperature, expressed as a percentage of the amount of water vapor required for saturation at the same temperature. In some instances, the value of ambient relative humidity may be 42%.

[0081] As used herein, the term "percentage point" refers to the unit of the arithmetic difference between two percentages. For example, for a given measurement, the difference between 88% and 98% transmittance values ​​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 portion of a total; in the example above, 88 constitutes 90% of 98 (calculated by dividing 88 by 98 and then multiplying by 100), and 98 constitutes 111% of 88 (calculated by dividing 98 by 88 and then multiplying by 100).

[0082] In one example, this disclosure provides a biocidal composition comprising a carrier, a copper (I) salt, and a copper auxiliary additive. In some examples, the copper auxiliary additive is combined with the copper (I) salt at a molar ratio of copper (I) ions to the copper auxiliary additive of 1:0.1 to 1:15. In other examples, the copper auxiliary additive may be combined with the copper (I) salt and added to the carrier at a total concentration of the two components of the biocidal composition of 1 g / L to 300 g / L. In other examples, the copper (I) salt may be pretreated with a pretreatment solution.

[0083] In one example, the copper (I) salt may comprise copper chloride (I), copper bromide (I), copper iodide (I), copper thiocyanate (I), copper acetate (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, chloro[1,3-bis(2,6-diisopropylphenyl)imidazolium-2-ylidene]copper (I), iodine (triethyl phosphite)copper (I), copper oxide (I), copper nitrate (I), and thiophene-2-carboxylic acid copper (I).

[0084] In one example, the biocidal composition may comprise a carrier, a copper(I) salt optionally pretreated with a pretreatment solution, and a copper auxiliary additive. In some examples, the biocidal composition may be a paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV-curable composition, UV-curable composition, or plastic (e.g., plastic articles). Plastic articles may be any articles disclosed elsewhere herein. In other examples, when the copper(I) salt is combined with a copper auxiliary additive and a carrier, or when the copper(I) salt and the copper auxiliary additive are combined with a carrier, the copper(I) salt optionally pretreated with a pretreatment solution may be combined with the copper auxiliary 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. In combining the copper(I) salt with a copper auxiliary additive and a carrier, or combining the copper(I) salt and the copper auxiliary additive with a carrier, examples of this disclosure may maintain antimicrobial efficacy (or prevent antimicrobial efficacy from decreasing below a certain level) and / or reduce color changes of the carrier. Examples of this disclosure can reduce changes in antimicrobial efficacy and / or carrier color between a period of time following the combination of copper (I) salt with copper auxiliary additives and a carrier, or the combination of copper (I) salt with copper auxiliary additives and a carrier, and the final antimicrobial efficacy and / or carrier color.

[0085] In one instance, a material (e.g., a coating, such as a dry film) may exhibit the logarithmic reduction described herein over a period of one month or longer, or over a period of three months or longer, or over any other period elsewhere described herein, under one or more of the following: the US Environmental Protection Agency's Test Method of Efficacy of Copper Alloy as a Sanitizer (2009) (also referred to herein as the "EPA Test"), the Japanese Industrial Standard (JIS) Z 2801 Test modified for bacteria, and / or the JIS Z 2801 Test modified for viruses. The time period (e.g., a one-month period or a three-month period) may begin at or after the material is applied as a layer to the surface. In such instances, the layer exhibits the logarithmic reduction described herein. Each of the EPA Test, the Japanese Industrial Standard (JIS) Z 2801 Test modified for bacteria, and the JIS Z 2801 Test modified for viruses is incorporated herein by reference in its entirety.

[0086] In one instance, 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 copper-assisted additives. The effectiveness of the disclosed compositions (e.g., coatings, such as dry films) as biocidal compositions can be measured as a function of the logarithmic reduction of the biocidal composition. The logarithmic reduction value of the biocidal composition may relate to the ability of the biocidal composition to kill various biological organisms to which the biocidal composition is exposed, but may also allow copper (I) salts to be used as a preservative of the composition during storage (e.g., in containers such as, but not limited to, tanks, cans, barrels, drums, bottles, or tubes). According to examples of this disclosure, the logarithmic reduction of the biocidal composition may be at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, in the range of 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 some instances, as described elsewhere herein, the logarithmic reduction can be maintained (e.g., prevented from falling below) or above any of the aforementioned values ​​over a given time period. The biocidal properties of the composition enable it to effectively kill substantially a wide variety of biological organisms, including bacteria, viruses, and fungi. When the coating is configured to have biocidal properties against bacteria, suitable examples of bacteria include Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin-resistant Staphylococcus aureus, Escherichia coli, and mixtures thereof. In some instances, under EPA testing, copper(I) salt exhibits at least a 3-log reduction, a 4-log reduction, a 5-log reduction, or even a 6-log reduction at concentrations of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, and Escherichia coli, or under JIS Z 2801 (2000) testing conditions or under a modified JIS Z 2801 test for bacteria, exhibiting a 3-log reduction or greater, or a 4-log reduction or greater (e.g., a 5-log reduction or greater). In other instances, under a modified JIS Z 2801 test for viruses, copper(I) salt exhibits a 2-log reduction or greater, a 3-log reduction or greater, a 4-log reduction or greater, or a 5-log reduction or greater at concentrations of Murine Novovirus or Severe Acute Respiratory Syndrome (“SARS” coronavirus 2) (“SARS-CoV-2”).Procedures for a modified JIS Z 2801 (2000) test for bacteria and a modified JIS Z 2801 (2000) test for viruses are provided in International Patent Application Publication No. WO 2021 / 055300 A1, “COLORSTABILIZATION OF BIOCIDAL COATINGS”, which is incorporated herein by reference in its entirety.

[0087] In brief, as used herein, the modified JIS Z 2801 test for bacteria comprises evaluating bacteria under modified conditions under the standard JIS Z 2801 (2000) test, wherein the modified conditions involve heating the glass or article to a temperature of 23°C to 37°C for 6 hours at 38% to 42% humidity. The modified JIS Z 2801 (2000) test for viruses comprises the following procedure. For each material being tested (e.g., a biocidal composition, a composition containing a copper(I) salt, a composition containing a copper adjuvant, a control composition), three samples of the material (in separate sterile Petri dishes) are inoculated with 20 pL aliquots of the test virus (wherein antimicrobial activity is measured) or a test medium containing 5% fetal bovine serum with or without the test virus (wherein cytotoxicity is measured) in an organic soil load. The inoculum is then covered with a membrane, and the membrane is pressed down so that the test virus and / or test medium spread on the membrane but do not extend beyond the edges of the membrane. Exposure time began at the time of inoculation of each sample. Inoculated samples were transferred to a control room set to room temperature or “ambient” temperature (20°C) and a relative humidity of 42% for 2 hours. Exposure time for control samples is discussed below. After the 2-hour exposure time, the membrane was aseptically clamped, and 2.00 mL aliquots of test virus and / or test medium were pipetted onto each material sample, covering each sample with the underside of the membrane (or the side of the membrane exposed to the sample). The surface of each sample was scraped individually with a sterile plastic cell scraper to collect the test virus or test medium. (In 10...) 2 (Dilution) Collect test viruses and / or test media, mix using a vortex mixer, and prepare sequential 10-fold dilutions. Then determine the antimicrobial activity and / or cytotoxicity of the dilutions.

[0088] To prepare control samples (also known as “zero-time virus controls”) for testing antimicrobial activity using a modified JIS Z 2801 test against viruses, three control samples (containing separate sterile Petri dishes) were each inoculated with 20 pL of test virus from an aliquot. Immediately after inoculation, 2.00 mL of test virus from an aliquot was pipetted onto each control sample. The surface of each sample was scraped separately using a sterile plastic cell scraper to collect the test virus. (At 10...) 2 (Dilution) The test virus was collected, mixed using a vortex mixer, and serially diluted 10-fold. The antimicrobial activity of the diluted solutions was determined.

[0089] To prepare a cytotoxic control sample (also known as a “2-hour control virus”) for a modified JIS Z 2801 test against a virus, one control sample (containing a separate sterile Petit's dish) was inoculated with 20 pL aliquots of test medium containing organic soil load (5% fetal bovine serum) instead of the test virus. The inoculum was covered with a membrane, and the membrane was pressed down so that the test medium spread across the membrane but did not extend beyond the edges. The exposure time began at the time of inoculation of each control sample. The control samples were transferred to a controlled chamber set to room temperature (20°C) and a relative humidity of 42% for a sustained 2-hour exposure time. After this exposure time, the membrane was picked up with sterile forceps, and 2.00 mL aliquots of test medium were pipetted onto each control sample and the underside of the membrane (the side exposed to the sample). The surface of each sample was scraped with a sterile plastic cell scraper to collect the test medium. (In 10...) 2 (Dilution) Collect the test medium, mix it using a vortex mixer, and prepare serial 10-fold dilutions. Determine the cytotoxicity of the dilutions.

[0090] A representative description of EPA testing is as follows: The copper(I) salt is ground into powder using a 2-inch jet mill. The jet-milled copper(I) salt powder is then added to a coating formulation (e.g., a commercially available BEHR). TMMix the 2050 latex paint. Control specimens coated with a copper(I) salt-free coating were prepared simultaneously with specimens coated with a copper(I) salt. A film was formed on a Leneta scrub chart (P121-10N) using a 7-mil wet film thickness pull-down bar. The film was dried at laboratory ambient temperature for 2 days, followed by antimicrobial testing. The dry film thickness was approximately 80 µm. 1-inch × 1-inch square specimens were cut from the center of the paint scrub test plate. The stainless steel carrier used as a reference was cleaned and sterilized by immersion in a 75% ethanol solution followed by rinsing with deionized water. Vials containing a Staphylococcus aureus (ATCC 6538) bacterial stock culture were stored at -80°C until use. 20 µL aliquots of the thawed bacterial culture were added to 10 mL of trypsin-soy broth. These bacterial suspensions were incubated three times consecutively in a track shaker at 36°C for 18–24 hours, and then once incubated in polypropylene snap-fit ​​tubes for 48 hours. The cultures were then mixed on a vortex mixer and allowed to settle. The upper two-thirds of the suspension was aspirated from each tube, and the OD was measured. 600 To estimate bacterial density, the culture was diluted with phosphate-buffered saline to bring the bacterial inoculum concentration close to the target value of 1.0 × 10⁻¹⁰. 7 CFU / mL. Mix 0.25 mL of 5% fetal bovine serum and 0.05 mL of Triton... TM X-100 was added to 4.70 mL of bacterial suspension to aid in inoculum spreading. Each test strip was inoculated with 20 µL of bacterial test culture. Using a curved sterile pipette tip, the inoculum volume was spread evenly to ensure complete and uniform coverage, spreading as close to the edges of the strip as possible. The strips were then incubated for 120 minutes in a controlled environment at 42% relative humidity and 23°C. After the 120-minute exposure period, the strips were neutralized in Letheen broth. A tenfold serial dilution of the neutralization solution was plated onto trypsin-soy agar plates using standard plate spreading techniques and incubated at 36°C for 24 hours to produce a countable number of viable colonies (approximately 20–200 colonies per plate). The logarithmic and percentage reduction measurements of antimicrobial efficacy determined the difference in CFU between stainless steel and glass-containing strips. The antimicrobial efficacy measurement, expressed as a log reduction, was repeated, and the results were averaged to obtain the mean log-kill value.

[0091] In one instance, a copper(I) salt can be combined with a copper auxiliary additive to prevent the antimicrobial efficacy from decreasing below a certain threshold (e.g., less than a 3 log reduction or any other value disclosed herein), and / or to limit the color shift of the biocidal composition relative to the color of a standard coating material (e.g., a material without a copper(I) salt or copper auxiliary additive). For example, the observed color can be made to deviate from the standard color by a CIE L. * a * b * ΔE * 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; within 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.

[0092] It is understood that CIE L * a * b * A color space is a color scale used to determine colors. (CIE L) * a * b * The three coordinates (or dimensions / components) represent the lightness (L) of the color. * =0 represents black, and L * =100 represents white), the position between red (sometimes also called magenta) and green (negative a). * The value represents green, while a positive 'a' represents green. * The value represents the position between red and yellow / blue (negative b). * The value represents blue, and is positive b. * The value represents yellow. L * The component closely matches human perception of brightness. (Compared to CIE L) * a * b * Color spaces are related to CIE L. * C * h * A color space is a cylindrical representation of three factors related to the perception of color: luminance, chroma, and hue. (CIE L) * C * h * The axial component is related to CIE L * a * b * Same brightness attribute L *The radial component is chromaticity, and the angular component is hue. Using CIE L * a * b * and CIE L * C * h * Color spaces can measure the color difference between a standard color and an observed color (e.g., ΔE). * Furthermore, it can measure the degree to which the desired color of the coating is altered by its components.

[0093] In one example, a biocidal composition is disclosed, the biocidal composition comprising: a carrier; a copper (I) salt; and a copper auxiliary additive.

[0094] In some instances, the use of copper-assisted additives can achieve the desired level of antimicrobial efficacy (e.g., through any of the tests disclosed herein, such as EPA tests).

[0095] In some instances, the carrier and the copper auxiliary additive are different. As used herein, “different” means that a given chemical species (e.g., an acrylic polymer) cannot be both a carrier and a copper auxiliary additive; rather, if the carrier is, for example, an acrylic polymer, the copper auxiliary additive cannot be an acrylic polymer, but must be another chemical species (e.g., diphenyl phosphate).

[0096] In some instances, the carrier may comprise or may be any of the carriers disclosed herein. For example, in some instances, the carrier comprises a polymer, monomer, adhesive, solvent, or any combination thereof. In some instances, the carrier is or comprises a paint. In some instances, the paint may be used for application to a surface (which may include an inner or outer surface). In some instances, the paint may be a dispersion of subdivided solids in a liquid medium (e.g., water, organic solvents, and / or inorganic solvents) that can be applied to a surface to form a film adhered to the surface. Examples of solids used in the paint may include polymers, pigments, fillers, extenders, driers, rheology modifiers, or any combination thereof. In some instances, the paint may be a latex paint or a coating. In some instances, the paint may be a direct contact metal (“DTM”) paint or coating. In some instances, the paint may be a liquid composition (e.g., an aqueous solution, an organic solvent, and / or an oil) or may be in the form of a coating (e.g., a dry film). Examples of solvents may include water and organic solvents. Examples of polymers may include acrylic or acrylate, polyvinyl chloride, polyvinyl acetate, polyurethane (e.g., polyurethane dispersion (PUD)), epoxy resin, alkyd resin (e.g., aqueous alkyd resin), fluoropolymer, polyester, any copolymer thereof, or any combination thereof. In some examples, the polymer is an emulsion polymer (e.g., latex, PUD, aqueous alkyd resin, or any combination thereof). In some examples, the biocidal composition comprises an emulsion polymer dispersed in a medium (e.g., organic solvent, water, and / or oil). In some examples, the biocidal composition is a paint comprising an emulsion polymer dispersed in a solvent (e.g., water, organic solvent, and / or oil). In some examples, the biocidal composition comprises a paint containing titanium dioxide, benzophenone, kaolin, and a binder containing a polymer (e.g., an acrylic polymer). In some examples, the biocidal composition comprises a paint containing titanium dioxide, 2-(2-butoxyethoxy)ethanol, and propoxylated propane-1,2-diol (MW < 2000).

[0097] In some instances, the biocidal composition may be in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV-curable composition, UV-curable composition, or plastic. In some instances, the biocidal composition is in liquid form under ambient conditions (1 atm (about 101.3 kPa) and 20°C). In some instances, the biocidal composition does not contain (e.g., and / or is not in the following forms) paint, and / or does not contain coating, and / or does not contain elastomer coating, and / or does not contain caulking compound, and / or does not contain sealant, and / or does not contain floor wax, and / or does not contain fabric treatment agent, and / or does not contain dye, and / or does not contain varnish, and / or does not contain primer, and / or does not contain UV-curable composition, and / or does not contain UV-curable composition, and / or does not contain plastic.

[0098] In some instances, the biocidal composition does not contain (e.g., and / or the carrier is not or does not contain) polymers, and / or does not contain monomers, and / or does not contain binders, and / or does not contain organic solvents, and / or does not contain inorganic solvents, and / or does not contain coatings, and / or does not contain water. In some instances, the biocidal composition does not contain a dispersion of finely divided solids in a liquid medium that can be applied to a surface to form a film; for example, the composition does not contain pigments, and / or does not contain fillers, and / or does not contain extenders, and / or does not contain drying agents, and / or does not contain rheology modifiers. In some instances, the biocidal composition does not contain latex paint and / or does not contain coatings. In some instances, the biocidal composition does not contain DTM coatings. In some instances, the biocidal composition does not contain paint in liquid form. In some instances, the biocidal composition does not contain acrylic acid, and / or does not contain acrylates, and / or does not contain polyvinyl chloride, and / or does not contain polyvinyl acetate, and / or does not contain polyurethane, and / or does not contain epoxy resins, and / or does not contain alkyd resins, and / or does not contain fluoropolymers, and / or does not contain polyesters, and / or does not contain copolymers, and / or does not contain emulsion polymers, and / or does not contain emulsion polymers dispersed in a medium. In some instances, the biocidal composition does not contain paints containing titanium dioxide, and / or does not contain paints containing benzophenone, and / or does not contain paints containing kaolin, and / or does not contain paints containing 2-(2-butoxyethoxy)ethanol, and / or does not contain paints containing propoxylated propane-1,2-diol.

[0099] In one instance, a copper(I) salt that has optionally been pretreated with a pretreatment solution may be combined with a copper auxiliary additive (e.g., one or more copper auxiliary additives).

[0100] In one instance, the copper auxiliary additive is or comprises a phosphate ester, a phosphite, a phosphine, an imidazole, any salt thereof, or any combination thereof. In some instances, any copper auxiliary additive in the aforementioned copper auxiliary additive may be hydrophobic, hydrophilic, or amphiphilic, and any of the aforementioned copper auxiliary additives (or any other copper auxiliary additives disclosed herein) may be characterized as hydrophobic, hydrophilic, or amphiphilic. For example, the copper auxiliary additive may be or may comprise hydrophilic phosphine, hydrophobic phosphite, hydrophobic phosphite, hydrophobic phosphate ester, or any combination thereof.

[0101] In some instances, the biocidal composition does not contain (e.g., and / or the copper cofactor is not) phosphate esters, and / or does not contain phosphites, and / or does not contain phosphine, and / or does not contain imidazole, and / or does not contain nitriles, and / or does not contain hydrophobic copper cofactors, and / or does not contain hydrophilic copper cofactors, and / or does not contain amphiphilic copper cofactors, and / or does not contain hydrophilic phosphine, and / or does not contain hydrophobic phosphites, and / or does not contain hydrophobic phosphate esters.

[0102] In one instance, the copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), or a compound of formula (IV), or any combination thereof.

[0103] In one instance, the copper auxiliary additive can be a compound of formula (I):

[0104]

[0105] Each R 1 Independently select from the following groups: hydrogen, alkali metals, C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl. In some instances, all R... 1 They are not both hydrogen. In other instances, at least one R 1 It is either hydrogen or an alkali metal. In other instances, R... 1 It is a combination of hydrogen and alkali metals.

[0106] In some instances, each R 1 Independently select from the following groups: hydrogen, alkali metals, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), aryl, and benzyl, provided that all R 1 They are not both hydrogen.

[0107] In some instances, at least one R 1 The α-carbon is a secondary or tertiary carbon.

[0108] In some instances, a compound of formula (I) may contain a compound of formula (Ia) or any salt thereof:

[0109] ;

[0110] Furthermore, any reference to “Equation (I)” in this document also includes Equation (Ia).

[0111] Some instances of compounds of formula (I) may contain independently chosen R 1 Specific combinations of these compounds cause the compounds of formula (I) to complex with copper, interact with copper, or otherwise affect copper (e.g., by influencing the persistence of a given oxidation state, such as copper (I)), but unlike R 1 Other specific combinations are desired or preferred, as is the case with 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 arising from the chemical structure of compounds of specific formula (I). In certain instances of compounds of formula (I), each R 1 It may not be hydrogen on its own, and / or may not be C1-C. 20 Any of the alkyl groups, and / or may not be aryl, and / or may not be aryl (C1-C4) alkyl. In some instances, the biocidal composition does not contain a compound of formula (I), and / or the copper auxiliary additive is not a compound of formula (I).

[0112] Examples of compounds of formula (I) may include 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, tri(2-ethylhexyl) phosphate, methyl phosphate, dimethyl phosphate, trimethyl phosphate, butyl phosphate (e.g., n-butyl, sec-butyl or tert-butyl), dibutyl phosphate (e.g., n-butyl, sec-butyl and / or tert-butyl), tributyl phosphate (e.g., n-butyl, sec-butyl and / or tert-butyl), phenyl phosphate, diphenyl phosphate, triphenyl phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, any salt thereof, or any combination thereof. In some instances, the biocidal composition does not contain (e.g., copper-assisted additives are not) one or more of the following: 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, tri(2-ethylhexyl) phosphate, methyl phosphate, dimethyl phosphate, trimethyl phosphate, butyl phosphate (e.g., n-butyl, sec-butyl, or tert-butyl), dibutyl phosphate (e.g., n-butyl, sec-butyl, and / or tert-butyl), tributyl phosphate (e.g., n-butyl, sec-butyl, and / or tert-butyl), phenyl phosphate, diphenyl phosphate, triphenyl phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, or any salt thereof.

[0113] In some instances, for any compound of formula (I), formula (II), formula (III), or formula (IV), C1-C 20 Alkyl groups can contain 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-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, 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 14 Alkyl, C2-C 13 Alkyl, C2-C 12 Alkyl, C2-C 11 Alkyl, C2-C 10 Alkyl, C2-C9 alkyl, C2-C8 alkyl, C2-C7 alkyl, C2-C6 alkyl, C2-C5 alkyl, C2-C4 alkyl, C2-C3 alkyl, 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-C9 alkyl, C3-C8 alkyl, C3-C7 alkyl, C3-C6 alkyl, C3-C5 alkyl, C3-C4 alkyl, C4-C 20 Alkyl, C4-C 19 Alkyl, C4-C 18 Alkyl, C4-C 17 Alkyl, C4-C 16 Alkyl, C4-C 15Alkyl, C4-C 14 Alkyl, C4-C 13 Alkyl, C4-C 12 Alkyl, C4-C 11 Alkyl, C4-C 10 Alkyl, C4-C9 alkyl, C4-C8 alkyl, C4-C7 alkyl, C4-C6 alkyl, C4-C5 alkyl, 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-C9 alkyl, C5-C8 alkyl, C5-C7 alkyl, C5-C6 alkyl, C6-C 20 Alkyl, C6-C 19 Alkyl, C6-C 18 Alkyl, C6-C 17 Alkyl, 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-C9 alkyl, C6-C8 alkyl, C6-C7 alkyl, 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-C9 alkyl, C7-C8 alkyl, 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-C14 Alkyl, C8-C 13 Alkyl, C8-C 12 Alkyl, C8-C 11 Alkyl, C8-C 10 Alkyl, C8-C9 alkyl, 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 -C 16 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, C12 -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 19 Alkyl, 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.

[0114] In some instances of compounds of formula (I), each R 1 It may not be C1 alkyl, and / or may not be C2 alkyl, and / or may not be C3 alkyl, and / or may not be C4 alkyl, and / or may not be C5 alkyl, and / or may not be C6 alkyl, and / or may not be C7 alkyl, and / or may not be C8 alkyl, and / or may not be C9 alkyl, 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.

[0115] Without being bound by any particular theory, it is considered that the presence or retention of copper (I) is promoted by employing 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 a 3 logarithmic reduction), minimizing the color difference of the biocidal composition, or any combination thereof. Antimicrobial efficacy can be measured, as described elsewhere herein, such as by using EPA testing.

[0116] In one instance, the copper auxiliary additive may be a compound of formula (II) or any salt thereof:

[0117]

[0118] Each R 2 Independently selected from the group consisting of: hydrogen, C1-C optionally substituted with fluorine. 20 Alkyl groups, and aryl groups (e.g., phenyl). In some instances, all R groups... 2 They are not both hydrogen.

[0119] In some instances, each R2 Independently selected from the group consisting of: hydrogen, C1-C8 alkyl groups optionally substituted with fluorine, and phenyl, provided that all R 2 They are not both hydrogen.

[0120] In some instances, each R 2 Independently selected from the group consisting of: hydrogen, C1-C5 alkyl groups optionally substituted with fluorine, and phenyl, provided that all R 2 They are not both hydrogen.

[0121] In some instances, at least one R 2 The α-carbon is a secondary or tertiary carbon.

[0122] Some instances of compounds of formula (II) may contain independently chosen R 2 Specific combinations of these compounds cause the compounds of formula (II) to complex with copper, interact with copper, or otherwise affect copper (e.g., by influencing the persistence of a given oxidation state, such as copper (I)), but unlike R 2 Other specific combinations are desired or preferred, as is the case with 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 arising from the chemical structure of compounds of specific formula (II). In certain instances of compounds of formula (II), each R 2 Independently, it may not be hydrogen, and / or may not be a C1 alkyl, and / or may not be a C1 alkyl with optional fluorine substitution, and / or may not be aryl (e.g., phenyl), and / or may not be a C2 alkyl, and / or may not be a C2 alkyl with optional fluorine substitution, and / or may not be a C3 alkyl, and / or may not be a C3 alkyl with optional fluorine substitution, and / or may not be a C4 alkyl, and / or may not be a C4 alkyl with optional fluorine substitution, and / or may not be a C5 alkyl, and / or may not be a C5 alkyl with optional fluorine substitution, and / or may not be a C6 alkyl, and / or may not be a C6 alkyl with optional fluorine substitution, and / or may not be a C7 alkyl, and / or may not be a C7 alkyl with optional fluorine substitution, and / or may not be a C8 alkyl, and / or may not be a C8 alkyl with optional fluorine substitution, and / or may not be a C9 alkyl, and / or may not be a C9 alkyl with optional fluorine substitution, and / or may not be a C9 alkyl. 10 Alkyl groups, and / or C groups that may not be optionally fluorinated, 10 Alkyl, and / or may not be C 11 Alkyl groups, and / or C groups that may not be optionally fluorinated, 11 Alkyl, and / or may not be C 12 Alkyl groups, and / or C groups that may not be optionally fluorinated, 12 Alkyl, and / or may not be C 13Alkyl groups, and / or C groups that may not be optionally fluorinated, 13 Alkyl, and / or may not be C 14 Alkyl groups, and / or C groups that may not be optionally fluorinated, 14 Alkyl, and / or may not be C 15 Alkyl groups, and / or C groups that may not be optionally fluorinated, 15 Alkyl, and / or may not be C 16 Alkyl groups, and / or C groups that may not be optionally fluorinated, 16 Alkyl, and / or may not be C 17 Alkyl groups, and / or C groups that may not be optionally fluorinated, 17 Alkyl, and / or may not be C 18 Alkyl groups, and / or C groups that may not be optionally fluorinated, 18 Alkyl, and / or may not be C 19 Alkyl groups, and / or C groups that may not be optionally fluorinated, 19 Alkyl, and / or may not be C 20 Alkyl groups, and / or C groups that may not be optionally fluorinated, 20 Alkyl groups. In some instances, the biocidal composition does not contain a compound of formula (II), and / or the copper auxiliary additive is not a compound of formula (II).

[0123] Examples of compounds of formula (II) may include trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tri(2-ethylhexyl) phosphite, triisopropyl phosphite, tri(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, or any salt thereof. In some instances, the biocidal composition does not contain (e.g., copper auxiliaries are not) one or more of the following: trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tri(2-ethylhexyl) phosphite, triisopropyl phosphite, tri(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, or any salt thereof.

[0124] Without being bound by any particular theory, it is considered that the presence or retention of copper (I) is promoted by employing a compound of formula (II) or any salt thereof, and that a biocidal composition containing a compound of formula (II) 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 a 3 logarithmic reduction), minimizing the color difference of the biocidal composition, or any combination thereof. Antimicrobial efficacy can be measured, as described elsewhere herein, such as by using EPA testing.

[0125] In one instance, the copper auxiliary additive may be a compound of formula (III) or any salt thereof:

[0126]

[0127] Each R 3 Independently selected from the group consisting of: hydrogen and C1-C optionally substituted with hydroxyl groups. 20 Alkyl groups. In some instances, all R groups are alkyl groups. 3 They are not both hydrogen.

[0128] In some instances, each R 3 Independently selected from the group consisting of: hydrogen and C1-C optionally substituted with hydroxyl groups. 10 Alkyl, provided that all R 3 They are not both hydrogen.

[0129] In some instances, each R 3 Independently selected from the group consisting of hydrogen and C1-C6 alkyl groups optionally substituted with hydroxyl groups, provided that all R 3 They are not both hydrogen.

[0130] In some instances, at least one R 3 The α-carbon is a secondary or tertiary carbon.

[0131] Some instances of compounds of formula (III) may contain independently chosen R 3 Specific combinations of these compounds cause the compounds of formula (III) to complex with copper, interact with copper, or otherwise affect copper (e.g., by influencing the persistence of a given oxidation state, such as copper (I)), but unlike R 3 Other specific combinations are desired or preferred, as is the case with 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 arising from the chemical structure of compounds of particular formula (III). In certain instances of compounds of formula (III), each R 3Independently, it may not be hydrogen, and / or may not be a C1 alkyl, and / or may not be a C1 alkyl optionally substituted with a hydroxyl group, and / or may not be a C2 alkyl, and / or may not be a C2 alkyl optionally substituted with a hydroxyl group, and / or may not be a C3 alkyl, and / or may not be a C3 alkyl optionally substituted with a hydroxyl group, and / or may not be a C4 alkyl, and / or may not be a C4 alkyl optionally substituted with a hydroxyl group, and / or may not be a C5 alkyl, and / or may not be a C5 alkyl optionally substituted with a hydroxyl group, and / or may not be a C6 alkyl, and / or may not be a C6 alkyl optionally substituted with a hydroxyl group, and / or may not be a C7 alkyl, and / or may not be a C7 alkyl optionally substituted with a hydroxyl group, and / or may not be a C8 alkyl, and / or may not be a C8 alkyl optionally substituted with a hydroxyl group, and / or may not be a C9 alkyl, and / or may not be a C9 alkyl optionally substituted with a hydroxyl group, and / or may not be a C9 alkyl. 10 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 10 Alkyl, and / or may not be C 11 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 11 Alkyl, and / or may not be C 12 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 12 Alkyl, and / or may not be C 13 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 13 Alkyl, and / or may not be C 14 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 14 Alkyl, and / or may not be C 15 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 15 Alkyl, and / or may not be C 16 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 16 Alkyl, and / or may not be C 17 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 17 Alkyl, and / or may not be C 18 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 18 Alkyl, and / or may not be C 19 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 19 Alkyl, and / or may not be C 20 Alkyl groups, and / or C groups that may not be optionally substituted with hydroxyl groups. 20 Alkyl groups. In some instances, the biocidal composition does not contain a compound of formula (III), and / or the copper auxiliary additive is not a compound of formula (III).

[0132] Examples of compounds of formula (III) may include tris(hydroxypropyl)phosphine and tributylphosphine. In some instances, the biocidal composition does not contain (e.g., copper auxiliaries are not) one or more of tris(hydroxypropyl)phosphine or tributylphosphine.

[0133] Without being bound by any particular theory, it is believed that the presence or retention of copper (I) is promoted by employing a compound of formula (III) or any salt thereof, and that a biocidal composition containing a compound of formula (III) 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 logarithmic reduction), minimizing the color difference of the biocidal composition, or any combination thereof.

[0134] In one instance, the copper auxiliary additive may be a compound of formula (IV) or any salt thereof:

[0135]

[0136] Each R 4 Independently select from the following groups: hydrogen and C1-C 20 Alkyl group; and wherein X is a counter ion.

[0137] In some instances, each R 4 Independently select C1-C 10 A group composed of alkyl groups.

[0138] In some instances, each R 4 The group consisting of C1-C6 alkyl groups is selected independently.

[0139] Examples of compounds of formula (IV) may include 1-butyl-3-methylimidazole bromide (“BMIM”) and 1-butyl-3-methylimidazole chloride. In some instances, the biocidal composition does not contain (e.g., copper auxiliaries are not) one or more of 1-butyl-3-methylimidazole bromide and 1-butyl-3-methylimidazole chloride.

[0140] In some instances, X may be selected from the group consisting of: fluorides, chlorides, bromides, iodides, bicarbonates, bisulfates, bisulfites, hydroxides, nitrates, nitrites, acetates, formates, cyanides, tetrafluoroborates, hexafluorophosphates, perchlorates, and trifluoromethanesulfonates.

[0141] Some instances of compounds of formula (IV) may contain independently selected R 4Specific combinations of these compounds cause the compounds of formula (IV) to complex with copper, interact with copper, or otherwise affect copper (e.g., by influencing the persistence of a given oxidation state, such as copper (I)), but unlike R... 4 Other specific combinations are desired or preferred, as is the case with 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 arising from the chemical structure of compounds of particular formula (IV). In certain instances of compounds of formula (IV), each R 4 It may not be hydrogen, and / or may not be C1 alkyl, and / or may not be C2 alkyl, and / or may not be C3 alkyl, and / or may not be C4 alkyl, and / or may not be C5 alkyl, and / or may not be C6 alkyl, and / or may not be C7 alkyl, and / or may not be C8 alkyl, and / or may not be C9 alkyl, 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 groups. In some instances, the biocidal composition does not contain a compound of formula (IV), and / or the copper auxiliary additive is not a compound of formula (IV).

[0142] Some instances of compounds of formula (IV) may contain specific counterions that cause the compound of formula (IV) to 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 as desired or preferred as other specific counterions, due to the combined effects of chemical phenomena as 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 compound of specific formula (IV). In some instances of compounds of formula (IV), the counter ion may not be a fluoride, and / or may not be a chloride, and / or may not be a bromide, and / or may not be an iodide, and / or may not be a bicarbonate, and / or may not be a bisulfate, and / or may not be a bisulfite, and / or may not be a hydroxide, and / or may not be a nitrate, and / or may not be a nitrite, and / or may not be an acetate, and / or may not be a formate, and / or may not be a cyanide, and / or may not be a tetrafluoroborate, and / or may not be a hexafluorophosphate, and / or may not be a perchlorate, and / or may not be a trifluoromethanesulfonate.

[0143] In one instance, the biocidal composition contains at least 0.01 at.% copper per 100 weight percent of the total composition. In some instances, the biocidal composition contains less than 10 at.% copper per 100 weight percent of the total composition. In some instances, the biocidal composition contains the following amounts (at.% based on 100 weight percent of the biocidal composition): 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 thereof.

[0144] In one instance, the copper(I) salt alone, the copper auxiliary additive alone, or the sum of both the copper(I) salt and the copper auxiliary additive can be described by any of the following values ​​and ranges: from 0.01 wt.% of the total 100 wt.% of the carrier or biocide composition to 20 wt.% of the carrier of the biocide composition, such as the following amounts (wt.% of 100 wt.% of the carrier or biocide 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 values ​​can refer to the absolute amount present or the amount added to the composition. The basis weight can be either the carrier or the biocidal composition, as this will become clear from the context, since in some instances the carrier is the major component of the biocidal composition. Therefore, in some instances, the amounts of one or more given components relative to the carrier or the biocidal composition will be similar values.

[0145] In one or more instances, the copper (I) salt and copper auxiliary additive may be present in a total amount of at least 10 g / L of carrier (or biocidal composition), or at least 15 g / L of carrier (or biocidal composition), or at least 20 g / L of carrier (or biocidal composition), or at least 25 g / L of carrier (or biocidal composition), or at least 30 g / L of carrier (or biocidal composition), or at least 35 g / L of carrier (or biocidal composition), or at least 40 g / L of carrier (or biocidal composition).

[0146] In one example, copper (I) salt and copper auxiliary additives may be present in the following total amounts (g / L carrier or biocidal composition): 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 may be represented as a carrier or a biocidal composition.

[0147] In one instance, the copper (I) salt may be present in the biocidal composition at an amount of at least 1 g / L of the biocidal composition or carrier. In some instances, the copper (I) salt may be present in the biocidal composition or carrier at an amount of less than 135 g / L of the biocidal composition or carrier. In some instances, copper (I) salts may be present in the biocidal composition or carrier in the following amounts (g / L): 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 - 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 g / L amounts; any subranges contained therein.

[0148] In one example, the molar ratio of copper to copper auxiliary additive in the biocidal composition or carrier can be 1:1 to 1:50, 1:1 to 1:49, 1:1 to 1:48, 1:1 to 1:47, 1:1 to 1:46, 1:1 to 1:45, 1:1 to 1:44, 1:1 to 1:43, 1:1 to 1:42, 1:1 to 1:41, 1:1 to 1:40, 1:1 to 1:39, 1:1 to 1:38, 1:1 to 1:37, 1:1 to 1:36, 1:1 to 1:35, 1:1 to 1:34, 1:1 to 1:33, 1:1 to 1:32, 1:1 to 1:31, 1:1 to 1:30, 1:1 to 1:29, 1:1 to 1:28, 1:1 to 1:27. 1:1 to 1:26, 1:1 to 1:25, 1:1 to 1:24, 1:1 to 1:23, 1:1 to 1:22, 1:1 to 1:21, 1:1 to 1:20, 1:1 to 1:19, 1:1 to 1:18, 1:1 to 1:17, 1:1 to 1:16, 1:1 to 1:15, 1:1 to 1:14.9, 1:1 to 1 1:14.8, 1:1 to 1:14.7, 1:1 to 1:14.6, 1:1 to 1:14.5, 1:1 to 1:14.4, 1:1 to 1:14.3, 1:1 to 1:14.2, 1:1 to 1:14.1, 1:1 to 1:14.0, 1:1 to 1:13.9, 1:1 to 1:13.8, 1:1 to 1:13. 7, 1:1 to 1:13.6, 1:1 to 1:13.5, 1:1 to 1:13.4, 1:1 to 1:13.3, 1:1 to 1:13.2, 1:1 to 1:13.1, 1:1 to 1:13.0, 1:1 to 1:12.9, 1:1 to 1:12.8, 1:1 to 1:12.7, 1:1 to 1:12.6, 1 :1 to 1:12.5, 1:1 to 1:12.4, 1:1 to 1:12.3, 1:1 to 1:12.2, 1:1 to 1:12.1, 1:1 to 1:12.0, 1:1 to 1:11.9, 1:1 to 1:11.8, 1:1 to 1:11.7, 1:1 to 1:11.6, 1:1 to 1:11.5, 1:1 to 1:11.4, 1:1 to 1:11.3, 1:1 to 1:11.2, 1:1 to 1:11.1, 1:1 to 1:11.0, 1:1 to 1:10.9, 1:1 to 1:10.8, 1:1 to 1:10.7, 1:1 to 1:10.6, 1:1 to 1:10.5, 1:1 to 1:10.4, 1:1 to 1:1 0.3, 1:1 to 1:10.2, 1:1 to 1:10.1, 1:1 to 1:10.0, 1:1 to 1:9.9, 1:1 to 1:9.8, 1:1 to 1:9.7, 1:1 to 1:9.6, 1:1 to 1:9.5, 1:1 to 1:9.4, 1:1 to 1:9.3, 1:1 to 1:9.2, 1:1 to 1:9.1. 1:1 to 1:9.0, 1:1 to 1:8.9, 1:1 to 1:8.8, 1:1 to 1:8.7, 1:1 to 1:8.6, 1:1 to 1:8.5, 1:1 to 1:8.4, 1:1 to 1:8.3, 1:1 to 1:8.2, 1:1 to 1:8.1, 1:1 to 1:8.0, 1:1 to 1:7.9, 1:1 to 1:7.8, 1:1 to 1:7.7, 1:1 to 1:7.6, 1:1 to 1:7.5, 1:1 to 1:7.4, 1:1 to 1:7.3, 1:1 to 1:7.2, 1:1 to 1:7.1, 1:1 to 1:7.0, 1:1 to 1:6.9 1:1 to 1:6.8, 1:1 to 1:6.7, 1:1 to 1:6.6, 1:1 to 1:6.5, 1:1 to 1:6.4, 1:1 to 1:6.3, 1:1 to 1:6.2, 1:1 to 1:6.1, 1:1 to 1:6.0, 1:1 to 1:5.9, 1:1 to 1:5.8, 1:1 to 1:5.7, 1:1 to 1:5.6, 1:1 to 1:5.5, 1:1 to 1:5.4, 1:1 to 1:5.3, 1:1 to 1:5.2, 1:1 to 1:5.1, 1:1 to 1:5.0, 1:1 to 1:4.9, 1:1 to 1:4.8, 1:1 to 1:4.7, 1:1 1:4.6, 1:1 to 1:4.5, 1:1 to 1:4.4, 1:1 to 1:4.3, 1:1 to 1:4.2, 1:1 to 1:4.1, 1:1 to 1:4.0, 1:1 to 1:3.9, 1:1 to 1:3.8, 1:1 to 1:3.7, 1:1 to 1:3.6, 1:1 to 1:3.5, 1:1 to 1:3.4, 1:1 to 1:3.3, 1:1 to 1:3.2, 1:1 to 1:3.1, 1:1 to 1:3.0, 1:1 to 1:2.9, 1:1 to 1:2.8, 1:1 to 1:2.7, 1:1 to 1:2.6, 1:1 to 1:2.5, 1:1 to 1 :2.4, 1:1 to 1:2.3, 1:1 to 1:2.2, 1:1 to 1:2.1, 1:1 to 1:2.0, 1:1 to 1:1.9, 1:1 to 1:1.8, 1:1 to 1:1.7, 1:1 to 1:1.6, 1:1 to 1:1.5, 1:1 to 1:1.4, 1:1 to 1:1.3, 1:1 to 1:1.2, 1:1 to 1:1.1, 1:1 to 1:0.9, 1:1 to 1:0.8, 1:1 to 1:0.7, 1:1 to 1:0.6, 1:1 to 1:0.5, 1:1 to 1:0.4, 1:1 to 1:0.3, 1:1 to 1:0.2, 1:1 to 1:0.1. 50:1 to 1:1, 49:1 to 1:1, 48:1 to 1:1, 47:1 to 1:1, 46:1 to 1:1, 45:1 to 1:1, 44:1 to 1:1, 43:1 to 1:1, 42:1 to 1:1, 41:1 to 1:1, 40:1 to 1:1, 39:1 to 1:1, 38:1 to 1:1, 37:1 to 1:1, 36:1 to 1:1, 35:1 to 1:1, 34:1 to 1:1, 33:1 to 1:1, 32:1 to 1:1, 31:1 to 1:1, 30:1 to 1:1, 29:1 to 1:1, 28:1 to 1:1, 27:1 to 1:1, 26:1 to 1:1, 25:1 to 1:1, 24:1 to 1:1, 23:1 The scores were 1:1, 22:1, 21:1, 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14.9, 14.8, 14.7, 14.6, and 14.5. :1 to 1:1, 14.4:1 to 1:1, 14.3:1 to 1:1, 14.2:1 to 1:1, 14.1:1 to 1:1, 14.0:1 to 1:1, 13.9:1 to 1:1, 13.8:1 to 1:1, 13.7:1 to 1:1, 13.6:1 to 1:1, 13.5:1 to 1:1, 13.4:1 to 1 :1, 13.3:1 to 1:1, 13.2:1 to 1:1, 13.1:1 to 1:1, 13.0:1 to 1:1, 12.9:1 to 1:1, 12.8:1 to 1:1, 12.7:1 to 1:1, 12.6:1 to 1:1, 12.5:1 to 1:1, 12.4:1 to 1:1, 12.3:1 to 1:1, 12.2:1 to 1:1, 12.1:1 to 1:1, 12.0:1 to 1:1, 11.9:1 to 1:1, 11.8:1 to 1:1, 11.7:1 to 1:1, 11.6:1 to 1:1, 11.5:1 to 1:1, 11.4:1 to 1:1, 11.3:1 to 1:1, 11.2:1 to 1:1, 11.1 :1 to 1:1, 11.0:1 to 1:1, 10.9:1 to 1:1, 10.8:1 to 1:1, 10.7:1 to 1:1, 10.6:1 to 1:1, 10.5:1 to 1:1, 10.4:1 to 1:1, 10.3:1 to 1:1, 10.2:1 to 1:1, 10.1:1 to 1:1, 10.0:1 to 1 :1, 9.9:1 to 1:1, 9.8:1 to 1:1, 9.7:1 to 1:1, 9.6:1 to 1:1, 9.5:1 to 1:1, 9.4:1 to 1:1, 9.3:1 to 1:1, 9.2:1 to 1:1, 9.1:1 to 1:1, 9.0:1 to 1:1, 8.9:1 to 1:1, 8.8:1 to 1:1, 8.7:1 to 1:1, 8.6:1 to 1:1, 8.5:1 to 1:1, 8.4:1 to 1:1, 8.3:1 to 1:1, 8.2:1 to 1:1, 8.1:1 to 1:1, 8.0:1 to 1:1, 7.9:1 to 1:1, 7.8:1 to 1:1, 7.7:1 to 1:1, 7.6:1 to 1:1, 7.5:1 to 1:1, 7.4:1 to 1:1, 7.3:1 to 1:1, 7.2:1 to 1:1, 7.1:1 to 1:1, 7.0:1 to 1:1, 6.9:1 to 1:1, 6.8:1 to 1:1, 6.7:1 to 1:1, 6.6:1 to 1:1, 6.5: 1 to 1:1, 6.4:1 to 1:1, 6.3:1 to 1:1, 6.2:1 to 1:1, 6.1:1 to 1:1, 6.0:1 to 1:1, 5.9:1 to 1:1, 5.8:1 to 1:1, 5.7:1 to 1:1, 5.6:1 to 1:1, 5.5:1 to 1:1, 5.4:1 to 1:1, 5.3:1 to 1:1, 5.2:1 to 1:1, 5.1:1 to 1:1, 5.0:1 to 1:1, 4.9:1 to 1:1, 4.8:1 to 1:1, 4.7:1 to 1:1, 4.6:1 to 1:1, 4.5:1 to 1:1, 4.4:1 to 1:1, 4.3:1 to 1:1, 4.2:1 to 1:1, 4.1:1 to 1:1, 4.0:1 to 1:1, 3.9:1 to 1:1, 3.8:1 to 1:1, 3.7:1 to 1:1, 3.6:1 to 1:1, 3.5:1 to 1:1, 3.4:1 to 1:1, 3.3:1 to 1:1, 3.2:1 to 1:1, 3.1:1 to 1:1, 3.0:1 to 1:1, 2.9:1 to 1:1, 2.8:1 to 1:1, 2.7:1 to 1:1, 2.6:1 to 1:1, 2.5:1 to 1:1, 2.4:1 to 1:1, 2.3:1 to 1:1, 2.2:1 to 1:1, 2.1:1 to 1:1 1, 2.0:1 to 1:1, 1.9:1 to 1:1, 1.8:1 to 1:1, 1.7:1 to 1:1, 1.6:1 to 1:1, 1.5:1 to 1:1, 1.4:1 to 1:1, 1.3:1 to 1:1, 1.2:1 to 1:1, 1.1:1 to 1:1, 0.9:1 to 1:1, 0.8:1 to 1:1, 0.7:1 to 1:1, 0.6:1 to 1:1, 0.5:1 to 1:1, 0.4:1 to 1:1, 0.3:1 to 1:1, 0.2:1 to 1:1 or 0.1:1 to 1:1; or any range formed by any two of the foregoing ratios, including any sub-ratios therein. The aforementioned ratio typically refers to the number of moles of copper (on an atomic basis) relative to the number of moles of copper auxiliary additives; however, this ratio can also be used to express the number of moles of copper(I) salt relative to the number of moles of copper auxiliary additives.

[0149] After combining a copper (I) salt and copper auxiliary additives with a carrier, as described herein, the composition (e.g., a biocidal composition) or the resulting material can be molded into a desired article (e.g., a plastic article) or applied to a surface. Where the composition contains, for example, paints, varnishes, UV-curable compositions, etc., such composition can be applied to a surface as a layer, wherein any layer can have a transmittance of visible light as described elsewhere herein. Examples of surfaces to which biocidal compositions can be applied include wood, polymers, metals, glass, ceramics, stone, concrete, cement, minerals, drywall, bitumen, or any combination thereof. Examples of articles that can be formed using the compositions described herein include housings or casings for electronic devices (e.g., mobile phones, smartphones, tablets, video players, information terminal devices, laptops), building structures (e.g., countertops, walls, decorations, ceilings, floors, facades, and finishes), appliances (e.g., cooktops, refrigerator doors, and dishwasher doors), information displays (e.g., whiteboards), automotive parts (e.g., dashboards, windshields, window components), and high-touch surfaces (e.g., computer mice, computer keyboards, railings, doors, door handles, door pushers, telephones, telephone buttons, or elevator buttons). The articles can be formed by any method known in the art, such as by molding the biocidal composition into granules or masterbatch and then extruding, molding (e.g., injection molding), or otherwise shaping the articles into a desired form. In some instances, the entire article may comprise the biocidal composition (e.g., the entire article is formed from the biocidal composition). In some instances, only a portion of the article may be formed from the biocidal composition (e.g., by adhering, laminating, coating, or otherwise attaching the biocidal composition to a larger article), thereby facilitating a lower amount of the biocidal composition used in the larger article. In some instances, a method of forming an article is disclosed, comprising providing granules or masterbatch of the biocidal composition and then forming the article therefrom by any known technique, such as extrusion or molding (e.g., injection molding). In some instances, a method of preparing granules is disclosed, comprising molding the biocidal composition into granular shapes. In some instances, a method of preparing masterbatch is disclosed, comprising mixing a concentrated form of the biocidal composition. In some aspects, the biocidal composition is not in the form of molded articles, such as injection-molded or extruded articles. In some aspects, the biocidal composition is in liquid form under ambient conditions (1 atm (about 101.3 kPa) and 20°C).

[0150] The compositions described herein may contain pigments to impart color. Therefore, coatings or layers made from such compositions can exhibit a variety of colors, depending on the carrier color, carrier mixture, and particle loading. Furthermore, it is considered that the compositions and / or coatings described herein will not exhibit an adverse effect on paint adhesion, as measured by ASTM D4541. In some instances, 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.

[0151] One or more examples of the biocidal compositions disclosed herein may comprise a copper (I) salt (which may optionally be pretreated with a pretreatment solution), a copper auxiliary additive, and a carrier having a loading level of the copper (I) salt, such that the composition may exhibit resistance or preservative properties against the presence or growth of contaminants (e.g., microorganisms). Contaminants include fungi, bacteria, viruses, molds, mildews, algae, and combinations thereof. In some instances, the presence of contaminants in materials (e.g., paints, varnishes) may cause color changes in the composition, may reduce the integrity of the composition, and may negatively affect various properties of the composition. By including a minimum loading of copper(I) salt (e.g., 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less; alternatively or additionally, the following amounts: 0% or more, e.g., greater than 0% by weight, 0.01% or more, 0.05% or more, 0.1% or more, 0.5% or more, 1% or more, 2% or more, 3% or more, or 4% or more, based on the weight of the carrier or composition) and copper auxiliary additives in a carrier, contaminants can be eliminated or reduced. In some instances, the composition may not contain certain components when contaminants are eliminated or reduced. Therefore, when used in known compositions that do not contain copper(I) salt, formulations in one or more examples of the compositions described herein can have greater flexibility and variation than previously possible.

[0152] According to examples of this disclosure, the biocidal composition may comprise a carrier, a copper auxiliary additive, and a copper(I) salt, which has been or has not been pretreated with a pretreatment solution before being combined with the copper auxiliary additive and the carrier. A copper(I) salt that has been pretreated with a pretreatment solution may be referred to as a "treated copper(I) salt." The treated copper(I) salt may be present in the pretreatment solution (e.g., dissolved and / or suspended therein), and the pretreatment solution can then be combined with the copper auxiliary additive and the carrier, optionally without the intermediate step of separating the treated copper(I) salt from the pretreatment solution.

[0153] In some instances, the pretreatment solution may contain ammonia-based materials, and examples may include ammonia and ammonium buffer solutions. For instance, the pretreatment solution may contain ammonium chloride and / or ammonium phosphate. Ammonium buffer solutions may be prepared using any suitable materials or combinations of materials to provide an ammonium buffer solution with the desired pH, and examples may include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, monoammonium phosphate (NH4H2PO4), ammonium carbonate, and ammonium hydroxide.

[0154] In some instances, the pretreatment solution may contain an ammonia-based and / or amine-based solution with a pH of 8 to 12, 8 to 11, 8 to 10, 8 to 9, 9 to 12, 9 to 11, 9 to 10, or 10 to 12.

[0155] In some instances, the pretreatment solution may contain Group (I) hydroxides and / or Group (II) hydroxides. In some instances, the pretreatment solution may contain a hard base, examples of which may include potassium hydroxide and sodium hydroxide. Group (I) hydroxides, Group (II) hydroxides, and / or hard bases may be used alone or in combination with other materials to provide a treatment solution adapted to react with copper when used for treating copper (I) salts. In some instances, Group (I) hydroxides, Group (II) hydroxides, and / or hard bases are used to form a pretreatment solution with a pH of at least 9.

[0156] In some instances, the pretreatment solution may be an alkaline buffer containing one or more components that provide a desired pH and / or a desired chemical group (e.g., amine-based or ammonium-based groups). Examples of suitable alkaline buffers may include phosphate buffers, borate buffers, ammonium buffers, carbonate buffers, and combinations thereof. For example, an alkaline buffer may contain ammonium dihydrogen phosphate, potassium dihydrogen phosphate monobasic, diammonium hydrogen phosphate, monoammonium phosphate (NH4H2PO4), ammonium carbonate, ammonium hydroxide, boric acid, sodium borate (e.g., borax decahydrate), potassium chloride, sodium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, phosphoric acid, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium carbonate, ammonium carbonate, potassium bicarbonate, sodium bicarbonate, and ammonium bicarbonate. In one instance, the alkaline buffer may contain potassium dihydrogen phosphate and disodium hydrogen phosphate. In another instance, the alkaline buffer may contain potassium dihydrogen phosphate and sodium hydroxide. In another example, the alkaline buffer may contain boric acid, potassium chloride, and sodium hydroxide. In another example, the alkaline buffer may contain ammonium chloride, ammonium dihydrogen phosphate, and potassium dihydrogen phosphate. In some examples, the pH of the alkaline buffer is at least 9. For example, the pH of the alkaline buffer may be at least 9, at least 9.5, at least 10, at least 10.5, or at least 11. In some examples, the pH of the alkaline buffer may be 9 to 12, 9.5 to 12, 10 to 12, 10.5 to 12, 11 to 12, 9 to 11.5, 9.5 to 11.5, 10 to 11.5, 10.5 to 11.5, 11 to 11.5, 9 to 11, 9.5 to 11, 10 to 11, 10.5 to 11, 9 to 10.5, 9.5 to 10.5, 10 to 10.5, 9 to 10, or 9.5 to 10.

[0157] The pH of the pretreatment solution can be between 7 and 12. For example, the pH of the pretreatment solution can be between 8 and 12 or between 8.5 and 10.5. In some instances, the pH of the pretreatment solution can be 7 to 12, 7 to 11.5, 7 to 11, 7 to 10.5, 7 to 10, 7 to 9.5, 7 to 9, 7 to 8, 7.5 to 12, 7.5 to 11.5, 7.5 to 11, 7.5 to 10.5, 7.5 to 10, 7.5 to 9.5, 7.5 to 9, 7.5 to 8, 8 to 12, 8 to 11.5, 8 to 11, 8 to 10.5, 8 to 10, or 8 to 9. 5, 8 to 9, 8.5 to 12, 8.5 to 11.5, 8.5 to 11, 8.5 to 10.5, 8.5 to 10, 8.5 to 9.5, 8.5 to 9, 9 to 12, 9 to 11.5, 9 to 11, 9 to 10.5, 9 to 10, 9 to 9.5, 9.5 to 12, 9.5 to 11.5, 9.5 to 11, 9.5 to 10.5, 9.5 to 10, 10 to 12, 10 to 11.5 or 10 to 11.

[0158] In some instances, the amount and / or pH of the pretreatment solution can be selected such that the pH of the combined mixture of the carrier and copper auxiliary additive, as well as the treated copper(I) salt (e.g., copper(I) salt already treated with the pretreatment solution), is within a predetermined range of the initial pH of the carrier (e.g., the pH of the carrier before being combined with the treated copper-containing material). For example, the amount and / or pH of the pretreatment solution for treating the copper(I) salt can be selected such that the pH of the mixture of the carrier and copper auxiliary additive, as well as the treated copper(I) salt, is within ±1 unit of the initial pH of the carrier. In some instances, the amount and / or pH of the pretreatment solution for treating the copper(I) salt can be selected such that the pH of the mixture of the carrier and copper auxiliary additive, as well as the treated copper(I) salt, is within ±0.5 or even 0.3 units of the initial pH of the carrier. Without wishing to be bound by any theory, it is considered that in some applications, the addition of a solution or suspension of the treated copper(I) salt that significantly affects the total volume and / or pH of the carrier may cause undesirable changes in one or more properties of the carrier. For example, when the carrier is paint, large changes in volume and / or pH after the addition of treated copper (I) salt may undesirably affect other components of the paint or the properties of the paint, such as the color or dispersibility (e.g., pigment dispersibility) of one or more materials in the paint.

[0159] In some instances, the copper(I) salt may be neutralized before being combined with the support. In some instances, and where it is not desirable to be bound by theory, neutralization is performed to prevent the copper(I) salt, which is more acidic or basic than the support, from destabilizing the support. For example, the copper(I) salt may be neutralized to a pH of 7–10, such as 7–8, 7–9, 8–10, 8–9, or 9–10, or any subrange thereof. In some instances, the pH of the copper(I) salt may be adjusted to within 3 pH units of the support (e.g., within 2.5, 2, 1.5, 1.2, 1, 0.8, 0.5, or 0.2 pH units).

[0160] Copper(I) salts can be treated in the pretreatment solution for any amount of time, for example, from 5 minutes to 24 hours or from 1 hour to 12 hours, and all ranges and subranges in between. In some instances, copper(I) salts can be pretreated in the pretreatment solution for more than 5 minutes, more than 10 minutes, more than 1 hour, more than 2 hours, more than 5 hours, more than 10 hours, more than 15 hours, more than 20 hours, more than 24 hours, or more than 48 hours. For example, copper(I) salt can be pretreated in a pretreatment solution for 5 minutes to 72 hours, 5 minutes to 48 hours, 5 minutes to 36 hours, 5 minutes to 24 hours, 5 minutes to 20 hours, 5 minutes to 10 hours, 5 minutes to 5 hours, 5 minutes to 2 hours, 10 minutes to 72 hours, 10 minutes to 48 hours, 10 minutes to 36 hours, 10 minutes to 24 hours, 10 minutes to 20 hours, 10 minutes to 10 hours, 10 minutes to 5 hours, 10 minutes to 2 hours, 60 minutes to 72 hours, 60 minutes to 48 hours, 60 minutes to 36 hours, 60 minutes to 24 hours, 60 minutes to 20 hours, 60 minutes to 10 hours, 60 minutes to 5 hours, 60 minutes to 5 hours, etc. The timeframes are: 60 minutes to 2 hours, 2 hours to 72 hours, 2 hours to 48 hours, 2 hours to 36 hours, 2 hours to 24 hours, 2 hours to 20 hours, 2 hours to 10 hours, 2 hours to 5 hours, 5 hours to 72 hours, 5 hours to 48 hours, 5 hours to 36 hours, 5 hours to 24 hours, 5 hours to 20 hours, 5 hours to 10 hours, 10 hours to 72 hours, 10 hours to 48 hours, 10 hours to 36 hours, 10 hours to 24 hours, 10 hours to 20 hours, 20 hours to 72 hours, 20 hours to 48 hours, 20 hours to 36 hours, 20 hours to 24 hours, 24 hours to 72 hours, or 24 hours to 48 hours. In some instances, the copper (I) salt can be treated in a pretreatment solution for a predetermined period of time and then immediately combined with a carrier and copper auxiliary additives. In other instances, the copper (I) salt can be treated in a pretreatment solution for a minimum time and immediately combined with the carrier and copper auxiliary additive, and / or stored for a period of time before combination with the carrier and copper auxiliary additive. In some instances, the mixture of treated copper (I) salt and pretreatment solution can be directly combined with the carrier and copper auxiliary additive without immediately separating the treated copper (I) salt from the pretreatment solution. In some instances, after the pretreatment period, before combining the mixture of treated copper (I) salt and pretreatment solution with the carrier and copper auxiliary additive, the mixture can be combined with one or more other materials (e.g., a solvent or another buffer).

[0161] Without wishing to be bound by any particular theory, it is assumed that copper(I) salts, when combined with copper auxiliary additives, will at least partially or completely dissolve, and that copper ions from copper(I) salts may cause changes in the antimicrobial efficacy and / or color of the carrier.

[0162] Without wishing to be bound by any particular theory, it is assumed that the treated copper (I) salt, pretreated with the pretreatment solution as described herein, can provide a complexing or precipitating agent that, when combined with a carrier and copper-based additives, can reduce or eliminate the formation of copper-based species that would otherwise cause changes in the antimicrobial efficacy and / or color of the carrier, or may cause the antimicrobial efficacy and / or color to remain substantially unchanged over a given time period (e.g., at least 7 days, at least 20 days, at least 30 days, at least 60 days, at least 90 days, at least 120 days, at least 150 days, at least 180 days, at least 270 days, at least 1 year, at least 1.5 years, at least 2.0 years, at least 2.5 years, at least 3.0 years, at least 3.5 years, at least 4.0 years, at least 4.5 years, or at least 5.0 years). In one instance, when copper(I) salts are pretreated with monoammonium phosphate, a copper-based complex of CuH₂PO₄ can be formed. This stabilizes the copper ions released from the copper(I) salt and prevents the formation of other copper-based complexes that would otherwise cause changes in the antimicrobial efficacy and / or color of the carrier. It is also believed that, when combined with a carrier and copper-based additives, copper(I) salts can reduce or eliminate the formation of copper-based complexes that would otherwise cause changes in the antimicrobial efficacy and / or color of the carrier, or may cause the antimicrobial efficacy and / or color to remain substantially unchanged over a given period of time. Stabilizing the antimicrobial efficacy and / or color of the carrier may include preventing the antimicrobial efficacy from decreasing below a certain level (e.g., below a 3 logarithmic reduction) and / or reducing color shift of the carrier after mixing. For example, in paint, varnish, or UV-curable applications, when copper is added to a paint, varnish, or UV-curable composition, copper may affect its antimicrobial efficacy and / or color upon initial mixing, and / or may affect its antimicrobial efficacy and / or color over time during storage and / or after use. In some instances, a combination of copper(I) salts and copper auxiliary additives may maintain antimicrobial efficacy, prevent antimicrobial efficacy from decreasing below a certain level (e.g., below 3 logarithmic reduction), reduce color changes in the mixture, or any combination thereof, compared to copper(I) salts without copper auxiliary additives or copper auxiliary additives without copper(I) salts. In some instances, treated copper(I) salts and copper auxiliary additives may reduce color changes in the carrier and / or increase the stability of the carrier color over time, compared to copper(I) salts without copper auxiliary additives or copper (I) salts without copper(I) salt.

[0163] In one instance, the biocidal composition may exhibit one or more of the following effects: (1) a greater than 3 log reduction in the concentration of microorganisms selected from Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-CoV-2, and mixtures thereof; (2) a minimized color change of the biocidal composition relative to the color change of a mixture of a carrier and a copper(I) salt in the absence of a copper auxiliary additive or a carrier and a copper auxiliary additive without copper(I) salt; or (3) any combination thereof. Antimicrobial efficacy may be measured, as described elsewhere herein, such as by using EPA testing.

[0164] In one instance, a biocidal composition containing a carrier, a copper (I) salt, and a copper auxiliary additive exhibits superior antimicrobial efficacy over time (e.g., at least 7 days, or any other time period disclosed herein, such as at least 30 days or at least 90 days) compared to otherwise identical compositions that do not contain a copper auxiliary additive or do not contain a copper (I) salt (e.g., copper in a specified amount, such as 0.01 at.% to 10 at.% or 0.01 at.% to 2 at.%; copper (I) salt in a composition; and / or a molar ratio of copper to copper auxiliary additive of 1:0.1 to 1:25). Similarly, in some instances, as disclosed elsewhere herein, such biocidal compositions also exhibit minimal color change (e.g., color difference and / or color shift) compared to otherwise identical compositions.

[0165] In one example, when the biocidal composition forms a coating (e.g., a dry film) or article within one day of preparing the biocidal composition and said coating or article is stored under 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), the biocidal composition is used to form a coating (e.g., a dry film) or article within one day of preparing the biocidal composition and said coating or article is stored under 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). 0 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 When a stored coating or stored article is formed after 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, the stored coating or article exhibits a concentration of microorganisms selected from the group consisting of a 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). A decrease of 5 log-reduction or greater; alternatively or additionally, a decrease of 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: Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-CoV-2, and mixtures thereof. Generally, and where it is not desired to be bound by theory, the above characteristics are considered to indicate an extension of the antimicrobial efficacy of the coating (e.g., dry film) or article containing the biocidal composition over time. Antimicrobial efficacy can be measured as described elsewhere herein, such as by using EPA testing.

[0166] As used herein, the terms “lasting X days” or “lasting X years” (where X is a number) mean that the extension of a specified property lasts at least X days (or X years). The extension of a specified property may last for a longer period of time, and after such a long period, the specified property (e.g., logarithmic decrease or color value) may begin to decrease; however, “lasting X days” (or “lasting X years”) is satisfied if the specified property exists within X days (or X years). In this respect, the terms “lasting X days” and “lasting at least X days” are synonymous.

[0167] In one instance, when the biocidal composition is stored as a liquid (e.g., aqueous) composition 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 When a stored liquid (e.g., aqueous) composition or suspension is formed within a day (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), the coating or article prepared from said stored liquid (e.g., aqueous) composition or suspension exhibits a concentration of microorganisms selected from the group consisting of more than 1 logarithmic reduction (e.g., greater than 2.5 logarithmic reduction, greater than 3 logarithmic reduction, greater than 3.5 logarithmic reduction, greater than 4 logarithmic reduction, etc.) within one day. A reduction of 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: Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, Escherichia coli, SARS-CoV-2, and mixtures thereof. Generally, without being bound by theory, the above characteristics are considered to indicate antimicrobial efficacy of the coating (e.g., dry film) or article after a period of storage of the biocidal composition in liquid (e.g., aqueous solution) form (e.g., paint cans stored on shelves or masterbatch awaiting extrusion). Antimicrobial efficacy can be measured, as described elsewhere herein, such as by using EPA testing.

[0168] In one instance, minimizing color change corresponds to the CIE ΔE of the biocidal composition. * Values ​​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 (V):

[0169] (V)

[0170] Where L * a * and b * It is a CIE L of biocidal composition * a * and b * Value, and L * 对照 a * 对照 and b * 对照 It is a CIE L composition that is otherwise identical without copper(I) salt or copper auxiliary additives. * a * and b * value.

[0171] In one example, the biocidal composition or the film prepared from said biocidal composition exhibits (1) transmittance as measured at each wavelength from 400 nm to 700 nm, and / or (2) average transmittance as measured in the wavelength range from 400 nm to 700 nm, which may be 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 up to Less than 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 30 µm. The average transmittance is calculated by summing the transmittance at each wavelength between 400 nm and 700 nm and dividing by the total number of such wavelengths.

[0172] In one example, when measured at a thickness of 30 µm, the transmittance exhibited by the biocidal composition or its membrane, as measured at each wavelength from 400 nm to 700 nm, can be within 20 percent of the second transmittance of the otherwise identical composition or its membrane without copper (I) salt or copper auxiliary additives; including, for example, within 19.5 percent, or within 19.0 percent, or within 18.5 percent, or within 18.0 percent, or within 17.5 percent, or within 17.0 percent, or within 16.5 percent, or within 16.0 percent, or within 15.5 percent, or within 15.0 percent, or within 14.5 percent, or within 14.0 percent, or within 13.5 percent, or within 1 Within 3.0 percentage points, or within 12.5 percentage points, or within 12.0 percentage points, or within 11.5 percentage points, or within 11.0 percentage points, or within 10.5 percentage points, or within 10.0 percentage points, or within 9.9 percentage points, or within 9.8 percentage points, or within 9.7 percentage points, or within 9.6 percentage points, or within 9.5 percentage points, or within 9.4 percentage points, or within 9.3 percentage points, or within 9.2 percentage points, or within 9.1 percentage points, or within 9.0 percentage points, or within 8.9 percentage points, or within 8.8 percentage points, or within 8.7 percentage points, or within 8.6 percentage points, or within 8.5 percentage points, or within 8.4 percentage points, or within 8.3 percentage points, or within 8. Within 8.2 percentage points, or within 8.1 percentage points, or within 8.0 percentage points, or within 7.9 percentage points, or within 7.8 percentage points, or within 7.7 percentage points, or within 7.6 percentage points, or within 7.5 percentage points, or within 7.4 percentage points, or within 7.3 percentage points, or within 7.2 percentage points, or within 7.1 percentage points, or within 7.0 percentage points, or within 6.9 percentage points, or within 6.8 percentage points, or within 6.7 percentage points, or within 6.6 percentage points, or within 6.5 percentage points, or within 6.4 percentage points, or within 6.3 percentage points, or within 6.2 percentage points, or within 6.1 percentage points, or within 6.0 percentage points, or within 5.9 percentage points, or within 5.8 percentage points. Within, or within 5.7 percentage points, or within 5.6 percentage points, or within 5.5 percentage points, or within 5.4 percentage points, or within 5.3 percentage points, or within 5.2 percentage points, or within 5.1 percentage points, or within 5.0 percentage points, or within 4.9 percentage points, or within 4.8 percentage points, or within 4.7 percentage points, or within 4.6 percentage points, or within 4.5 percentage points, or within 4.4 percentage points, or within 4.3 percentage points, or within 4.2 percentage points, or within 4.1 percentage points, or within 4.0 percentage points, or within 3.9 percentage points, or within 3.8 percentage points, or within 3.7 percentage points, or within 3.6 percentage points, or within 3.5 percentage points, or within 3.4 percentage points, or within 3.Within 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. Within one point, 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.

[0173] In one example, the thickness of the film of the biocidal composition can be from 30 µm to 3000 µm, including, for example, 40 µm, or 50 µm, or 60 µm, or 70 µm, or 80 µm, or 90 µm, or 100 µm, or 110 µm, or 120 µm, or 130 µm, or 140 µm, or 150 µm, or 160 µm, or 170 µm, or 180 µm, or 190 µm, or 200 µm, or 210 µm, or 220 µm, or 230 µm, or 240 µm, or 250 µm, or 260 µm, or 270 µm, or 280 µm, or 290 µm, or 300 µm, or 310 µm, or 320 µm, or 330 µm, or 340 µm, or 350 µm. µm, or 360 µm, or 370 µm, or 380 µm, or 390 µm, or 400 µm, or 410 µm, or 420 µm, or 430 µm, or 440 µm, or 450 µm, or 460 µm, or 470 µm, or 480 µm, or 490 µm, or 500 µm, or 510 µm, or 520 µm, or 530 µm, or 540 µm, or 550 µm, or 560 µm, or 570 µm, or 580 µm, or 590 µm, or 600 µm, or 610 µm, or 620 µm, or 630 µm, or 640 µm, or 650 µm, or 660 µm, or 670 µm, or 680 µm, or 690 µm, or 700 µm µm, or 710 µm, or 720 µm, or 730 µm, or 740 µm, or 750 µm, or 760 µm, or 770 µm, or 780 µm, or 790 µm, or 800 µm, or 810 µm, or 820 µm, or 830 µm, or 840 µm, or 850 µm, or 860 µm, or 870 µm, or 880 µm, or 890 µm, or 900 µm, or 910 µm, or 920 µm, or 930 µm, or 940 µm, or 950 µm, or 960 µm, or 970 µm, or 980 µm, or 990 µm, or 1000 µm, or 1050 µm, or 1100 µm, or 1150 µm, or 1200 µm µm, or 1250 µm, or 1300 µm, or 1350 µm, or 1400 µm, or 1450 µm, or 1500 µm, or 1550 µm, or 1600 µm, or 1650 µm, or 1700 µm, or 1750 µm, or 1800 µm, or 1850 µm, or 1900 µm, or 1950 µm, or 2000 µm, or 2050 µm, or 2100 µmµm, or 2150 µm, or 2200 µm, or 2250 µm, or 2300 µm, or 2350 µm, or 2400 µm, or 2450 µm, or 2500 µm, or 2550 µm, or 2600 µm, or 2650 µm, or 2700 µm, or 2750 µm, or 2800 µm, or 2850 µm, or 2900 µm, or 2950 µm to 3000 µm; or 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 µm, or up to 170 µm, or up to 180 µm, or up to 190 µm, or up to 200 µm, or up to 210 µm, or up to 220 µm, or up to 230 µm, or up to 240 µm, or up to 250 µm, or up to 260 µm, or up to 270 µm, or up to 280 µm, or up to 290 µm, or up to 300 µm, or up to 310 µm, or up to 320 µm, or up to 330 µm, or up to 340 µm, or up to 350 µm, or up to 360 µm, or up to 370 µm, or up to 380 µm, or up to 390 µm, or up to 400 µm, or up to 410 µm, or up to 420 µm, or up to 430 µm, or up to 440 µm, or up to 450 µm, or up to 460 µm µm, or up to 470 µm, or up to 480 µm, or up to 490 µm, or up to 500 µm, or up to 510 µm, or up to 520 µm, or up to 530 µm, or up to 540 µm, or up to 550 µm, or up to 560 µm, or up to 570 µm, or up to 580 µm, or up to 590 µm, or up to 600 µm, or up to 610 µm, or up to 620 µm, or up to 630 µm, or up to 640 µm, or up to 650 µm, or up to 660 µm, or up to 670 µm, or up to 680 µm, or up to 690 µm, or up to 700 µm, or up to 710 µm, or up to 720 µm, or up to 730 µm, or up to 740 µm, or up to 750 µm, or up to 760 µm µm, or up to 770 µm, or up to 780 µm, or up to 790 µm, or up to 800 µm, or up to 810 µm, or up to 820 µm, or up to 830 µm, or up to 840 µm, or up to 850 µm, or up to 860 µm, or up to 870 µm, or up to 880 µm, or up to 890 µm, or up to 900 µm, or up to 910 µm, or up to 920 µm, or up to 930 µm, or up to 940 µm, or up to 950 µm, or up to 960 µm, or up to 970 µmµm, or up to 980 µm, or up to 990 µm; or up to 1000 µm, or up to 1050 µm, or up to 1100 µm, or up to 1150 µm, or up to 1200 µm, or up to 1250 µm, or up to 1300 µm, or up to 1350 µm, or up to 1400 µm, or up to 1450 µm, or up to 1500 µm, or up to 1550 µm, or up to 1600 µm, or up to 1650 µm, or up to 1700 µm, or up to 1750 µm, or up to 1800 µm, or up to 1850 µm, or up to 1900 µm, or up to 1950 µm, or up to 2000 µm, or up to 2050 µm, or up to 2100 µm, or up to 2150 µm, or up to 2200 µm. µm, or up to 2250 µm, or up to 2300 µm, or up to 2350 µm, or up to 2400 µm, or up to 2450 µm, or up to 2500 µm, or up to 2550 µm, or up to 2600 µm, or up to 2650 µm, or up to 2700 µm, or up to 2750 µm, or up to 2800 µm, or up to 2850 µm, or up to 2900 µm, or up to 2950 µm, or a range formed by any two of the aforementioned thicknesses; including any sub-ranges therein.

[0174] In one example, a method for preparing a biocidal composition is disclosed, the method comprising combining a copper (I) salt, a copper auxiliary additive, and a carrier. In some examples, the copper (I) salt is first combined with the copper auxiliary additive to form a mixture, and then the mixture is combined with the carrier to form a biocidal composition. In other examples, the copper (I) salt and the carrier are first combined to form a mixture, and then the mixture is combined with the copper auxiliary additive to form a biocidal composition. In still other examples, the carrier and the copper auxiliary additive are first combined to form a mixture, followed by the addition of the copper (I) salt.

[0175] In one example, a method is disclosed comprising applying a biocidal composition to a surface. The biocidal composition may comprise any of the components described elsewhere herein. In one example, the surface is or comprises wood, polymers (e.g., plastics or rubber), metals (e.g., steel, iron, copper, gold, silver, aluminum, tin, platinum, alloys thereof, or any combination thereof), glass (e.g., lithium aluminum silicate glass, borosilicate glass, chemically strengthened glass, or ion-exchange glass), ceramics, glass-ceramic, stone, concrete, cement, minerals, drywall, bitumen, or any combination thereof. In one example, the method of application to the surface may be any suitable method, including brushing (e.g., with a brush or applicator), spraying, spin coating, dip coating, etc., or any combination thereof. For example, the composition may be sprayed onto the surface. In some aspects of application to the surface, such as in sprayed compositions, copper (I) species (e.g., ions or salts) may be present at least partially in a solubilized form (e.g., promoted by complexation with copper auxiliary additives), although such copper (I) species may alternatively or additionally be present in a suspended form.

[0176] In one example, a method for improving or maintaining the antimicrobial efficacy of a biocidal composition (any biocidal composition disclosed herein) is disclosed, the method comprising: combining a carrier, a copper (I) salt, and a copper auxiliary additive, wherein the biocidal composition contains copper in an amount of 0.01 at.% to 10 at.%, and the carrier and the copper auxiliary additive are distinct. In some examples, the molar ratio of the amount of copper to the amount of the copper auxiliary additive is from 1:0.1 to 1:25. In some examples, the copper (I) salt is first combined with the copper auxiliary 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 otherwise identical composition in the absence of the copper auxiliary additive, or an otherwise otherwise identical composition without the copper (I) salt, or an otherwise otherwise identical composition without both the copper auxiliary additive and the copper (I) salt. In other examples, a method is provided to minimize color changes in a biocidal composition, wherein the copper auxiliary additive is any compound or formula disclosed herein (e.g., any compound of formulas (I) through (IV), such as compounds of formula (I), (II), (III), (IV), or any combination thereof). In other examples, a method is provided to minimize color changes in a biocidal composition, wherein the copper auxiliary additive is any compound disclosed herein, such as 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, methyl phosphate, dimethyl phosphate, trimethyl phosphate, butyl phosphate (e.g., n-butyl, sec-butyl, or tert-butyl), dibutyl phosphate (e.g., n-butyl, sec-butyl, and / or tert-butyl), tributyl phosphate (e.g., n-butyl, sec-butyl, and / or tert-butyl). Phenyl phosphate, diphenyl phosphate, triphenyl phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tri(2-ethylhexyl) phosphite, triisopropyl phosphite, tris(hydroxypropyl)phosphine, tributylphosphine, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole bromide, any salt thereof, or any combination thereof. In other examples, a method is provided to minimize color change of a biocidal composition, wherein the composition exhibits a greater than 3 logarithmic reduction in the 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. Antimicrobial efficacy can be measured, as described elsewhere herein, such as by using an EPA test. In other examples, a method is provided to minimize color changes in a biocidal composition, wherein the CIE ΔE of the biocidal material is... * Values ​​less than 10, such as those measured according to formula (V):

[0177] (V)

[0178] Where L * a * and b * It is a biocidal material CIE L * a * and b * Value, and L * 对照 a * 对照 and b * 对照 It is a CIE L composition that is otherwise identical without copper(I) salt or copper auxiliary additives. * a * and b * value.

[0179] In one instance, the biocidal composition exhibits a ΔE that may 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 formula (V):

[0180] (V)

[0181] Where L * a * and b * This refers to the CIE value of the biocidal composition after preparation, and then, within one day of preparation, the biocidal composition is stored at ambient temperature and 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, and L) * 对照 a * 对照 and b * 对照 It is the CIE value of a composition that is otherwise identical without copper (I) salt or copper auxiliary additives.

[0182] In one instance, this disclosure provides a biocidal additive formulation comprising a copper (I) salt and a copper auxiliary additive. In some aspects, the biocidal additive formulation may be a relatively concentrated formulation to be added to a carrier to provide a biocidal composition (also referred to herein as a "pre-solution"). In this aspect, in some aspects, the biocidal additive formulation may be in the form of a package that can be added by an end user to, for example, paint cans, clear compositions, etc., to impart antimicrobial properties to the paint can or clear composition without substantially affecting its color and / or transparency. Such biocidal additive formulations may also be added by paint or coating manufacturers during or after the production of large quantities of paint or coating compositions to impart, for example, desired antimicrobial properties. Examples of biocidal additive formulation forms may include powders, slurries, gels, liquids, concentrates, and solutions. In some aspects, the biocidal additive formulation comprises a dissolved copper (I) salt in the form of a copper complex, wherein the copper (I) salt is coordinated or otherwise associated with a copper auxiliary additive that promotes the solubility of the copper (I) salt. Without being bound by theory, it is considered that in some respects, it is desirable to first prepare a biocidal additive formulation for addition to a composition, rather than simply adding a copper salt to the composition, or simply adding the copper salt and copper auxiliary additive separately to the composition. For example, it is considered that in some cases, adding the copper salt alone or adding the copper salt and additive separately to the same composition (without premixing) may not allow the copper auxiliary additive to adequately promote the availability and / or persistence of copper(I) ions. For example, adding it alone may not allow the copper auxiliary additive to find and associate with the copper salt. However, in some respects, the separate addition of the copper salt and copper auxiliary additive may be sufficient, for example, when the additive is present at a sufficiently high concentration and / or the medium of the composition does not otherwise inhibit the ability of the additive and copper salt to aggregate together, such as due to viscosity, diffusion, or some other reason. In some instances, the biocidal additive formulation may contain an antioxidant package. The antioxidant package may contain a single component or a ternary mixture. Examples of antioxidant packages may include a primary antioxidant; a phenol, such as BHT; and a secondary antioxidant, such as Ultranox. TM 626, Weston TM430 ZP; thioester-based antioxidants (thiosynergists), such as dioctadecyl 3,3'-thiodipropionate; ascorbic acid esters, such as ascorbyl palmitate; or any combination thereof. In some instances, the biocidal additive formulation may contain a reducing agent. Examples of reducing agents may include ascorbic acid, hydroxylamine hydrochloride, various phosphines, sulfite compounds, oxalic acid, sodium thiosulfate, or any combination thereof. In some instances, the biocidal additive formulation may be in a sealed container containing an inert atmosphere. In some instances, the biocidal additive formulation is in liquid form under ambient conditions (1 atm (approximately 101.3 kPa) and 20°C).

[0183] In one example, the molar concentration of the copper(I) salt dissolved 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. mM, or 185 mM, or 190 mM, or 195 mM to 200 mM; or 20 mM to 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 mM, or up to 165 mM, or up to 170 mM, or up to 175 mM, or up to 180 mM, or up to 185 mM, or up to 190 mM, or up to 195 mM; or a range formed by any two of the aforementioned molar concentrations; including any subranges therein.

[0184] In some instances, the biocidal additive formulation may contain a copper auxiliary additive at a molar concentration 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. 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 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 up to 0.115 mM, or up to 0.120 mM, or up to 0.125 mM, or up to 0.130 mM, or up to 0.135 mM, or up to 0.140 mM, or up to 0.145 mM, or up to 0.150 mM, or up to 0.155 mM, or up to 0.160 mM, or up to 0.165 mM, or up to 0.170 mM, or up to 0.175 mM, or up to 0.180 mM, or up to 0.185 mM, or up to 0.190 mM, or up to 0.195 mM, or up to 0.200 mM, or up to 0.205 mM, or up to 0.210 mM, or up to 0.215 mM, or up to 0.220 mM, or up to 0.225 mM, or up to 0.230 mM, or up to 0.235 mM, or up to 0.240 mM, or up to 0.245 mM, or up to 0.250 mM, or up to 0.255 mM, or up to 0.260 mM, or up to 0.265 mM, or up to 0.270 mM, or up to 0.275 mM, or up to 0.280 mM, or up to 0.285 mM, or up to 0.290 mM, or up to 0.295 mM, or up to 0.300 mM, or up to 0.305 mM, or up to 0.310 mM, or up to 0.315 mM, or up to 0.320 mM, or up to 0.325 mM, or up to 0.330 mM, or up to 0.335 mM, or up to 0.340 mM, or up to 0.345 mM, or up to 0.350 mM, or up to 0.355 mM, or up to 0.360 mM, or up to 0.365 mM, or up to 0.370 mM, or up to 0.375 mM, or up to 0.380 mM, or up to 0.385 mM, or up to 0.390 mM, or up to 0.395 mM, or up to 0.400 mM, or up to 0.405 mM, or up to 0.410 mM, or up to 0.415 mM, or up to 0.420 mM, or up to 0.425 mM, or up to 0.430 mM, or up to 0.435 mM, or up to 0.440 mM, or up to 0.445 mM, or up to 0.450 mM, or up 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. The concentrations are defined as follows: mM, or up to 0.580 mM, or up to 0.585 mM, or up to 0.590 mM, or up to 0.595 mM; or a range formed by any two of the aforementioned molar concentrations; including any subranges thereof.

[0185] In some aspects, based on the total weight of the composition, the complex of copper (I) salt and copper auxiliary additive is present in the composition (e.g., paints, coatings, films, solutions, suspensions, etc.) in the following amounts (wt.%): 0.01-2, 0.01-1.8, 0.01-1.6, 0.01-1.4, 0.01-1.2, 0.01-1, 0.01-0.8, 0.01-0.6, 0.01-0.4, 0.01-0.2, 0.01-0.1, 0.01-0.08, 0.01-0.06, 0.01-0.04, 0.01-0.02, 0.02-2, 0.02-1.8, 0.02-1.6, 0.02-1.4, 0.02-1.2, 0. 0.02-1, 0.02-0.8, 0.02-0.6, 0.02-0.4, 0.02-0.2, 0.02-0.1, 0.02-0.08, 0.02-0.06, 0.02-0.04, 0.04-2, 0.04-1.8, 0.04-1.6, 0.04-1.4, 0.04-1.2, 0. 04-1, 0.04-0.8, 0.04-0.6, 0.04-0.4, 0.04-0.2, 0.04-0.1, 0.04-0.08, 0.04-0.06, 0.06-2, 0.06-1.8, 0.06-1.6, 0.06-1.4, 0.06-1.2, 0.06-1, 0.06- 0.8, 0.06-0.6, 0.06-0.4, 0.06-0.2, 0.06-0.1, 0.06-0.08, 0.08-2, 0.08-1.8, 0.08-1.6, 0.08-1.4, 0.08-1.2, 0.08-1, 0.08-0.8, 0.08-0.6, 0.08-0. 4, 0.08-0.2, 0.08-0.1, 0.1-2, 0.1-1.8, 0.1-1.6, 0.1-1.4, 0.1-1.2, 0.1-1, 0.1-0.8, 0.1-0.6, 0.1-0.4, 0.1-0.2, 0.2-2, 0.2-1.8, 0.2-1.6, 0.2-1.4 0.2-1.2, 0.2-1, 0.2-0.8, 0.2-0.6, 0.2-0.4, 0.4-2, 0.4-1.8, 0.4-1.6, 0.4-1.4, 0.4-1.2, 0.4-1, 0.4-0.8, 0.4-0.6, 0.6-2, 0.6-1.8, 0.6-1.6, 0.6- 1.4, 0.6-1.2, 0.6-1, 0.6-0.8, 0.8-2, 0.8-1.8, 0.8-1.6, 0.8-1.4, 0.8-1.2, 0.8-1, 1-2, 1-1.8, 1-1.6, 1-1.4, 1-1.2, 1.2-2, 1.2-1.8, 1.2-1.6, 1.2-1.4, 1.4-2, 1.4-1.8, 1.4-1.6, 1.6-2, 1.6-1.8, or 1.8-2. In some aspects, such amounts are 0.06-0.6, 0.08-0.4, or 0.1-0.4. Such amounts refer to copper(I) salts (containing counterions) and copper auxiliary additives (e.g., a complex of CuBr and triphenyl phosphite containing the total mass of copper(I) ions, bromide ions, and triphenyl phosphite). In some aspects, such amounts can be achieved in a given composition by adding a biocidal additive formulation to the composition.

[0186] In some instances, biocidal additive formulations may contain copper(I) salts and copper auxiliary additives in any ratio disclosed elsewhere herein.

[0187] In some instances, the biocidal additive formulation may contain a solvent at a molar concentration of 0.8 mM to 8.00 mM, comprising, 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. 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 5.15mM, 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 up to 1.80 mM, or up to 1.85 mM, or up to 1.90 mM, or up to 1.95 mM, or up to 2.00 mM, or up to 2.05 mM, or up to 2.10 mM, or up to 2.15 mM, or up to 2.20 mM, or up to 2.25 mM, or up to 2.30 mM, or up to 2.35 mM, or up to 2.40 mM, or up to 2.45 mM, or up to 2.50 mM, or up to 2.55 mM, or up to 2.60 mM, or up to 2.65 mM, or up to 2.70 mM, or up to 2.75 mM, or up to 2.80 mM, or up to 2.85 mM, or up to 2.90 mM, or up to 2.95 mM, or up to 3.00 mM, or up to 3.05 mM, or up to 3.10 mM, or up to 3.15 mM, or up to 3.20 mM, or up to 3.25 mM, or up to 3.30 mM, or up to 3.35 mM, or up to 3.40 mM, or up to 3.45 mM, or up to 3.50 mM, or up to 3.55 mM, or up to 3.60 mM, or up to 3.65 mM, or up to 3.70 mM, or up to 3.75 mM, or up to 3.80 mM, or up to 3.85 mM, or up to 3.90 mM, or up to 3.95 mM, or up to 4.00 mM, or up to 4.0.05 mM, or up to 4.10 mM, or up to 4.15 mM, or up to 4.20 mM, or up to 4.25 mM, or up to 4.30 mM, or up to 4.35 mM, or up to 4.40 mM, or up to 4.45 mM, or up to 4.50 mM, or up to 4.55 mM, or up to 4.60 mM, or up to 4.65 mM, or up to 4.70 mM, or up to 4.75 mM, or up to 4.80 mM, or up to 4.85 mM, or up to 4.90 mM, or up to 4.95 mM, or up to 5.00 mM, or up to 5.05 mM, or up to 5.10 mM, or up to 5.15 mM, or up to 5.20 mM, or up to 5.25 mM, or up to 5.30 mM, or up to 5.35 mM, or up to 5.40 mM. mM, or up to 5.45 mM, or up to 5.50 mM, or up to 5.55 mM, or up to 5.60 mM, or up to 5.65 mM, or up to 5.70 mM, or up to 5.75 mM, or up to 5.80 mM, or up to 5.85 mM, or up to 5.90 mM, or up to 5.95 mM, or up to 6.00 mM, or up to 6.05 mM, or up to 6.10 mM, or up to 6.15 mM, or up to 6.20 mM, or up to 6.25 mM, or up to 6.30 mM, or up to 6.35 mM, or up to 6.40 mM, or up to 6.45 mM, or up to 6.50 mM, or up to 6.55 mM, or up to 6.60 mM, or up to 6.65 mM, or up to 6.70 mM, or up to 6.75 mM. mM, or up to 6.80 mM, or up to 6.85 mM, or up to 6.90 mM, or up to 6.95 mM, or up to 7.00 mM, or up to 7.05 mM, or up to 7.10 mM, or up to 7.15 mM, or up to 7.20 mM, or up to 7.25 mM, or up to 7.30 mM, or up to 7.35 mM, or up to 7.40 mM, or up to 7.45 mM, or up to 7.50 mM, or up to 7.55 mM, or up to 7.60 mM, or up to 7.65 mM, or up to 7.70 mM, or up to 7.75 mM, or up to 7.80 mM, or up to 7.85 mM, or up to 7.90 mM, or up to 7.95 mM; or a range formed by any two of the foregoing molar concentrations; including any subranges therein. Examples of organic solvents in biocidal compositions and biocidal additive formulations may include acetonitrile and ethyl acetate.

[0188] In one example, this disclosure provides a biocidal composition comprising a carrier; a copper (I) salt; and a copper auxiliary additive different from the carrier. The copper auxiliary additive may be a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof.

[0189] ;

[0190] ;

[0191] ;

[0192] ;

[0193] Each R 1 It can be independently selected from hydrogen, C1-C 20 Alkyl, aryl and aryl (C1-C4) alkyl; wherein each R 2 It can be independently selected from C1-C that are optionally substituted with fluorine. 20 Alkyl groups, and aryl groups (e.g., phenyl groups); wherein each R 3 It can be independently selected from C1-C cells that are optionally substituted with hydroxyl groups. 20 Alkyl; wherein each R 4 It can be independently selected from C1-C 20 Alkyl group; wherein X is an anti-counterionic group; and wherein after storing the biocidal composition or its film or article at ambient temperature and relative humidity for 50 days, the biocidal composition, its film or article exhibits antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing.

[0194] In some instances, the copper (I) salt may be copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) tetrafluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof.

[0195] In some instances, the copper auxiliary additive may be 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof.

[0196] In some instances, the biocidal composition may be in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV-curable composition, UV-curable composition, or plastic.

[0197] In some instances, the carrier may comprise acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof.

[0198] In some instances, the copper(I) salt may be copper(I) bromide; the copper auxiliary additive may be trimethyl phosphite, triethyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after 60 days of storage may be at least 3 logarithmic.

[0199] In some instances, the copper auxiliary additive may be triethyl phosphite; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after 150 days of storage may be at least 3 logarithmic.

[0200] In some instances, the copper(I) salt may be tetra(acetonitrile)copper(I)hexafluorophosphate; the copper auxiliary additive may be 2-ethylhexyl phosphate; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after one year of storage may be at least 3 logarithmic.

[0201] In some instances, the copper(I) salt may be copper(I) bromide; the copper auxiliary additive may be trimethyl phosphite, triethyl phosphite, tris(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and the biocidal composition may exhibit a ΔE of less than 6, as calculated according to the following:

[0202] ;and

[0203] L * a * and b * The CIE value of the biocidal composition can be determined after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It can be the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

[0204] In some instances, each R 1 It can be selected from hydrogen, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl; each R 2 It may be selected from C1-C5 alkyl (or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) and phenyl, optionally fluorinated; each R3 It may be selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) optionally substituted with hydroxyl groups; and each R 4 It can be selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl).

[0205] In another example, this disclosure provides a biocidal composition comprising a carrier; a copper (II) salt; and a copper auxiliary additive different from the carrier; wherein, after the biocidal composition or its membrane has been stored at ambient temperature and relative humidity for 90 days, the biocidal composition or its membrane exhibits antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing; and wherein, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the biocidal composition or its membrane or article exhibits a transmittance of at least 98%.

[0206] In some instances, the thickness of the film formed by the biocidal composition can be from 30 µm to 1000 µm.

[0207] In some instances, the copper auxiliary additive may be a compound of formula (II), a compound of formula (III), or any combination thereof:

[0208] ;

[0209] ;

[0210] Each R 2 It may be independently selected from C1-C5 alkyl (or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) and phenyl, which are optionally fluorinated; and wherein each R 3 It can be independently selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) that are optionally substituted with hydroxyl groups.

[0211] In some instances, the copper (I) salt may be copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof.

[0212] In some instances, the copper auxiliary additive may be triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, or any combination thereof.

[0213] In some instances, the copper (I) salt may be copper bromide (I), copper iodide (I), or both; and the copper auxiliary additive may be triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof.

[0214] In some instances, the biocidal composition may exhibit a ΔE of less than 6, as calculated according to the following:

[0215] ;

[0216] L * a * and b * The CIE value of the biocidal composition can be determined after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It may be a composition that is otherwise identical without the copper (I) salt or the copper auxiliary additive; and the antimicrobial efficacy exhibited by the biocidal composition or its film after 150 days of storage may be at least 3 logarithmic.

[0217] In some instances, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the transmittance exhibited by the biocidal composition or its membrane can be within 10 percentage points of the second transmittance of the otherwise identical composition or its membrane without the copper (I) salt or the copper auxiliary additive.

[0218] In yet another example, this disclosure provides a biocidal composition comprising a carrier, a copper (I) salt, and a copper auxiliary additive different from the carrier. The copper auxiliary additive may be a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof.

[0219] ;

[0220] ;

[0221] ;

[0222] ;

[0223] Each R 1 It can be independently selected from hydrogen, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl; wherein each R 2 It can be independently selected from C1-C5 alkyl (or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) and phenyl, which are optionally fluorinated; wherein each R 3 It can be independently selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) optionally substituted with hydroxyl groups; wherein each R 4 The biocidal composition may be independently selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl); wherein X may be an anti-counterion; wherein the copper (I) salt may be copper halide (I), tetra(acetonitrile) copper (I) salt or any combination thereof; and wherein after storing the biocidal composition or its film or article at ambient temperature and ambient relative humidity for 50 days, the biocidal composition, the film or article thereof exhibits an antimicrobial efficacy of at least 3 logarithmic, as measured by EPA testing.

[0224] In some instances, the copper(I) salt may be copper chloride(I), copper bromide(I), copper iodide(I), tetra(acetonitrile)copper(I) hexafluorophosphate, tetra(acetonitrile)copper(I) tetrafluoroborate, tetra(acetonitrile)copper(I) perchlorate, tetra(acetonitrile)copper(I) trifluoromethanesulfonate, tetra(acetonitrile)copper(I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

[0225] In some instances, the copper auxiliary additive may be 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphite, trimethyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof.

[0226] In some instances, the biocidal composition may be in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV-curable composition, UV-curable composition, or plastic.

[0227] In some instances, the carrier may comprise acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof.

[0228] In some instances, the copper (I) salt may be copper bromide (I), copper iodide (I), or both; the copper auxiliary additive may be trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and the antimicrobial efficacy exhibited by the biocidal composition or its film or article after 60 days of storage may be at least 3 logarithmic.

[0229] In yet another example, this disclosure provides a biocidal additive formulation comprising a copper (I) salt and a copper auxiliary additive. After storing a biocidal composition comprising the biocidal additive formulation and a carrier, a film or article thereof comprising the biocidal composition, and at ambient temperature and relative humidity for one year, the biocidal composition, the film thereof, or the article thereof exhibits an antimicrobial efficacy of at least 3 logarithmic, as measured by EPA testing. The biocidal composition exhibits a ΔE that may be less than 6, as calculated according to the following:

[0230] ;and

[0231] L * a * and b * The CIE value of the biocidal composition can be determined after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It can be the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

[0232] In some instances, the copper auxiliary additive may be a compound of formula (I), a compound of formula (II), a compound of formula (III), or any combination thereof:

[0233] ;

[0234] ;

[0235] ;

[0236] Each R 1 It can be independently selected from hydrogen, C1-C 20 Alkyl, aryl, and benzyl; wherein each R 2 It can be independently selected from C1-C cells that are optionally substituted with hydroxyl groups or fluorine groups. 20Alkyl groups, and aryl groups (e.g., phenyl groups); and wherein each R 3 It can be independently selected from C1-C 20 alkyl.

[0237] In some instances, the copper(I) salt may be copper bromide(I), copper iodide(I), tetra(acetonitrile)copper(I) hexafluorophosphate, tetra(acetonitrile)copper(I) tetrafluoroborate, tetra(acetonitrile)copper(I) perchlorate, tetra(acetonitrile)copper(I) trifluoromethanesulfonate, tetra(acetonitrile)copper(I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

[0238] In some instances, the copper auxiliary additive may be 2-ethylhexyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof. In some instances, the molar concentration of the copper(I) salt dissolved in the biocidal additive formulation may be at least 20 mM.

[0239] In some instances, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the transmittance of the membrane of the biocidal composition can be at least 98%.

[0240] Although this disclosure has been described with reference to examples, accompanying drawings and diagrams, it is not limited thereto, but can be modified and altered by those skilled in the art without departing from the spirit and scope of this disclosure.

[0241] This article considers various aspects, some of which are elaborated in the following paragraphs. With explicit consideration, any aspect or part thereof can be combined to form a combination.

[0242] The first aspect relates to a biocidal composition comprising: a carrier; a copper (I) salt; and a copper auxiliary additive different from said carrier; wherein said copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof:

[0243] ;

[0244] ;

[0245] ;

[0246] ;

[0247] Each R 1 Independently selected from hydrogen, C1-C 20 Alkyl, aryl and aryl (C1-C4) alkyl; wherein each R2 Independently selected from C1-C cells optionally substituted with fluorine. 20 Alkyl groups, and aryl groups (e.g., phenyl groups); wherein each R 3 Independently selected from C1-C cells optionally substituted with hydroxyl groups. 20 Alkyl; wherein each R 4 Independently selected from C1-C 20 Alkyl group; wherein X is an anti-counterionic group; and wherein after storing the biocidal composition or its film or article at ambient temperature and ambient relative humidity for 50 days or at least 50 days (or any other time period disclosed herein), the biocidal composition, its film or article exhibits antimicrobial efficacy of at least 3 logarithmic killing, as measured by EPA testing.

[0248] The second aspect relates to the biocidal composition according to aspect 1, wherein the copper (I) salt is copper chloride (I), copper bromide (I), copper iodide (I), copper tetra(acetonitrile) (I) hexafluorophosphate, copper tetra(acetonitrile) (I) tetrafluoroborate, copper tetra(acetonitrile) (I) perchlorate, copper tetra(acetonitrile) (I) trifluoromethanesulfonate, copper tetra(acetonitrile) (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof.

[0249] The third aspect relates to a biocidal composition according to any one of the preceding aspects, wherein the copper auxiliary additive is 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof.

[0250] The fourth aspect relates to a biocidal composition according to any one of the preceding aspects, wherein the biocidal composition is in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV curing composition, UV curable composition or plastic.

[0251] The fifth aspect relates to a biocidal composition according to any one of the preceding aspects, wherein the carrier comprises acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof.

[0252] The sixth aspect relates to a biocidal composition according to any one of the preceding aspects, wherein the copper (I) salt is copper (I) bromide; wherein the copper auxiliary additive is trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and wherein the biocidal composition or the film or article thereof exhibits at least 3 logarithmic antimicrobial efficacy after storage for 60 days or at least 60 days (or any other time period disclosed herein).

[0253] The seventh aspect relates to a biocidal composition according to any one of the preceding aspects, wherein the copper auxiliary additive is triethyl phosphite, triphenyl phosphite, or both; and wherein the biocidal composition or its film or article exhibits at least 3 logarithmic antimicrobial efficacy after storage for 150 days or at least 150 days (or any other time period disclosed herein).

[0254] The eighth aspect relates to the biocidal composition according to aspects 1 to 5, wherein the copper(I) salt is tetra(acetonitrile)copper(I)hexafluorophosphate; wherein the copper auxiliary additive is 2-ethylhexyl phosphate; and wherein the biocidal composition or the film or article thereof exhibits at least 3 logarithmic antimicrobial efficacy after 1 year of storage.

[0255] The ninth aspect relates to the biocidal composition according to aspects 1 to 6, wherein the copper (I) salt is copper (I) bromide; wherein the copper auxiliary additive is trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and wherein the biocidal composition exhibits a ΔE less than 6, as calculated according to the following:

[0256] ;and

[0257] Where L * a * and b * The CIE value of the biocidal composition is the value obtained after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days or at least 150 days (or any other time period disclosed herein), and L * 对照 a * 对照 and b * 对照 It is the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

[0258] The tenth aspect relates to a biocidal composition according to any one of the foregoing aspects, wherein each R 1Selected from hydrogen, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl; wherein each R 2 Selected from C1-C5 alkyl (or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) and phenyl, optionally fluorinated; wherein each R 3 Selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) optionally substituted with hydroxyl groups; and wherein each R 4 Selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl).

[0259] The eleventh aspect relates to a biocidal composition comprising: a carrier; a copper (I) salt; and a copper auxiliary additive different from said carrier; wherein, after the biocidal composition or its membrane has been stored at ambient temperature and ambient relative humidity for 90 days or at least 90 days (or any other time period disclosed herein), said biocidal composition or said membrane exhibits antimicrobial efficacy of at least 3 logarithmic killing, as measured by EPA testing; and wherein, when measured at a thickness of 30 µm, as measured at each wavelength from 400 nm to 700 nm, said biocidal composition or said membrane or article exhibits a transmittance of at least 98%.

[0260] The twelfth aspect relates to a biocidal composition according to aspect 11 or any of the preceding aspects, wherein the thickness of the biocidal composition is from 30 µm to 1000 µm.

[0261] The thirteenth aspect relates to a biocidal composition according to aspect 11 or 12 or any of the preceding aspects, wherein the copper auxiliary additive is a compound of formula (II), a compound of formula (III), or any combination thereof:

[0262] ;

[0263] ;

[0264] Each R 2 Independently selected from C1-C5 alkyl groups optionally substituted with fluorine, and phenyl groups; and wherein each R 3 Independently selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups.

[0265] The fourteenth aspect relates to a biocidal composition according to aspects 11 to 13 or any one of the preceding aspects, wherein the copper (I) salt is copper chloride (I), copper bromide (I), copper iodide (I), copper tetra(acetonitrile) (I) hexafluorophosphate, copper tetra(acetonitrile) (I) tetrafluoroborate, copper tetra(acetonitrile) (I) perchlorate, copper tetra(acetonitrile) (I) trifluoromethanesulfonate, copper tetra(acetonitrile) (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof.

[0266] The fifteenth aspect relates to a biocidal composition according to any one of aspects 11 to 14 or any of the preceding aspects, wherein the copper auxiliary additive is triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, or any combination thereof.

[0267] The sixteenth aspect relates to a biocidal composition according to aspects 11 to 15 or any of the preceding aspects, wherein the copper (I) salt is copper (I) bromide; and wherein the copper auxiliary additive is triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof.

[0268] The seventeenth aspect relates to a biocidal composition according to aspects 11 to 16 or any of the preceding aspects, wherein the biocidal composition exhibits a ΔE of less than 6, as calculated according to the following:

[0269] ;

[0270] Where L * a * and b * The CIE value of the biocidal composition is the value obtained after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days or at least 150 days (or any other time period disclosed herein), and L * 对照 a * 对照 and b * 对照 It is the CIE value of the otherwise identical composition that does not contain the copper (I) salt or the copper auxiliary additive; and the antimicrobial efficacy of the biocidal composition or the membrane thereof after storage for 150 days or at least 150 days (or any other time period disclosed herein) is at least 3 logarithmic.

[0271] The eighteenth aspect relates to a biocidal composition according to aspects 11 to 17 or any of the preceding aspects, wherein, when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the biocidal composition or the membrane thereof exhibits a transmittance within 10 percentage points of the second transmittance of the otherwise identical composition or the membrane thereof without the copper (I) salt or the copper auxiliary additive.

[0272] The nineteenth aspect relates to a biocidal composition comprising: a carrier; a copper (I) salt; and a copper auxiliary additive different from said carrier; wherein said copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof:

[0273] ;

[0274] ;

[0275] ;

[0276] ;

[0277] Each R 1 Independently selected from hydrogen, C1-C 13 Alkyl (or C1-C8 alkyl, or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl), phenyl, and benzyl; wherein each R 2 Independently selected from C1-C5 alkyl (or C1-C6 alkyl, or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl) and aryl (e.g., phenyl) optionally substituted with fluorine; wherein each R 3 Independently selected from C1-C6 alkyl groups (or C2-C5 alkyl groups, or C2-C4 alkyl groups, or C1-C4 alkyl groups) optionally substituted with hydroxyl groups; wherein each R 4 Independently selected from C1-C6 alkyl (or C2-C5 alkyl, or C2-C4 alkyl, or C1-C4 alkyl); wherein X is an anti-counterion; wherein the copper (I) salt is copper halide (I), tetra(acetonitrile) copper (I) salt or any combination thereof; and wherein after storing the biocidal composition or its film or article at ambient temperature and ambient relative humidity for 50 days or at least 50 days (or any other time period disclosed herein), the biocidal composition, the film or article thereof exhibits an antimicrobial efficacy of at least 3 logarithmic, as measured by EPA testing.

[0278] The twentieth aspect relates to a biocidal composition according to aspect 19 or any of the preceding aspects, wherein the copper (I) salt is copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

[0279] The twenty-first aspect relates to a biocidal composition according to aspect 19 or 20 or any of the preceding aspects, wherein the copper auxiliary additive is 2-ethylhexyl phosphate, diphenyl phosphate, dibenzyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof.

[0280] The twenty-second aspect relates to a biocidal composition according to aspects 19 to 21 or any of the preceding aspects, wherein the biocidal composition is in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV curing composition, UV curable composition or plastic.

[0281] The twenty-third aspect relates to a biocidal composition according to aspects 19 to 22 or any of the preceding aspects, wherein the carrier comprises acrylate, polyvinyl chloride, organic solvent, water, or any combination thereof.

[0282] The twenty-fourth aspect relates to a biocidal composition according to aspects 19 to 23 or any of the preceding aspects, wherein the copper (I) salt is copper (I) bromide; wherein the copper auxiliary additive is trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite or any combination thereof; and wherein the biocidal composition or the film or article thereof exhibits at least 3 logarithmic antimicrobial efficacy after storage for 60 days or at least 60 days (or any other time period disclosed herein).

[0283] The twenty-fifth aspect relates to a biocidal additive formulation comprising a copper (I) salt and a copper auxiliary additive; wherein, after storing a biocidal composition comprising the biocidal additive formulation and a carrier, a film or article of the biocidal composition, or the article thereof at ambient temperature and relative humidity for one year, the biocidal composition, the film or the article thereof exhibits an antimicrobial efficacy of at least 3 logarithmic killing, as measured by EPA testing; wherein the biocidal composition exhibits a ΔE less than 6, as calculated according to the following:

[0284] ;and

[0285] Where L * a * and b * The CIE value of the biocidal composition is the value obtained after the preparation of the biocidal composition and subsequent storage of the biocidal composition at ambient temperature and relative humidity for 150 days or at least 150 days (or any other time period disclosed herein), and L * 对照 a * 对照 and b * 对照 It is the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

[0286] The twenty-sixth aspect relates to a biocidal additive formulation according to aspect 25 or any of the preceding aspects, wherein the copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), or any combination thereof:

[0287] ;

[0288] ;

[0289] ;

[0290] Each R 1 Independently selected from hydrogen, C1-C 20 Alkyl, aryl and aryl (C1-C4) alkyl; wherein each R 2 Independently selected from C1-C cells that are optionally substituted with hydroxyl groups or fluorine groups. 20 Alkyl and aryl; and wherein each R 3 Independently selected from C1-C 20 alkyl.

[0291] The twenty-seventh aspect relates to a biocidal additive formulation according to aspect 25 or 26 or any of the preceding aspects, wherein the copper (I) salt is copper bromide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

[0292] The twenty-eighth aspect relates to a biocidal additive formulation according to aspects 25 to 27 or any of the preceding aspects, wherein the copper auxiliary additive is 2-ethylhexyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof.

[0293] The twenty-ninth aspect relates to a biocidal additive formulation according to aspects 25 to 28 or any of the preceding aspects, wherein the molar concentration of the copper (I) salt dissolved in the biocidal additive formulation is at least 20 mM.

[0294] The thirtieth aspect relates to a membrane of a biocidal composition according to aspects 25 to 29 or any of the preceding aspects, wherein the membrane has a transmittance of at least 98% when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm.

[0295] The thirty-first aspect involves any combination of two or more of the foregoing aspects or any part thereof.

[0296] The compositions and methods described above can be better understood in conjunction with the following examples, which are non-limiting examples provided as illustrations of the concepts disclosed herein. The methods shown are applicable to other examples of the biocidal compositions of this disclosure. The procedures described as general methods describe a method that is generally considered effective in preparing the compositions. However, those skilled in the art will understand that it may be necessary to modify the procedures of any given example of this disclosure, for example, by changing the order or steps used and / or the chemical reagents.

[0297] Example

[0298] Example 1

[0299] I. General considerations.

[0300] All experiments were conducted in a fume hood using undextrose 18.3 MΩ Millipore-grade water. All Cu... 2+ The salt dissolved completely in the water. All the Cu... 1+ A salt (copper(I) salt) was added to the two-phase CH3CN / H2O mixture. Solubility experiments of the copper salt to produce in-situ complexes were conducted in glass drams or scintillation vials. For photochemical studies, glass vials and approximately 6" × 3" paint samples cut with stainless steel bent blunt tweezers were immersed in capped Dewar flasks packed in 2-liter stainless steel liquid nitrogen transport containers.

[0301] For the paint study, one gallon of inner eggshell enamel, ultra-pure white® 2050, Behrpremium plus, and PPG Diamond white paint were purchased. Copper salts obtained from Aldrich included: copper acetate (I) (97%), copper tetra(acetonitrile) (I) heptafluorophosphate (97%), and copper thiocyanate (I) (99%). Copper salts purchased from Sigma-Aldrich included copper bromide (I) (>98%), copper chloride (I) (reagent grade, 97%), copper iodide (I) (purity, >99.95%), copper sulfate pentahydrate (II) (ACS reagent), and copper acetate monohydrate (II). Acetonitrile (anhydrous, 99.8%) and ethylamine diamine (reagent plus, >99%) were purchased from Sigma-Aldrich. Tributylphosphine (“TBP”) (mixture of isomers, 97%) and tris(hydroxypropyl)phosphine (“THPP”) (>80%) were both purchased from Aldrich. Trimethyl phosphite (“TMP”) (>99%), triethyl phosphite (“TEP”) (for synthesis, ≥97.0%, GC), tris(2,2,2-trifluoroethyl) phosphite (“PO-CF3”), and tris(2,4-di-tert-butylphenyl) phosphite (“TDPP”) were all purchased from Sigma-Aldrich.

[0302] Trace amounts of copper oxide (I) (Cu₂O), dibenzyl phosphate (“DBzP”) (99%), and dibutyl phosphate (“DBP”) (≥97.0%, T) were all purchased from Sigma-Aldrich. Microcrystalline diphenyl phosphate (“DPP”) with a purity of 97% was purchased from Thermos Scientific. 2-Ethylhexyl phosphate (ester mixture for synthesis) (“2-EHP”) and 1-(+)-ascorbic acid EMD ACS grade were purchased from Millipore Corporation, a subsidiary of Merck KGaA. Citric acid monohydrate (granular / certified ACS) was purchased from Fisher Scientific. 2-Amino-2-methyl-1-propanol (“AMP-95”) was purchased from Angus Chemical Company. The 50% w / w sodium hydroxide (“NaOH”) solution was purchased from Fisher Chemical.

[0303] II. Preparation of complexes.

[0304] A. Preparation of in-situ [copper(I) salt + phosphine] complex.

[0305] In air, towards Cu(I)X (where X is...) - OAc) (56 mg, 0.457 mmol), Cl - (44.3 mg, 0.447 mmol), I - (85.7 mg, 0.450 mmol) or SCN - Tributylphosphine (TBP) (112 µL, 0.448 mmol) or tris(hydroxypropyl)phosphine (THPP) (87.2 µL, 0.476 mmol) was added to a stirred solution in CH3CN (2.0 mL, 38.3 mmol). The turbid mixture was stirred for 5 minutes and then H2O (3.0 mL) was added. For some samples, the turbid or colored solution became colorless, which was used as an indicator of the completion of the reaction / complexation. Some reaction times for Cu(I)X salts and TBP: for Cu(I)OAc + TBP, 2 hours; for Cu(I)Cl + TBP, < 5 minutes; for Cu(I)I + TBP, up to 3 days; for Cu(I)SCN + TBP, < 1 minute; for Cu(I)X + THPP, < 1 minute.

[0306] Once the precursor [Cu(I)X + phosphine] solution was prepared, it was added directly to the paint and thoroughly mixed with a glass rod, then further mixed with a glass rod using a top mixer equipped with a PTFE-coated stirrer set to 915 rpm. Once the precursor solution was fully mixed with the paint formulation, an initial pull was performed using a 7-mil pull rod. The pull was cured for at least 7 days before recording the International Commission on Illumination (CIE) L*a*b* color space coordinate measurements using an X-Rite VS450 non-contact spectrophotometer (45 / 0 geometry).

[0307] B. Preparation of in-situ [copper(I) salt + phosphite] complex.

[0308] In air, trimethyl phosphite (TMP) (53.0 µL, 0.449 mmol), triethyl phosphite (TEP) (77.0 µL, 0.449 mmol or 231 µL, 1.35 mmol), or tri(2,2,2-trifluoroethyl) phosphite (PO-CF3) (99.0 µL, 0.449 mmol) was added to a stirred solution of Cu(I)Br (64.8 mg, 0.452 mmol) in CH3CN (2.0 mL, 38.3 mmol). The turbid mixture was stirred for 5 minutes and then H2O (3.0 mL) was added. Water in this reaction can be replaced by an equal volume of alcohol (such as ethanol). All the green mixture [CH3CN containing Cu(I)Br] became completely colorless in about 2 hours, except for [CuBr + 3 equivalents of TEP] (which required 3+ hours to complete the reaction).

[0309] Once the precursor [Cu(I)X + phosphite] solution is prepared, it is added directly to the paint being stirred at 1100 rpm by overhead mixing. All other procedures remain the same as for the [Cu(I)X + phosphine] system described above.

[0310] C. Preparation of in-situ [copper(I) salt + phosphate ester] complex.

[0311] Adding Cu(I)Br (64.8 mg, 0.452 mmol) to a stirred solution of dibenzyl phosphate (DBzP) (1125.2 mg, 0.450 mmol), diphenyl phosphate (DPP) (112.6 mg, 0.450 mmol), or 2-EHP (0.450 mmol) in CH3CN (2.0 mL, 38.3 mmol) turned the turbid mixture dark green. Adding H2O (3.0 mL) to the turbid mixture turned it colorless. Unlike phosphite or phosphine systems, a neutralizing agent was added to the paint prior to the addition of the Cu mixture. All other procedures described are the same as for phosphite and phosphine systems.

[0312] D. Preparation of [copper(I) salt + phosphite] precursor solution for UV-curable films.

[0313] In air, triethyl phosphite (TEP) (411.3 µL, 2.40 mmol) was added to a stirred solution of Cu(I)Br (114.7 mg, 0.800 mmol) in EtOH (2.0 mL, 34.3 mmol). This was then added to an 11D UV-curable formulation to a maximum of 10% ethanol added to the mixture. The copper-containing mixture was stirred and pulled down with a rod, as with paints and coatings, prior to UV curing of the film.

[0314] Two UV-curable, transparent, and colorless coatings were prepared by spin coating using 20% ​​by weight of copper(I) iodide (triethyl phosphite) (“CuI(TEP)”) dissolved in propylene glycol methyl ether acetate (“PGMEA”). The coatings were: (1) a multi-purpose, more reactive, and flexible (Ultrabond® 721, acrylate-based); and (2) a glass / metal coating (Ultrabond® 740, methacrylate-based), having CuI(TEP), PGMEA, and a UV-curable resin as provided in Table 1 below. The films remained colorless, similar to the original coating materials, and upon curing, exhibited substantially complete sterilization, such as… Figure 11 As shown in the image. The coating has a slight haze, which can be addressed by improving material compatibility.

[0315] Table 1

[0316]

[0317] III. Comparison of complexes containing copper(I) salts with mixtures containing copper-containing glass.

[0318] In the examples described herein, a complex containing a copper (I) salt can be compared to a mixture comprising a plurality of copper-containing glass or glass-ceramic particles. As used herein, unless obviously contradicted by the context, the term “copper-containing glass” is intended to include “copper-containing glass-ceramic.” In this respect, the “ceramic” portion of a copper-containing glass-ceramic may, in some respects, comprise cuprite crystals.

[0319] In some instances, copper-containing materials may comprise copper-containing glass or copper-containing glass-ceramic particles. The copper-containing glass or glass-ceramic particles may be biocidal inorganic glass or glass-ceramic powder containing copper particles. Although individual copper-containing glass particles can be effectively used as a biocide, such copper-containing glass may have potential disadvantages related to the color of the resulting composition and the stability of copper (I).

[0320] Copper-containing glasses or glass-ceramic particles can independently contain Cu metal, Cu... 1+ Cu 2+ or Cu 1+and Cu 2+ The total amount of Cu species can be 10% by weight or more of the copper-containing material. However, as will be discussed in more detail below, Cu... 2+ The amount can be minimized or reduced so that copper-containing glass or glass-ceramic particles can be essentially Cu-free. 2+ Copper can be non-complexed, or it can have ligands bonded to it to form a complex. 1+ Ions can be present on or within the surface and / or bulk of copper-containing glass or glass-ceramic particles. Copper-containing glass or glass-ceramic particles can comprise copper-containing glass or glass-ceramic, copper metal, copper oxide (I), copper oxide (II), or combinations thereof. In some instances, copper-containing glass or glass-ceramic particles may comprise only one of copper-containing glass or glass-ceramic, copper metal, copper oxide (I), or copper oxide (II). In some instances, Cu... 1+ Ions can exist in glass or glass-ceramic networks and / or glass or glass-ceramic matrices containing copper-containing glass or glass-ceramic particles. 1+ Cu 1+ Ions are atomically bonded to atoms in glass or glass-ceramic mixtures. When Cu 1+ When Cu ions are present in a glass or glass-ceramic matrix, 1+ Ions can be dispersed in Cu in a glass or glass-ceramic matrix 1+ It exists in crystalline form. In some instances, Cu... 1+ Crystals can contain cuprite (Cu₂O). In the presence of Cu… 1+ In certain instances of crystals, the material may be referred to as glass-ceramic or ceramic, where glass-ceramic or ceramic is intended to refer to a specific type of glass or glass-ceramic having crystals that can or may not undergo conventional ceramicizing processes, through which one or more crystalline phases are introduced and / or generated in the glass or glass-ceramic by said conventional ceramicizing processes. When Cu 1+ When ions exist in a non-crystalline form, the material can be called a copper-containing glass. In some instances, Cu... 1+ Crystals and Cu that do not associate with crystals 1+ Both ions can exist in the copper-containing glass or glass-ceramic described herein.

[0321] Copper-containing glasses or glass-ceramics may contain copper oxides in amounts expressed in mol% within the following ranges: 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 2... 6, 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 ranges formed by any two of the foregoing mol%; and all subranges therein. Copper oxides may be present in copper-containing glasses or glass-ceramics in amounts of 20 mol%, 25 mol%, 30 mol%, or 35 mol%. Copper oxides may comprise CuO, Cu2O, and / or combinations thereof. Copper-containing glass or glass-ceramic particles may contain cuprous oxide in an amount ranging from 29.0% to 36.0% by weight of the copper-containing glass or glass-ceramic particles. The copper oxide in the copper-containing glass or glass-ceramic forms Cu present in the resulting glass or glass-ceramic. 1+ Ions. Copper can exist in various forms (including Cu). 0 Cu 1+ and Cu 2+ It exists in glass or glass-ceramics or combinations thereof.

[0322] The copper-containing glass or glass-ceramic portion of individual particles can be formed from a glass composition that may contain, but is not limited to, in mol% amounts of SiO2 in the range of 30 to 70, Al2O3 in the range of 0 to 20, copper oxides in the range of 10 to 50, CaO in the range of 0 to 15, MgO in the range of 0 to 15, P2O5 in the range of 0 to 25, B2O3 in the range of 0 to 25, K2O in the range of 0 to 20, ZnO in the range of 0 to 5, Na2O in the range of 0 to 20, and / or Fe2O3, nanoparticles thereof, and / or mixtures thereof. In such examples, the amount of copper oxides is greater than the amount of Al2O3. In some examples, the glass composition may contain a certain amount of R2O, wherein R may contain K, Na, Li, Rb, Cs, and combinations thereof.

[0323] In some instances, the glass composition may contain one or more divalent cationic oxides, such as alkaline earth metal oxides and / or ZnO. In some instances, the glass composition may contain NiO, TiO2, Fe2O3, Cr2O3, or Co3O4 in amounts ranging from 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] Copper-containing glasses or glass-ceramics formed from glass compositions may contain multiple Cu atoms. 1+ Ions. In some instances, this type of Cu 1+ Ions form part of the glass network. In some instances, Cu is dispersed in the glass matrix. 1+ The ion is Cu 1+ Crystal. Cu 1+ It can exist in the form of cuprite. Cuprite present in copper-bearing glass-ceramics can form a phase different from the glass matrix or glass phase. In other instances, cuprite can form part of one or more glass phases, or can associate with one or more glass phases.

[0325] Copper-containing glass can be produced by any suitable method. For example, copper-containing glass can be produced using a melting pot commonly used for melting glass compositions such as soda-lime silicates. In some instances, copper-containing glass can be formed into sheets using forming processes known in the art. Forming methods can include float glass processes and down-drawing processes such as fusion drawing and slot drawing. After forming, copper-containing glass can be formed into sheets and can be shaped, polished, or otherwise processed to achieve a desired end use. In some instances, copper-containing glass can be ground into powder or particulate form. In some instances, particulate copper-containing glass can be combined with other materials or carriers.

[0326] IV. Result.

[0327] A. Antimicrobial efficacy

[0328] This article provides representative measurements of the antimicrobial efficacy of examples of biocidal compositions, and provides representative antimicrobial efficacy.

[0329] like Figure 1As demonstrated, after 50 days of storage of the biocidal composition or films prepared therefrom at ambient temperature and relative humidity, in Behr 2050® paint or as a dry film, triethyl phosphite (EtO) 3P with copper iodide (I), and tributylphosphine (TBP) with copper acetate (I), copper chloride (I), and copper iodide (I) each exhibited antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing. For copper iodide (I) and TBP, Figure 1 The antimicrobial efficacy was shown to increase from the initial drop-down value to the value after 50 days of storage. In contrast, THPP with each of copper iodide (I), copper chloride and copper thiocyanate (I), and TBP with copper thiocyanate (I) did not show antimicrobial efficacy after storage.

[0330] like Figure 2 As demonstrated, compared to 1 wt% copper bromide(I) (which exhibited >2 log-kill after storage), the 11D UV-curable film prepared with a precursor solution containing 3 wt% copper bromide(I) and 3 molar equivalents of triethyl phosphite (TEP) exhibited at least 3 log-kill after 60 days of storage at ambient temperature and relative humidity. Copper metal was used as a positive control, and glass coverslips were added as a negative control. After 30 days at room temperature, a 2:3 acetonitrile:water solution containing 26.4 g / L of copper bromide(I) and 3 molar equivalents of TEP in Behr DTM paint exhibited at least 3 log-kill. Figure 7 As shown in the figure. In contrast, copper bromide (I) at any concentration in Behr DTM paint with each of the following 2:3 acetonitrile:water solutions exhibited logarithmic kill values ​​below 3 logarithmic kills: .

[0331] Furthermore, the UV-curable film prepared from a precursor solution containing ethanol, 0.6 wt% copper bromide (I), and 3 molar equivalents of TEP exhibited at least 5 logarithmic kills within 90 days, while the film prepared from a precursor solution containing 0.2 wt% copper bromide (I) and 3 molar equivalents of TEP exhibited less than 3 logarithmic kills at 7, 30, and 90 days. Figure 10 As shown in Table 2 below.

[0332] Table 2

[0333]

[0334]

[0335] like Figure 3As shown, the antimicrobial efficacy of examples of biocidal compositions as dry film compositions was tested initially and 5 months after application as a dry film, and after 5 months of storage in paint cans, followed by 7 days after application as a dry film. Examples of biocidal compositions contained copper bromide (I) and each of PO-CF3, trimethyl phosphite (TMP), and triethyl phosphite (TEP) in each of Behr 2050® and PPG Diamond® paints. After 5 months (or 150 days), each composition containing copper bromide (I) and PO-CF3, TMP, or TEP exhibited at least 3 logarithmic killing, demonstrating antimicrobial efficacy values ​​comparable to those of biocidal compositions containing copper metal or copper-containing glass.

[0336] like Figure 4 Examples of biocidal compositions comprising tetra(acetonitrile)copper(I)hexafluorophosphate and 2-ethylhexyl phosphate (2-EHP) in a molar ratio of 1:1 or 1:10, as shown in the paper, exhibited at least 3 logarithmic antimicrobial efficacy after storage at ambient temperature for more than one year.

[0337] Examples of biocidal compositions comprising PVC plastisol, tetra(acetonitrile)copper(I)hexafluorophosphate, and 2-EHP were evaluated for their antimicrobial efficacy after 4 months of storage at ambient temperature and relative humidity, and exhibited at least 3 logarithmic killing after 4 months of storage. Figure 5 As shown in the figure. Furthermore, after storage for 7 days under accelerated aging conditions (65°C and 65% relative humidity), the biocidal composition also exhibited at least 3 logarithmic killing effect, such as... Figure 6 As shown in the image.

[0338] B. Total color difference (ΔE) of paints containing biocidal compositions.

[0339] Using an X-Rite VS450 non-contact colorimetric spectrophotometer, the ΔE values ​​of various examples of the biocidal compositions prepared in Behr 2050® and PPG Diamond® paint cans were determined according to formula (V):

[0340] (V)

[0341] Where L * a * and b * The values ​​are values ​​for examples of biocidal compositions prepared (“time zero”) and stored for 5 months (or 150 days, “time end”) after the preparation of the biocidal composition using the copper(I) species and copper auxiliary additives listed in Table 3 below, and L * 对照 a * 对照 and b *对照 The values ​​are for compositions that are otherwise identical, but do not contain copper(I) species or copper auxiliary additives. Three points were measured on the film of each composition, and the average value was recorded.

[0342] Table 3

[0343]

[0344]

[0345] As shown in Table 3, for each example of a biocide composition containing copper bromide (I) and one of PO-CF3, TMP, TEP, or TDDP, the ΔE is... * The value is lower than the ΔE of the corresponding composition containing CCG and one of PO-CF3, TMP, TEP or TDDP. * value.

[0346] C. Ultraviolet transmittance of membranes prepared from biocidal compositions.

[0347] An example of a UV-curable film was prepared from a biocidal composition comprising copper(I) bromide and triethyl phosphite. Transmittance (%) was measured at each wavelength from 400 nm to 700 nm in the visible range of the electromagnetic spectrum using an x-Rite Ci7800 spectrophotometer (D65 light source (daylight), 10-degree viewing angle, SCI, 25 mm aperture). The thickness of the film for which the transmittance (%) was measured was 30 µm. The transmittance (%) of the glass substrate on which the UV-curable film was applied was subtracted from the transmittance (%) of the UV-curable film. Figure 8 As shown, the 30 µm thick film has a transmittance of at least 98% at each wavelength from 400 nm to 700 nm.

[0348] D. UV-Vis absorption of biocidal additives

[0349] In one example, the molar concentration of copper(I) in the biocidal additive formulation can be from 20 mM to 200 mM; the molar concentration of the copper auxiliary additive can be from 0.06 mM to 0.6 mM; and the molar concentration of the solvent can be from 0.8 mM to 8 mM. Optical properties may vary. In some examples, the biocidal additive formulation can be colorless and transparent; in others, it can have a slight color. Examples of biocidal additive formulations containing copper(I) bromide and triethyl phosphite are colorless, have no significant absorption in the visible range, and appear similar to... Figure 9The absorption spectrum 4 shown in the figure (although spectrum 4 is actually data from different additive formulations). Figure 9 The study also presents absorption data for copper(II) sulfate dissolved in water (spectrum 1); copper(I) acetate oxidized during dissolution in water / acetonitrile (spectrum 2); and a commercial copper(I) complex in a 2:3 acetonitrile:water solution (spectrum 3).

[0350] Example 2

[0351] This example demonstrates a biocidal composition comprising a copper (I) salt and a phosphite of formula (II).

[0352] For example, the use of the copper-assisted additive triphenyl phosphite (TPP) demonstrated improved solvent solubility of copper(I) and excellent antimicrobial (AM) efficacy. It is believed that when copper(I) and TPP were prepared according to this example, a Cu(I)-TPP complex was formed.

[0353] Preparation of the Cu-TPP complex precursor solution (397.4 mM). At room temperature, purified triphenyl phosphite (0.308 g, 0.992 mmol) was added dropwise to a solution of CuBr (0.114 mg, 0.795 mmol) in butyl acetate, ethyl acetate, or toluene (2 mL). The mixture was sonicated for 5 min to accelerate the dissolution of the copper salt particles. The blue-green suspension was then stirred on a drum mixer at approximately 190 rpm. Depending on the solvent chosen, the reaction resulted in a color change from blue-green to colorless at different times; 45 min in butyl acetate or ethyl acetate, and approximately 10 min in toluene. The resulting complex is interchangeably referred to herein as Cu-TPP or CuBr-TPP.

[0354] Preparation of the concentrated Cu-TPP complex precursor solution (794.7 mM): CuBr (0.228 mg, 1.59 mmol) and 2 ml of n-butyl acetate, ethyl acetate, or toluene were used, following the previously described procedure. The final homogeneous solution was colorless.

[0355] Preparation of copper (I)-containing paint samples. (To BEHR) TM In a mixture of 2050 latex paint (50.0 g) at approximately 1150 rpm, an aliquot of the previously prepared Cu-TPP precursor solution was slowly added. The mixture was stirred until the added copper solution was incorporated into the paint. A dry film was prepared using a 7-mil stainless steel scraper. The dry film was allowed to cure before measuring antimicrobial efficacy using the EPA test. Six samples were tested, and details are summarized in Table 4.

[0356] Table 4.

[0357]

[0358]

[0359] Paint color and AM effectiveness results. To determine whether the Cu-TPP precursor solution was AM effective, the AM effectiveness was evaluated when Cu-TPP was incorporated into the latex paint film and cured (Table 4). Figure 12 BEHR containing 0.1 wt.% Cu-TPP was prepared using a low-concentration Cu-TPP storage solution (397.4 mM). TM Behr 2050 latex paint was used to observe whether there was a quantifiable difference in solvent-induced AM compared to copper-loaded results targeting <3 logarithmic kill. Surprisingly, 0.1 wt.% Cu-TPP paint films achieved complete kill in both tested solvents. Furthermore, in this study, complete kill was defined as at most 5 logarithmic kill. High-dose (0.2 wt%) Cu-TPP was also studied in both solvent systems in the Behr 2050 paint study, confirming the consistency of previous complete kill measurements. No differences were observed in paint color, the manner in which the copper precursor solution was incorporated into the film, or the final quality of the dried paint film during the preparation and drying of AM paint films (Table 5). Another set of validation studies was conducted using a more concentrated (795 mM) copper precursor solution. To determine whether the same AM performance could be obtained with a copper precursor solution concentrate, Behr... TM Samples of Cu-TPP were prepared in 2050 paint at the same dosage (0.2 wt.%) for complete AM eradication. From these studies, it was observed that these samples also acquired the same physical properties as those described for lower dosages of Cu-TPP (0.1 wt%), and also achieved complete AM eradication efficacy during testing. Overall, these results support the notion that this form of copper phosphite complex not only forms a very concentrated precursor solution, but also that Cu-TPP exhibits high AM activity upon incorporation into coatings such as paints.

[0360]

[0361] 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.

[0362] 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.

[0363] 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: carrier; Copper(I) salt; as well as Copper auxiliary additives, different from those used in the carrier; The copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof: ； ； ； ； Each R 1 Independently selected from hydrogen, C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl; Each R 2 Independently selected from C1-C cells optionally substituted with fluorine. 20 Alkyl and aryl; Each R 3 Independently selected from C1-C cells optionally substituted with hydroxyl groups. 20 alkyl; Each R 4 Independently selected from C1-C 20 alkyl; Where X is a counter ion; and Wherein, after storing the biocidal composition or its film or article at ambient temperature and relative humidity for 50 days, the biocidal composition, its film or article exhibits an antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing.

2. The biocidal composition according to claim 1, wherein the copper (I) salt is copper chloride (I), copper bromide (I), copper iodide (I), copper tetra(acetonitrile) (I) hexafluorophosphate, copper tetra(acetonitrile) (I) tetrafluoroborate, copper tetra(acetonitrile) (I) perchlorate, copper tetra(acetonitrile) (I) trifluoromethanesulfonate, copper tetra(acetonitrile) (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof.

3. The biocidal composition according to claim 1 or 2, wherein the copper auxiliary additive is 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof.

4. The biocidal composition according to any one of claims 1 to 3, wherein the biocidal composition is in the form of paint, coating, elastomeric coating, caulking compound, sealant, floor polish, fabric treatment, dye, varnish, primer, UV curing composition, UV curable composition or plastic.

5. The biocidal composition according to any one of claims 1 to 4, wherein the carrier comprises acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof.

6. The biocidal composition according to any one of claims 1 to 5, The copper(I) salt mentioned therein is copper(I) bromide; The copper auxiliary additive mentioned above is trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and The biocidal composition or its film or article exhibits at least 3-logarithmic antimicrobial efficacy after 60 days of storage.

7. The biocidal composition according to any one of claims 1 to 6, The copper auxiliary additive is triethyl phosphite, triphenyl phosphite, or both; and The biocidal composition or its film or article exhibits at least 3-logarithmic antimicrobial efficacy after 150 days of storage.

8. The biocidal composition according to any one of claims 1 to 5, The copper(I) salt therein is tetra(acetonitrile)copper(I)hexafluorophosphate; The copper auxiliary additive is 2-ethylhexyl phosphate; and The biocidal composition or its film or article exhibits at least 3 logarithmic antimicrobial efficacy after 1 year of storage.

9. The biocidal composition according to any one of claims 1 to 6, The copper(I) salt mentioned therein is copper(I) bromide; The copper auxiliary additive mentioned above is trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and The biocidal composition exhibits a ΔE of less than 6, as calculated below: ;and Where L * a * and b * The CIE value of the biocidal composition is the value obtained after the biocidal composition has been prepared and then stored at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It is the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

10. The biocidal composition according to any one of claims 1 to 5, wherein each R 1 Selected from hydrogen, C1-C 13 Alkyl, phenyl, and benzyl; Each R 2 Selected from C1-C5 alkyl groups optionally substituted with fluorine, and phenyl groups; Each R 3 Selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups; and Each R 4 Selected from C1-C6 alkyl groups.

11. A biocidal composition comprising: carrier; Copper(I) salt; as well as Copper auxiliary additives, different from those used in the carrier; Wherein, after the biocidal composition or its film has been stored at ambient temperature and relative humidity for 90 days, the biocidal composition or its film exhibits an antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing; and When measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the biocidal composition or the membrane or article thereof exhibits a transmittance of at least 98%.

12. A membrane of the biocidal composition according to claim 11, wherein the membrane has a thickness of 30 µm to 1000 µm.

13. The biocidal composition according to claim 11 or 12, wherein the copper auxiliary additive is a compound of formula (II), a compound of formula (III), or any combination thereof: ； ； Each R 2 Independently selected from C1-C5 alkyl groups optionally substituted with fluorine, and phenyl groups; and Each R 3 Independently selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups.

14. The biocidal composition according to any one of claims 11 to 13, wherein the copper (I) salt is copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, copper acetate (I), or any combination thereof.

15. The biocidal composition according to any one of claims 11 to 14, wherein the copper auxiliary additive is triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, or any combination thereof.

16. The biocidal composition according to any one of claims 11 to 14, The copper(I) salt therein is copper(I) bromide; and The copper auxiliary additive mentioned therein is triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof.

17. The biocidal composition according to any one of claims 11 to 16, The biocidal composition exhibits a ΔE of less than 6, as calculated below: ； Where L * a * and b * The CIE value of the biocidal composition is the value obtained after the biocidal composition has been prepared and then stored at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It is the CIE value of a composition that is otherwise identical, without the copper(I) salt or the copper auxiliary additive; and The biocidal composition or its film exhibits at least 3-logarithmic antimicrobial efficacy after 150 days of storage.

18. The biocidal composition according to any one of claims 11 to 17, wherein when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm, the biocidal composition or the membrane thereof exhibits a transmittance within 10 percentage points of the second transmittance of the otherwise identical composition or the membrane thereof without the copper (I) salt or the copper auxiliary additive.

19. A biocidal composition comprising: carrier; Copper(I) salt; as well as Copper auxiliary additives, different from those used in the carrier; The copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), a compound of formula (IV), or any combination thereof: ； ； ； ； Each R 1 Independently selected from hydrogen, C1-C 13 Alkyl, phenyl, and benzyl; Each R 2 Independently selected from C1-C5 alkyl groups optionally substituted with fluorine, and phenyl groups; Each R 3 Independently selected from C1-C6 alkyl groups optionally substituted with hydroxyl groups; Each R 4 Independently selected from C1-C6 alkyl groups; Where X is the counter ion; The copper(I) salt thereon is copper(I) halide, tetra(acetonitrile)copper(I) salt, or any combination thereof; and Wherein, after storing the biocidal composition or its film or article at ambient temperature and relative humidity for 50 days, the biocidal composition, its film or article exhibits an antimicrobial efficacy of at least 3 logarithmic kill, as measured by EPA testing.

20. The biocidal composition according to claim 19, wherein the copper (I) salt is copper chloride (I), copper bromide (I), copper iodide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

21. The biocidal composition according to claim 19 or 20, wherein the copper auxiliary additive is 2-ethylhexyl phosphate, diphenyl phosphate, dibutyl phosphate, dibenzyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, tributylphosphine, tri(3-hydroxypropyl)phosphine, 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, or any combination thereof.

22. The biocidal composition according to any one of claims 19 to 21, wherein the biocidal composition is in the form of paint, coating, elastomer coating, caulking compound, sealant, floor wax, fabric treatment agent, dye, varnish, primer, UV curing composition, UV curable composition or plastic.

23. The biocidal composition according to any one of claims 19 to 22, wherein the carrier comprises acrylate, polyvinyl chloride, latex, organic solvent, water, or any combination thereof.

24. The biocidal composition according to any one of claims 19 to 23, The copper(I) salt mentioned therein is copper(I) bromide; The copper auxiliary additive mentioned above is trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof; and The biocidal composition or its film or article exhibits at least 3-logarithmic antimicrobial efficacy after 60 days of storage.

25. A biocidal additive formulation comprising a copper (I) salt and a copper auxiliary additive; Wherein, after storing the biocidal composition comprising the biocidal additive formulation and the carrier, the membrane or article of the biocidal composition at ambient temperature and relative humidity for 1 year, the biocidal composition or the membrane or article thereof exhibits an antimicrobial efficacy of at least 3 logarithmic killing, as measured by EPA testing; The biocidal composition exhibits a ΔE of less than 6, as calculated below: ;and Where L * a * and b * The CIE value of the biocidal composition is the value obtained after the biocidal composition has been prepared and then stored at ambient temperature and relative humidity for 150 days, and L * 对照 a * 对照 and b * 对照 It is the CIE value of a composition that is otherwise identical, without the copper (I) salt or the copper auxiliary additive.

26. The biocidal additive formulation according to claim 25, wherein the copper auxiliary additive is a compound of formula (I), a compound of formula (II), a compound of formula (III), or any combination thereof: ； ； ； Each R 1 Independently selected from hydrogen, C1-C 20 Alkyl, aryl, and aryl (C1-C4)alkyl; Each R 2 Independently selected from C1-C cells that are optionally substituted with hydroxyl groups or fluorine groups. 20 Alkyl and aryl; and Each R 3 Independently selected from C1-C 20 alkyl.

27. The biocidal additive formulation according to claim 25 or 26, wherein the copper (I) salt is copper bromide (I), tetra(acetonitrile)copper (I) hexafluorophosphate, tetra(acetonitrile)copper (I) tetrafluoroborate, tetra(acetonitrile)copper (I) perchlorate, tetra(acetonitrile)copper (I) trifluoromethanesulfonate, tetra(acetonitrile)copper (I) hydrogen oxalate-oxalate-acetonitrile, or any combination thereof.

28. The biocidal additive formulation according to any one of claims 25 to 27, wherein the copper auxiliary additive is 2-ethylhexyl phosphate, triethyl phosphite, trimethyl phosphite, triphenyl phosphite, tri(2,2,2-trifluoroethyl) phosphite, or any combination thereof.

29. The biocidal additive formulation according to any one of claims 25 to 28, The molar concentration of the copper (I) salt dissolved in the biocidal additive formulation is at least 20 mM.

30. A membrane of a biocidal composition according to any one of claims 25 to 29, wherein the transmittance of the membrane is at least 98% when measured at a thickness of 30 µm, such as at each wavelength from 400 nm to 700 nm.

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