WO2023101932A1 - Copper containing compounds and compositions for wet-state paint and polymer emulsion preservation - Google Patents

Abstract

The present disclosure is generally directed to a polymer emulsion composition. The polymer emulsion composition includes a copper containing compound. The polymer emulsion composition further includes a biocide including one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol. The polymer emulsion composition further includes a solvent. Notably, the copper containing compound is present in the polymer emulsion composition in an amount of less than about 10,000 ppm and the biocide is present in the polymer emulsion composition in an amount of less than about 10,000 ppm. Moreover, the polymer emulsion composition is substantially free of glass.

Description

COPPER CONTAINING COMPOUNDS AND COMPOSITIONS FOR WET¬

STATE PAINT AND POLYMER EMULSION PRESERVATION

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to the benefit of U.S. Provisional Application No. 63/285,726, filed December 3, 2021, and to the benefit of U.S. Patent Application No. 63/309,029, filed February 11, 2022, each of which is expressly incorporated herein by reference in its entirety.

FIELD

[0002] The present disclosure relates generally to copper containing compounds and compositions for wet-state preservation. The present disclosure also relates generally to combinations of copper containing compounds and biocides for wet-state paint and polymer emulsion preservation.

BACKGROUND

[0003] Paints and coatings are used to protect a surface from corrosion, oxidation, or other types of deterioration and to provide decorative effects. Such coatings can include water-based latex coatings, oil-based coatings, enamels, urethanes, epoxy coatings, and the like. Water-based paints or coatings, generally referred to as latex paints or coatings, include a dispersion of resin combined with various paint additives, such as coalescent, wetting agents and rheology modifiers. Water-based paints or coatings can also include a dispersion of dry powders of pigment, fillers and extenders. Typically, the resin dispersion is either a latex formed by emulsion polymerization or a resin in emulsion form. The dry powder dispersion is made by milling the dry ingredients into water. The two dispersions are blended to form an emulsion or latex paint.

[0004] At every stage of their service lives, latex paints, along with other paints and coatings, may be subject to the growth of microorganisms, particularly in humid locations or areas. However, latex paints are particularly susceptible to the growth of microorganisms even in environments having a relatively low humidity due to the presence of water in the dry powder dispersion. Moreover, the surface of latex paints may become discolored by microorganisms, affecting the aesthetic quality of the surface and/or durability of the paint. For this reason, biocides may be incorporated into latex paint formulations in order to reduce the growth of microorganisms within the latex paint and preserve the aesthetic quality of the surface. However, it is desirable to employ a latex paint that has a high degree of antimicrobial efficacy against a relatively wide variety of microorganisms. Moreover, with respect to government regulation and production costs, it may be desirable to employ a combination of biocides, allowing the resulting latex paint to employ a reduced amount of biocides, while still achieving a desired degree of antimicrobial efficacy.

[0005] Accordingly, there is a need for employing improved additive compositions in polymer emulsions.

SUMMARY

[0006] In general, the present disclosure is directed to a polymer emulsion composition and a biocidal composition. The compositions of the present disclosure may be incorporated in an in-can, wet-state preservation additive for a latex emulsion composition, such as a latex paint composition. Notably, the compositions of the present disclosure advantageously exhibit antimicrobial properties. Specifically, employing copper containing compounds, in combination with various biocides, in a polymer emulsion composition as described by the present disclosure has been found to result in a polymer emulsion composition exhibiting a broad range of biocidal activity against many different microorganisms. Moreover, the compositions of the present disclosure may advantageously exhibit such antimicrobial properties while surprisingly avoiding undesirable color impacts. Furthermore, the components of the compositions of the present disclosure may also exhibit a beneficial potentiation in order to advantageously utilize a reduced amount of biocides while still achieving a desired degree of antimicrobial efficacy.

[0007] In one example embodiment, a polymer emulsion composition includes a copper containing compound. The polymer emulsion composition further includes a biocide including one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol. The polymer emulsion composition further includes a solvent. Notably, the copper containing compound is present in the polymer emulsion composition in an amount of less than about 10,000 ppm and the biocide is present in the polymer emulsion composition in an amount of less than about 10,000 ppm. Moreover, the polymer emulsion composition is substantially free of glass.

[0008] In a first example aspect, the copper containing compound may include at least one of basic copper carbonate, copper naphthenate, cupric oxide, copper thiocyanate, copper hydroxide, copper 8-quinolinolate, copper sulphate, copper nitrate, and copper bis(5-oxo-L-prolinato).

[0009] In a second example aspect, the copper containing compound may include basic copper carbonate.

[0010] In a third example aspect, the copper containing compound and the biocide may be present in the polymer emulsion composition at a weight ratio of from about 1 :0.001 to about 1 : 1000.

[0011] In a fourth example aspect, the copper containing compound includes micronized copper compound particles, in which 50% or more of the micronized copper compound particles have a median particle size of less than about 1 micron. [0012] In a fifth example aspect, the biocide may include the quaternary ammonium compound, and the quaternary ammonium compound may include one or more of dialkyl dimethyl ammonium chloride, dialkyl dimethyl ammonium carbonate, dialkyl dimethyl ammonium bicarbonate, alkyl dimethyl benzyl ammonium chloride, and dialkyl methyl poly(oxyethyl) ammonium propionate.

[0013] In a sixth example aspect, the biocide may include the isothiazolone compound, and the isothiazolone compound may include one or more of 2-methyl-4- isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5- dichloro-2-n-octylisothiazolin-3-one (DCOIT), 5-chloro-2-n-octyl-4-isothiazolin-3- one (COIT), 2-octyl-2H-isothiazolin-3-one (OIT), l,2-benzothiazolin-3-one (BIT), N- methyl-l,2-benzisothiazolin-3-one (MBIT), and 2-butyl-l,2-benzisothiazolin-3(2H)- one (BBIT).

[0014] In a seventh example aspect, the biocide may include the haloalkylnyl compound, and the haloalkylnyl compound may include 3-iodo-2-propynyl butyl carbamate (IPBC). [0015] In an eighth example aspect, the biocide may include the triazine compound, and the triazine compound may include 1,3,5-triazine.

[0016] In a ninth example aspect, the biocide may include the azole compound, and the azole compound may include a 1,2,4-triazole compound, the 1,2,4-triazole compound comprising one or more of cyproconazole, fenbuconazole, propiconazole, tebuconazole, triadimefon, tri ti conazole, and difenoconazole.

[0017] In a tenth example aspect, the azole compound may be complexed with the copper containing compound.

[0018] In an eleventh example aspect, the azole compound may include micronized azole particles, in which 50% or more of the micronized azole particles have a median particle size of less than about 1 micron.

[0019] In a twelfth example aspect, the biocide may include the aryl urea compound, and the aryl urea compound may include (3 -(3, 4-di chlorophenyl)- 1,1- dimethylurea.

[0020] In a thirteenth example aspect, the biocide may include the succinate dehydrogenase inhibitor, and the succinate dehydrogenase inhibitor may include a carboxamide compound.

[0021] In a fourteenth example aspect, the pH of the polymer emulsion composition may be from about 8.0 to about 9.5.

[0022] In a fifteenth example aspect, the polymer emulsion composition may further include an inorganic oxide compound.

[0023] In a sixteenth example aspect, the inorganic oxide compound may include one or more of zinc oxide and iron oxide.

[0024] In a seventeenth example aspect, the polymer emulsion composition may further include an adjuvant compound.

[0025] In an eighteenth example aspect, the adjuvant compound may include one or more of 2-dicyandiamide and zinc ethyltrifluoroacetate.

[0026] In a nineteenth example aspect, the solvent includes water.

[0027] In a twentieth example aspect, a latex paint composition may include the polymer emulsion composition.

[0028] Each of the example aspects recited above may be combined with one or more of the other example aspects recited above in certain embodiments. For instance, all of the twenty example aspects recited above, i.e., the first through nineteen examples aspects, may be combined with one another in some embodiments. As another example, any combination of two, three, four, five, or more of the twenty example aspects recited above may be combined in other embodiments. Thus, the example aspects recited above may be utilized in combination with one another in some example embodiments. Alternatively, the example aspects recited above may be individually implemented in other example embodiments. Accordingly, it will be understood that various example embodiments may be realized utilizing the example aspects recited above.

[0029] In another example embodiment, a biocidal composition includes a copper containing compound including basic copper carbonate. The biocidal composition further includes a biocide including one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol. The biocidal composition further includes one or both of an inorganic oxide compound and an adjuvant compound. The inorganic oxide compound includes one or both of zinc oxide and iron oxide, and the adjuvant compound includes one or both of 2-dicyandiamide and zinc ethyltrifluoroacetate. Notably, the biocidal composition is substantially free of glass.

[0030] These and other features, embodiments and advantages of the present invention will become better understood with reference to the following description and appended claims.

DETAILED DESCRIPTION

[0031] Reference will now be made in detail to example embodiments of the disclosure. It is to be understood by one of ordinary skill in the art that the present disclosure is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.

[0032] The present disclosure is generally directed to a polymer emulsion composition and a biocidal composition. The polymer emulsion composition includes a copper containing compound. The polymer emulsion composition further includes a biocide including one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol. The polymer emulsion composition further includes a solvent. Notably, the copper containing compound is present in the polymer emulsion composition in an amount of less than about 10,000 ppm and the biocide is present in the polymer emulsion composition in an amount of less than about 10,000 ppm. Moreover, the polymer emulsion composition is substantially free of glass.

[0033] The polymer emulsion composition and the biocidal composition of the present disclosure advantageously exhibit antimicrobial properties. Specifically, the polymer emulsion composition and the biocidal composition have a broad range of biocidal activity against many different microorganisms. Moreover, the copper containing compound in combination with the biocide may advantageously limit growth of microorganisms without staining the polymer emulsion composition. The copper containing compounds as described herein are conventionally understood to impart color, such as a green hue, to paints and coating. However, the polymer emulsion composition and the biocidal composition of the present disclosure may advantageously exhibit antimicrobial properties while surprisingly avoiding the color impact conventionally expected with the copper containing compounds.

[0034] In addition, the polymer emulsion composition and biocidal composition of the present disclosure may include various other components, such as an inorganic oxide compound and an adjuvant compound. Of particular advantage, the polymer emulsion composition and the biocidal composition of the present disclosure may exhibit a potentiation interaction and a relatively high degree antimicrobial efficacy against a wide variety of microorganisms.

[0035] As used herein, a potentiation interaction refers to the fact that copper containing compound and the biocide combined together have a total effect that is greater than the biocidal properties of the biocide acting alone. In other words, the copper containing compound and the biocides of the present disclosure, optionally in combination with one or both of the inorganic oxide compound and the adjuvant compound, operate together so as to have greater antimicrobial activity in the presence of each against a certain microorganism than in comparison to the antimicrobial activity of the copper containing compound alone or the antimicrobial activity of the biocide alone at the same concentrations. Due to this potentiation effect, the amount of the copper containing compound and biocide present in the composition can be reduced while still producing the desired efficacy.

[0036] The combination of biocides and additives combined together in accordance with the present disclosure includes at least a copper containing compound and a biocide. In some example embodiments, a second biocide and/or a third biocide may be present to further enhance the effects. Consequently, the amount of the copper containing compound contained in the compositions can be reduced or minimized. In addition, due to the potentiation effect, the amount of the biocide can also be reduced or minimized. In other words, the polymer emulsion composition and the biocidal composition include a total amount of the copper containing compound and the biocide together that is less than if only one were present, while still having the same or better efficacy against one or more microorganisms.

[0037] In accordance with example aspects of the present disclosure, the copper containing compound generally includes a copper compound, such as an inorganic copper compound. The copper containing compound may include inorganic copper salts, such as carbonate, bicarbonate, sulphate, nitrate, chloride, hydroxide, borate, fluoride or oxide. Alternatively, the copper containing compound may include simple organic salts, such as formate or acetate, or as a complex such as N-nitroso-N- cyclohexyl-hydroxylamine-copper (copper-HDO).

[0038] Other examples of the copper containing compound include copper sulfates, such as basic copper sulfate and copper sulfate pentahydrate, copper oxides, such as cuprous oxide and cupric oxide, and copper salts, such as copper salts of fatty and rosin acids, copper ethylenediamine complex, copper triethanolamine complex, copper ethylenediaminetetraacetate, and copper thiocyanate. Still other examples of the copper containing compound include copper octanoate, copper diammonia diacetate complex, copper ethanolamine complex, copper naphthenate, and copper 8-quinolinoate.

[0039] In one example aspect, the copper containing compound includes at least one of basic copper carbonate, copper naphthenate, cupric oxide, copper thiocyanate, copper hydroxide, copper 8-quinolinolate, copper sulphate, copper nitrate, and copper bis(5-oxo-L-prolinato). In a preferred example aspect, the copper containing compound includes basic copper carbonate. [0040] The copper containing compounds described herein are not conventionally employed in paint and coating products due to the perceived ability of copper containing compounds to impact and, in some cases, entirely change the color of the resulting paint or coating. Of particular advantage, the present inventors have found that employing the copper containing compounds herein in the polymer emulsion compositions according to example aspects of the present disclosure surprisingly has little to no effect on the color of the resulting paint or coating. Thus, despite the presence of copper containing compounds, the latex paint may advantageously be a “pure white” base paint or a paint that may be tinted to a desired color. In one example aspect, the copper containing compound preferably includes basic copper carbonate or is basic copper carbonate. However, the copper containing compound may include other copper containing compounds, both sparingly soluble copper containing compounds and soluble copper containing compounds, that have little to no effect on the color of the resulting paint or coating.

[0041] In one example aspect, the copper containing compound may include micronized copper compound particles. The micronized copper compound particles may have a particle size of about 0.01 microns to about 25.0 microns, such as from about 0.01 microns to about 10 microns, such as from about 0.05 microns to about 10 microns, such as from about 0.1 microns to about 10.0 microns, such as from about 0.01 microns to about 1.0 micron, such as from about 0.05 microns to about 1.0 micron, such as from about 0.1 microns to about 1.0 micron, such as from about 0.2 microns to about 1.0 micron.

[0042] Advantageously, the present inventors have discovered that the copper containing compounds as described herein may be added directly to the polymer emulsion compositions and the biocidal compositions. Thus, in a preferred example aspect, the copper containing compound of the present disclosure is substantially free of a medium or matrix, such as glass. However, in another example aspect, the copper containing compound may be present in the form of a dispersion or solution.

[0043] As noted above, the biocide includes one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol. [0044] In another example aspect, the biocide includes a quaternary ammonium compound. For example, the biocide may include a quaternary ammonium halide, a quaternary ammonium carbonate/bicarbonate, or a benzyl ammonium halide.

[0045] Quaternary ammonium compounds, also known as “quats”, typically include at least one quaternary ammonium cation with an appropriate anion. Quats will generally have the following general formula:

[0046] The groups Ri, R2, R3 and R4 can vary within wide limits and examples of quaternary ammonium compounds that have antimicrobial properties will be well known to the person of ordinary skill in the art. Typically, two of Ri, R2, R3 and R4 are lower alkyl, meaning having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl groups. In addition, two of Ri, R2, R3 and R4 are longer chain alkyl groups of 6 to 24 carbon atoms, or a benzyl group. A" is a monovalent anion or one equivalent of a polyvalent anion of an inorganic or organic acid. Suitable anions for A" are in principle all inorganic or organic anions, in particular halides, for example chloride or bromide, carboxylates, sulfonates, phosphates or a mixture thereof.

[0047] In another example aspect, the quaternary ammonium compound may have the following R groups: Ri is benzyl or Ce-is-alkyl, R2 is Ci-is-alkyl or — [(CH2)2 — O]nRs where n=l-20, R3 and R4 independently of one another are Ci-4-alkyl, R5 is hydrogen or unsubstituted or substituted alkyl or phenyl, and A" is a monovalent anion or one equivalent of a polyvalent anion of an inorganic or organic acid.

[0048] In another example aspect, the quaternary ammonium compound may include a dialkyl ammonium compound, such as a dimethyl dialkyl ammonium compound. In one embodiment, the dimethyl dialkyl ammonium compound may have between about 8 and about 12 carbon atoms, such as from about 8 to about 10 carbon atoms in each of the alkyl groups. [0049] Examples of dimethyl dialkyl ammonium compounds which may be used as the biocide include dimethyl dioctyl ammonium compounds such as dimethyl dioctyl ammonium chloride, dimethyl didecyl ammonium compounds such as dimethyl didecyl ammonium chloride and the like. Mixtures of dimethyl dialkyl ammonium compounds may also be used and other anions, such as those described above may also be used. Commercially available dimethyl dialkyl ammonium compounds include, for example, BARD AC™ LF-80, BARD AC™ 22 and BARD AC™ 208M which are available from Arxada, LLC (formerly Lonza Specialty Ingredients).

[0050] In another example aspect, the biocide may include a quaternary ammonium carbonate, which can be represented by the following formula:

CO-3

wherein R¹ is a C1-C20 alkyl or aryl -substituted alkyl group and R² is a C8-C20 alkyl group, and preferably wherein R¹ is the same as R² and R¹ is a C8-C12 alkyl group, as well as compositions further including the corresponding quaternary ammonium bicarbonate

[0051] wherein R¹ is the same or a different C1-C20 alkyl or aryl -substituted alkyl group as above and R² is the same or a different C8-C20 alkyl group as above, but preferably wherein R¹ is the same as R² and R¹ is a C8-C12 alkyl group.

[0052] A quaternary ammonium carbonate/bicarbonate may include a di C8-C12 alkyl ammonium carbonate/bicarbonate. For example, in one particular example embodiment, the composition includes didecyl dimethyl ammonium carbonate and didecyl dimethyl ammonium bicarbonate. [0053] In other example embodiments, however, the carbonate/bicarbonate salts of quaternary ammonium cations may be selected from dioctyldimethylammonium carbonate, decyloctyldimethylammonium carbonate, benzalkonium carbonate, benzethonium carbonate, stearalkonium carbonate, cetrimonium carbonate, behentrimonium carbonate, dioctyldimethylammonium bicarbonate, decyloctyldimethylammonium bicarbonate, benzalkonium bicarbonate, benzethonium bicarbonate, stearalkonium bicarbonate, cetrimonium bicarbonate, behentrimonium bicarbonate, and mixtures of one or more such carbonate salts.

[0054] Preferably, the quaternary ammonium compound may include one or more of didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium carbonate, didecyl dimethyl ammonium bicarbonate, and alkyl dimethyl benzyl ammonium chloride.

[0055] In an example embodiment, the biocide may include a benzyl ammonium compound, such as an alkyl dimethyl benzyl ammonium compound. In general, the alkyl group may include from about 10 to about 18 carbon atoms, such as from about 12 to about 16 carbon atoms.

[0056] Examples of alkyl dimethyl benzyl ammonium compounds useable as the biocide include C12 alkyl dimethyl benzyl ammonium chloride, C14 alkyl dimethyl benzyl ammonium chloride, and Ci6 alkyl dimethyl benzyl ammonium chloride. In addition, a mixture of these alkyl dimethyl benzyl ammonium compounds can be used. Commercially available alkyl dimethyl benzyl ammonium compounds include, for example BARQUAT®DM-80 and BARQUAT® 50-65B, which are available from Arxada, LLC (formly Lonza Specialty Ingredients). These commercially available alkyl dimethyl benzyl ammonium compounds are blends of C12, C14, and Ci6 alkyl dimethyl benzyl ammonium chlorides. Generally, it is preferable that the alkyl dimethyl benzyl ammonium compound, when a blend, includes higher concentrations of C 12 alkyl and C14 alkyl components than Ci6 alkyl components. It is noted that other anions, including those mentioned above may also be used.

[0057] In another example aspect, the biocide includes an isothiazolone compound. Suitable isothiazolinones are represented by the following general formula:

[0058] where: R¹ denotes hydrogen, optionally substituted Ci-Cis alkyl, C2- Cs alkenyl or alkynyl, C2-C8 haloalkynyl, optionally substituted C3-C12 cycloalkyl, optionally substituted aralkyl having up to 10 carbon atoms, or optionally substituted aryl having up to 10 carbon atoms;

R² and R³ independently denote hydrogen, halogen or C1-C4 alkyl; or together R² and R³ may provide a 1,2 benzisothiazolin-3-one group (i.e. R² and R³ may combine to form — (CH)4 — ).

[0059] In one example aspect, R² and R³ independently denote chloro or hydrogen, or together R² and R³ may provide a 1,2 benzisothiazolin-3-one group.

[0060] Thus, in an example aspect, R1 substituents are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, cyclohexyl, 4-methoxyphenyl, 4- chlorophenyl, 3, 4-di chlorophenyl, benzyl, 4-methoxybenzyl, 4-chlorobenzyl, 3,4- di chlorobenzyl, phenethyl, 2-(4-methoxyphenyl)ethyl, 2-(4-chlorophenyl)ethyl, 2-(3,4- dichlorophenyl)ethyl, hydroxymethyl, chloromethyl and chloropropyl.

[0061] In one such example aspect, the R1 substituents in the compound of the above formula denotes hydrogen, optionally substituted Cl -Cl 8 alkyl, optionally substituted aralkyl having up to 10 carbon atoms, or optionally substituted aryl having up to 10 carbon atoms. In a further aspect, R1 denotes hydrogen or optionally substituted C1-C18 alkyl. Additionally or alternatively, R1 is hydrogen or Cl- C8 alkyl, with hydrogen, methyl, butyl and octyl being the most preferred R1 substituents.

[0062] Thus, in one aspect, isothiazolinones used in the polymer emulsion compositions and/or biocidal compositions according to the present disclosure are those represented by the general formula above, where R1 denotes hydrogen or Cl- C8 alkyl, and R2 and R3 independently denote chloro or hydrogen, or together R2 and R3 may provide a 1,2 benzisothiazolin-3-one group. [0063] In one example aspect, isothiazolinones used in the polymer emulsion compositions and/or the biocidal compositions according to the present disclosure are those represented by the general formula above, where R1 denotes hydrogen, methyl, butyl or octyl, and R2 and R3 independently denote chloro or hydrogen, or together R2 and R3 may provide a 1,2 benzisothiazolin-3-one group.

[0064] Furthermore, as discussed above, in one example aspect, the isothiazolinone of the formula above is a benzisothiazolinone of the following general formula:

[0065] where, R is hydroxy, halogen (especially chlorine), Cl-4-alkyl or Cl -flalkoxy;

R1 is as hereinbefore defined; and n is from 0 to 4.

[0066] R, when present in an aspect, is located in one or both of the 5 and 6 positions of the phenyl ring of the benzisothiazolinone. However, in a further aspect, n is zero.

[0067] In one example aspect, a benzisothiazolinone of are those in which R1 is H or Cl-5-alkyl, or where R1 is H or C3-5-alkyl. Examples of these compounds include, for example l,2-benzisothiazolin-3-one, N-n-butyl-, N-methyl-, N-ethyl-, N-n-propyl-, N-isopropyl-, N-n-pentyl-, N-cyclopropyl-, N-isobutyl-, and N-tert-butyl-1,2- benzisothiazolin-3-one. Thus, in one aspect, the benzisothiazolinone is 1,2- benzisothiazolin-3-one.

[0068] For instance, in one example aspect, isothiazolones include, but are not limited to, methylisothiazol-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), octylisothiazol-3-one (OIT), l,2-benzisothiazol-3(2H)-one (BIT), N-methyl-l,2-benzisothiazol-3-one (MBIT) and N-(n-butyl)-l,2-benzisothiazol-3-one (BBIT). Particularly preferred isothiazolones include, but are not limited to, methylisothiazol-3-one (MIT), 5-chloro- 2-methyl-4-isothiazolin-3-one (CMIT), octylisothiazol-3-one (OIT), 1,2- benzisothiazol-3(2H)-one (BIT), N-methyl-l,2-benzisothiazol-3-one (MBIT) and N- (n-butyl)-l,2-benzisothiazol-3-one (BBIT). Even more preferred isothiazol-3-ones are 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), octylisothiazolone (OIT), 1,2- benzisothiazol-3(2H)-one (BIT) and N-(n-butyl)-l,2-benzisothiazol-3-one (BBIT), more preferably octylisothiazolone (OIT), l,2-benzisothiazol-3(2H)-one (BIT) and N- (n-butyl)-l,2-benzisothiazol-3-one (BBIT), or combinations thereof.

[0069] Preferably, the isothiazolone compound may include one or more of 2- methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), 5-chloro-2-n-octyl-4-isothiazolin- 3-one (COIT), 2-octyl-2H-isothiazolin-3-one (OIT), l,2-benzothiazolin-3-one (BIT), N-methyl-l,2-benzisothiazolin-3-one (MBIT), and 2-butyl-l,2-benzisothiazolin-3(2H)- one (BBIT).

[0070] In another example aspect, the biocide includes a haloalkylnyl compound. The haloalkylnyl carbamate may include an iodoalkynl carbamate having the following general formula:

[0071] wherein m is 1 , 2 or 3; n is 1 , 2 or 3; and R is hydrogen (H); an unsubstituted or substituted alkyl, aryl, aralkyl alkylaryl, alkenyl, cycloalkyl, or cycloalkenyl or an alkoxy aryl all having from one to not more than 20 carbon atoms, and m and n may be the same or different.

[0072] Suitable R substituents for the iodoalkynyl carbamate compound include alkyls such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cycloalkyls such as cyclohexyl, aryls, alkaryls and aralkyls such as phenyl, benzyl, tolyl, cumyl, halogenated alkyls and aryls, such as chlorobutyl and chlorophenyl, and alkoxy aryls such as ethoxyphenyl and the like. Thus, suitable carbamate compounds are selected from the group consisting of 3-iodo- 2-propynyl butyl carbamate (IPBC), 3-iodo-2- propynyl hexyl carbamate (IPHC), 3- iodo -2-propynyl cyclohexyl carbamate (IPCC), 3-iodo-2-propynyl phenyl carbamate (IPPhC), 3-iodo-2-propynyl benzyl carbamate (IP Benzyl C), 3-iodo-2-propynyl propyl carbamate (IPPC), 4-iodo-3- butynyl propyl carbamate (IBPC), 3-iodo-2-propynyl-4- chloro phenyl carbamate (IPCI PhC), 3-iodo-2-propynyl-4-chloro butyl carbamate (IPCI BC) and mixtures thereof.

[0073] Preferably, the haloalkylnyl compound may include 3-iodo-2-propynyl butyl carbamate (IPBC).

[0074] In another example aspect, the biocide includes a triazine compound. For example, the triazine compound may include 1,3,5-triazine.

[0075] In another example aspect, the biocide includes an azole compound (i.e., a compound including an azole group). The azole may be an imidazole or a 1,2,4- triazole and is preferably represented by the following general formula:

[0076] where:

[0077] X denotes CR4 or N;

[0078] R1 denotes hydrogen or a linear, branched, cyclic, aromatic or any combination thereof, saturated or unsaturated, substituted or unsubstituted Cl to C40 group,

[0079] any of the carbon atoms other than those bound to the nitrogen atom shown in formula (IV) may be replaced with an optionally substituted hetero atom;

[0080] R2 denotes hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C6-C10 aromatic, C5- C10 heteroaromatic or C1-C4 alkyl carbamate; and

[0081] R3 and R4 denote hydrogen; or

[0082] together R3 and R4 may provide a benzimidazole group (i.e. R3 and R4 may combine to form — (CH)4 — ).

[0083] The polymer emulsion composition and the biocidal composition of the present disclosure may include one or more azole compounds, such as mixtures of an imidazole and a 1,2,4-triazole, or mixtures of two or more 1,2,4-triazoles. Using a mixture of azoles may allow a broader range of activity against microorganisms in some example aspects. However, in one example aspect, the compositions of the present disclosure utilizes one or more l,2,4-triazole(s) alone or in combination with an imidazole.

[0084] The imidazole compound incorporates a five-membered diunsaturated ring composed of three carbon atoms and two nitrogen atoms at non-adjacent positions. The imidazole compound may be a benzimidazole. In one aspect, the azole can include thiabendazole, imazalil, carbendazim and prochloraz.

[0085] The 1,2,4-triazole compound incorporates a five-membered diunsaturated ring composed of three nitrogen atoms and two carbon atoms at non-adjacent positions.

[0086] In one example aspect, triazole compounds include a triazole compound selected from compounds of the following general formula:

[0087] wherein R5 represents a branched or straight chain Cl -5 alkyl group (e.g. t- butyl) and R6 represents a phenyl group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or Cl- 3 alkyl (e.g. methyl), Cl -3 alkoxy (e.g. methoxy), phenyl or nitro groups.

[0088] Alternatively, the triazole compound can be selected from compounds of the following general formula:

[0089] wherein R⁷ is as defined for R⁶ above and R⁸ represents a hydrogen atom or a branched or straight chain C1-5 alkyl group (e.g. n-propyl). [0090] Particularly, in one example aspect, the azole can include one or more triazoles including, but not limited to, triadimefon, triadimenol, triazbutil, propi conazole, cy proconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, ipconazole, prothioconazole and mixtures thereof.

[0091] In a further example aspect, triazoles include propi conazole, azaconazole, hexaconazole, tebuconazole, cyproconazole, triadimefon, ipconazole, prothioconazole, difenoconazole, and mixtures thereof, such as, in one example aspect, propi conazole, tebuconazole, cyproconazole, difenoconazole and mixtures thereof.

[0092] Preferably, the azole compound may include a 1,2,4-triazole compound, the 1,2,4-triazole compound may include one or more of cyproconazole, fenbuconazole, propi conazole, tebuconazole, triadimefon, triticonazole, and difenoconazole.

[0093] Moreover, notwithstanding in the type or amount of azole(s) selected, the azole may be present in micronized form, alone or in combination with a dispersing agent. For instance, in an aspect, the azole particles have a size of about 10 microns or less, such as about 8 microns or less, such as about 6 microns or less, such as about 5 microns or less, such as about 4 microns or less, such as about 3 microns or less, such as about 2 microns or less, such as about 1 micron or less. Additionally or alternatively, at least about 10% or more of the azole particles have a size of about 1 micron or less, such as about 25% or more, such as about 50% or more, such as about 60% or more, such as about 70% or more, such as about 80% or more, such as about 90% or more, such as about 95% or more.

[0094] Furthermore, in one example aspect, the polymer emulsion composition or the biocidal composition may also include a dispersing agent. In one aspect, the dispersing agent is an alkanolamine, such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine. In one example aspect, the dispersing agent is an ethanolamine, such as monoethanolamine. However, it should be understood that other dispersing agents as known in the art may be used.

[0095] Additionally, or alternatively, the dispersing agent may be complexed with some or all of one or more components of the composition. For instance, in one aspect, the dispersing agent may be complexed with at least a portion of the azole, the copper containing compound, or both the azole and the copper containing compound.

However, it should be understood that, in one example aspect, at least a portion of the dispersing agent may be “free” in solution in the sense that at least a portion is not complexed with another component.

[0096] In another example aspect, the biocide includes a urea derivative, such as an aryl urea compound. For example, the aryl urea compound may include (3 -(3, 4- di chi orophenyl)- 1, 1 -dimethylurea (Diuron).

[0097] In another example aspect, the biocide includes a succinate dehydrogenase inhibitor. Generally, any active substance which inhibits succinate dehydrogenase in a mitochondrial respiration chain may be employed. However, in one example aspect of the present disclosure, the succinate dehydrogenase inhibitor includes a carboxamide compound. Suitable carboxamide compounds include carboxanilides, carboxylic morpholides, benzoic acid amides, and other carboxamides.

[0098] Exemplary carboxanilides include, for example, benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, fluxapyroxad, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxy-carboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-l-methyl-lH-pyrazole-4- carboxamide and N-(2-(l,3,3-trimethyl-butyl)-phenyl)-l,3-dimethyl-5-fluoro-lH- py razol e-4-carb oxami de .

[0099] Exemplary carboxylic morpholides include, for example, dimethomorph, flumorph, and pyrimorph.

[00100] Exemplary benzoic acid amides include, for example, flumetover, fluopicolide, fluopyram, and zoxamide.

[00101] Exemplary “other” carboxamides include, for example, carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofam, niacinamide, nicotienamide and N-(6-m ethoxy-pyri din-3 -yl) cyclopropanecarboxylic acid amide.

[00102] In another example aspect, the polymer emulsions and compositions described herein are substantially free of pyrithione compounds, such as copper pyrithione. [00103] The relative amounts of the copper containing compound and the biocide can vary significantly based on many factors. The factors include the type of biocides used, the end use application (type of paint, coating, etc.), and the desired microorganism(s) to be controlled.

[00104] For example, the copper containing compound may be present in compositions of the present disclosure, including the polymer emulsion and biocidal composition, in an amount of less than about 10,000 ppm, such as less than about 7,500 ppm, such as less than about 5,000 ppm, such as less than about 2,500 ppm, such as about less than about 1,000 ppm, such as about less than 600 ppm, such as less than about 500 ppm, such as less than about 400, such as less than about 300 ppm, such as less than about 200 ppm, such as less than about 100 ppm, such as less than about 75 ppm, such as less than about 50 ppm, such as less than about 25 ppm, such as about 10 ppm.

[00105] In another example aspect, the biocide may be present in compositions of the present disclosure, including the polymer emulsion and biocidal composition, in an amount of less than about 10,000 ppm, such as less than about 7,500 ppm, such as less than about 5,000 ppm, such as less than about 2,500 ppm, such as about less than about 1,000 ppm, such as about less than 600 ppm, such as less than about 500 ppm, such as less than about 400, such as less than about 300 ppm, such as less than about 200 ppm, such as less than about 100 ppm, such as less than about 75 ppm, such as less than about 50 ppm, such as less than about 25 ppm, such as about 10 ppm.

[00106] In another example aspect, the copper containing compound and the biocide may be present in the polymer emulsion composition or biocidal composition at a weight ratio of from about 1000: 1 to about 1 : 1000, such as from about 500:1 to about 1 :500, such as from about 20:1 to about 1 :20, such as from about 15:1 to about 1 : 15, such as from about 5: 1 to about 1 :5, such as from about 3: 1 to about 1 :3, such as from about 2: 1 to about 1 :2, such as about 1 : 1.

[00107] In one example aspect, the biocidal composition further includes an inorganic oxide compound. For example, the inorganic oxide compound may include one or both of zinc oxide and iron oxide. [00108] In another example aspect, the copper containing compound and the iron oxide are present in the polymer emulsion composition at a weight ratio of from about 10: 1 to about 30: 1, such as from about 15: 1 to about 25: 1.

[00109] In another example aspect, the copper containing compound and the zinc oxide compound are present in the polymer emulsion composition at a weight ratio of from about 10: 1 to about 1 : 10, such as about 1 :1.

[00110] In another example aspect, the inorganic oxide compound used in the invention is in the form of particles having a particle size 0.01 microns to 25.0 microns. In one embodiment particle size of the inorganic oxide compound used in the compositions disclosed herein can be between 0.01 to 10 microns, 0.05 to 10 microns, between 0.1 to 10.0 microns, between 0.01 to 1.0 micron, between 0.05 to 1.0 microns, between 0.1 to 1.0 microns, between 0.2 to 1.0 microns.

[00111] In another example aspect, the inorganic oxide compound is present in the polymer emulsion composition at a concentration of about 10 ppm to about 10,000 ppm, such as from about 15 ppm to about 7,000 ppm, such as from about 50 ppm to about 5,000 ppm.

[00112] In another example aspect, notwithstanding in the type or amount of inorganic oxide compound employed, the inorganic oxide compound may be present in micronized form, alone or in combination with a dispersing agent. For instance, in one embodiment the inorganic oxide compound may have a particle size D50 of about 25 microns or less, such as about 10 microns or less, such as about 6 microns or less, such as about 5 microns or less, such as about 4 microns or less, such as about 3 microns or less, such as about 2 microns or less, such as about 1 micron or less.

[00113] In one example aspect, the biocidal composition further includes an adjuvant compound. For instance, the adjuvant compound may include a guanidine enhancer having the structure of Compound I, Compound I having the formula:

HR2N-(C=NHR3)-NR1H

(Compound I)

[00114] wherein, R3 is H, CN, Ci-C3o-alkyl, Ci-C3o-alkenyl, Ci-C3o-alkynyl, C7- C3o-alkylaryl, or Ce-Ci2-aryl; R1 is H, CN, Ci-C3o-alkyl, Ci-C3o-alkenyl, C1-C30- alkynyl, C?-C3o-alkylaryl, or Ce-Ci2-aryl; R2 is H, CN, Ci-C3o-alkyl, Ci-C3o-alkenyl, Ci-C3o-alkynyl, C?-C3o-alkylaryl, or Ce-Ci2-aryl; and wherein at least one of R3, Rl, or R2 is C.

[00115] In one example aspect, the adjuvant compound and the copper containing compound are present in the polymer emulsion composition at a weight ratio of from about 1 : 1 to about 1000: 1.

[00116] In another examples aspect, the adjuvant compound is present in the polymer emulsion composition at a concentration of about 100 ppm to about 10,000 ppm, such as from about 200 ppm to about 10,000 ppm, such as from about 1,000 ppm to about 10,000 ppm.

[00117] As used herein, references to chemical formulas use standard element symbols according to the periodic table (e.g., C denotes carbon, N denotes nitrogen, etc.). Further, references to chemical formula are based on standard bonding such that carbon can make up to four (4) bonds and nitrogen can make up to three (3) bonds unless otherwise specified. As such, references to CN, should be understood as indicating a cyano group where carbon includes a triple bond with nitrogen and the remaining carbon bond can indicate attachment of the cyano group to a chemical structure.

[00118] The guanidine enhancer includes one or more of the following: 1- cyanoguanidine, a salt of 1 -cyanoguanidine, 2-cyanoguanidine (also referred to as dicyandiamide), and a salt of 2-cyanoguanidine. Both 1 -cyanoguanidine and 2- cyanoguanidine are derivatives of Compound I, where R2 or Rl is CN and R3 is H, and Rl and R2 are H and R3 is CN, respectively. As should be understood, conversion between 1 -cyanoguanidine and 2-cyanoguanidine may occur via tautomerization in aqueous solution or exposure to other proton donating solvents and so compositions that include only one tautomer, may display conversion over time to a mixture of both. Further, while exemplified using 1 -cyanoguanidine and 2-cyanoguanidine, generally tautomer forms of species derived from Compound I can be included as guanidine enhancers in accordance with example implementations of the present disclosure. Tautomer forms of Compound I include structures (a) and (b), which have the formulas:

Compound 1(b)

[00119] wherein, R3 is H, CN, Ci-C3o-alkyl, Ci-C3o-alkenyl, Ci-C3o-alkynyl, C7- C3o-alkylaryl, or Ce-Ci2-aryl; R1 is H, CN, Ci-C3o-alkyl, Ci-C3o-alkenyl, C1-C30- alkynyl, C?-C3o-alkylaryl, or Ce-Ci2-aryl; R2 is H, CN, Ci-C3o-alkyl, Ci-C3o-alkenyl, Ci-C3o-alkynyl, C?-C3o-alkylaryl, or Ce-Ci2-aryl; and wherein at least one of R3, Rl, or R2 is CN.

[00120] In general, guanidine compounds can react with a proton donor to form a salt having a guanidinium cation carrying a positive charge, paired with an anion carrying a negative charge. Thus, in certain polymer emulsion compositions or biocidal compositions, the guanidine enhancer can be a salt of Compound I such as a salt of 1- cyanoguanidine and/or a salt of 2-cyanoguanidine.

[00121] Some examples of anions that can be included as the salt of 1- cyanoguanidine or the salt of 2-cyanoguanidine can include inorganic anions such as a halide (e.g., chloride, bromide, fluoride, iodide, etc.), nitrate, sulfate, etc. Alternatively or additionally, the anion can include an organic anion such as acetate or carboxylate anions derived from fatty acids such as octanoic acid, decanoic acid, or dodecanoic acid. Preferably, the guanidine enhancer includes 2-dicyandiamide.

[00122] In another example aspect, the adjuvant compound may include trifluoroacetic acid or a salt thereof. For instance, the adjuvant compound may include zinc ethyltrifluoroacetate.

[00123] In another example aspect, the adjuvant compound may include a tetramethylguanidine (TMG), such as 1,1,3,3-tetramethylguanidine and/or 2-tert-butyl- 1, 1,3,3-tetramethylguanidine.

[00124] In another example aspect, the adjuvant compound may include a cystamine enhancer, such as cystamine dihydrochloride.

[00125] In one example aspect, the pH of the polymer emulsion composition or the biocidal composition is from about 4.5 to about 12.0, such as from about 5.0 to about 9.5, such as from about 6.0 to about 9.5, such as from about 7.0 to about 9.5, such as from about 8.0 to about 9.5. As known in the art, pH builders, pH buffers, and other pH adjusting agents may be used to obtain and stabilize the above pH values.

[00126] The polymer emulsion composition of the present disclosure further includes a solvent. In the polymer emulsion of the present disclosure, the solvent may include a wide variety of suitable organic and/or inorganic solvents. In one example aspect, the solvent includes water.

[00127] In another example aspect, the polymer emulsion composition of the present disclosure may be a latex paint composition. Generally, the latex paint composition further includes a latex binder (e.g., a polymer including one or more acrylate, vinyl acetate, vinyl chloride, and/or styrene butadiene monomers). Optionally, the latex paint can further include an emulsifier and/or surfactant to improve distribution of the latex binder throughout the polymer emulsion composition. In this manner, the emulsifier and/or surfactant can be used to produce a more homogenous mixture that can provide a more even coating of the resulting latex paint coating. Optionally, the latex paint composition can include a thickening agent to adjust the viscosity of the latex paint to improve adhesion of the wet paint to an applicator (e.g., a brush or roller). Optionally, the latex paint composition can include one or more pigments (e.g., TiO2) for providing a color to the latex paint composition. Optionally, the latex paint composition can include a cosolvent (e.g., ethylene glycol) that can improve solubility of components of the latex paint composition.

[00128] In one example aspect, the polymer emulsion composition may constitute from about 5 wt. % to about 40 wt. % of the latex paint composition, such as from about 20 wt. % to about 30 wt. % of the latex paint composition.

[00129] Another aspect of example implementations can include a type of latex binder. The latex binder can include various polymers suitable for latex paints such as an acrylates (e.g., polymethylmethacrylate), that can be formed as a homopolymer or co-polymer. For example, a co-polymer can include incorporation of another monomer (e.g., butadiene styrene). In some implementations, the acrylate can be modified to include one or more nitrile groups. Thus, latex binders can include various acrylates, acrylate butadiene styrene copolymers, and acrylonitrile butadiene styrene copolymers. Additionally, these latex binders are provided for example purposes, and additional latex binders may be used alone or in combination with implementations of the disclosure.

[00130] As an example for illustration, an implementation of the present disclosure can include an latex paint including a latex binder with an acrylate. The acrylate can include a polymer or copolymer that includes one or more acrylate monomers.

Example aspects of the acrylate polymer or copolymer can include a mass fraction of an acrylate monomer. For instance, the acrylate can include a copolymer that includes an acrylate monomer (e.g., methyl methacrylate) and a second monomer (e.g., butadiene styrene). The mass fraction of the acrylate monomer to the total weight of the copolymer can define the mass fraction. In some acrylates the mass fraction of acrylate monomer to the total weight of the copolymer can be no less than about twenty (20) wt% and no greater than about one hundred (100) wt% such as no less than about thirty (30) wt% and no greater than about eighty (80) wt%, no less than about forty (40) wt% and no greater than about seventy (70) wt%, or no less than about forty five (45) wt% and no greater than about sixty (60) wt% (e.g., one hundred (100) wt%, ninety five (95) wt%, ninety (90) wt%, eighty five (85) wt%, eighty (80) wt%, seventy five (75) wt%, seventy (70) wt%, sixty five (65) wt%, sixty (60) wt%, fifty five (55) wt%, or fifty (50) wt%). In particular, certain implementations can include an acrylate having a mass fraction of acrylate monomer to the total weight of acrylate greater than fifty (50) wt%.

[00131] In implementations of the present disclosure, the latex paint can include or may be formulated to include an amount of pigment. For instance, certain example latex paints can include a pigment, the pigment including titanium dioxide (TiO2) at a concentration of no less than five (5) wt% TiO2 and no greater than sixty (60) wt% TiO2 based on the total weight of the latex paint. TiO2 can be used to impart whiteness and/or opacity to example implementations and may also be included to build viscosity. In general, example implementations can include no less than five (5) wt% and no greater than sixty (60) wt% TiO2 such as no less than fifteen (15) wt% and no greater than fifty five (55) wt% TiO2, no less than twenty (20) wt% and no greater than fifty (50) wt% TiO2, or no less than twenty five (25) wt% and no greater than forty five (45) wt% TiO2.

[00132] In other example embodiments, the polymer emulsion composition of the present disclosure may be an adhesive.

[00133] In one example aspect, the biocidal composition according to the present disclosure may be manufactured and sold as a biocidal additive composition that includes the copper containing compound, the biocide, and one or both of the inorganic oxide compound and the adjuvant compound, and the additive composition may be substantially free of other materials. Thus, the additive composition may be a three- part additive composition or a four-part additive composition in such example embodiments. The three-part or four-part additive composition may be provided as an ingredient for forming a latex paint composition or a polymer emulsion composition. Moreover, the three-part additive composition or the four-part additive composition may be added to other components to form a latex paint composition or a polymer emulsion composition. As noted above, the polymer emulsion composition and/or the latex paint composition may advantageously provide broad spectrum antimicrobial control in the composition.

[00134] As evidence of potentiation of a copper containing compound and the biocide, the inhibitory concentrations of the biocide is lower in the presence of the copper containing compound when tested against a target microorganism. . [00135] The preceding description is exemplary in nature and is not intended to limit the scope, applicability or configuration of the disclosure in any way. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the disclosure. [00136] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention is related.

[00137] As used in this application and in the claims, the singular forms “a”, “an”, and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises”. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optional ingredients, components or limitations described herein or otherwise useful in biocidal compositions.

[00138] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percentages, and so forth, as used in the specification or claims are to be understood as being modified by the term “about”. Accordingly, unless otherwise indicated, implicitly or explicitly, the numerical parameters set forth are approximations that may depend on the desired properties sought and/or limits of detection under standard test conditions/methods. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited.

[00139] As used herein, “optional” or “optionally” means that the subsequently described material, event or circumstance may or may not be present or occur, and that the description includes instances where the material, event or circumstance is present or occurs and instances in which it does not. As used herein, “w/w%” and “wt%” mean by weight as relative to another component or a percentage of the total weight in the composition.

[00140] The term “about” is intended to mean approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[00141] The term “substantially free of’ when used to describe the amount of substance in a material is not to be limited to entirely or completely free of and may correspond to a lack of any appreciable or detectable amount of the recited substance in the material. Thus, e.g., a material is “substantially free of’ a substance when the amount of the substance in the material is less than the precision of an industry- accepted instrument or test for measuring the amount of the substance in the material. In certain example embodiments, a material may be “substantially free of’ a substance when the amount of the substance in the material is 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%, less than 0.5%, or less than 0.1% by weight of the material.

[00142] The phrase “effective amount” means an amount of a compound that promotes, improves, stimulates, or encourages a response to the particular condition or disorder or the particular symptom of the condition or disorder.

[00143] The terms “potentiator” and “adjuvant” as used herein refers to an additive that can affect the performance of an active compound when used in combination with the active compound but does not exhibit any biocidal activity itself and/or does not exhibit significant biocidal activity itself in the compositions of the invention.

[00144] The term “biocidal agent” as used herein refers to any chemical compound that prevents the growth of organisms on a coating surface and/or that prevents the growth of organisms “in-can” in a paint or coating prior to surface application.

[00145] The terms “antifouling paint” and “antifouling coating” are used interchangeably herein.

[00146] As used herein, the terms “first”, “second”, and “third” may be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components.

[00147] Here and throughout the specification and claims, range limitations are combined and interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise. For example, all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.

[00148] As used herein, the term “D50” or “D50 particle size” refers to the volume median particle size, where 50% of the particles of the sample volume have a size below that range or value.

[00149] Analogously, as used herein, the term “D95” or “D95 particle size” refers to a value where 95% of the particles of the sample volume have a size below that range or value.

[00150] As used herein, the term “particle size” as used herein, unless specifically stated otherwise, refers to the median particle size D50. Particle size can be measured using a laser scattering particle size analyzer, such as a HORIBA LA 910 particle size analyzer.

[00151] The terms “median particle size” and “average particle size” and D50 are used herein interchangeably.

[00152] As used herein, the term “micronized” as used herein means a median particle size (D50) in the range of 0.01 to 25 microns.

[00153] This written description uses examples to disclose the present disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

[00154] Furthermore, certain aspects of the present disclosure may be better understood according to the following examples, which are intended to be non-limiting and exemplary in nature. Moreover, it will be understood that the compositions described in the examples may be substantially free of any substance not expressly described. EXAMPLE 1

[00155] The antibacterial efficacies of emulsion compositions in wet paint were evaluated using an modified IBRG P016/001/draft test method 2.0 (A Method for Evaluating the Resistance of Aqueous based Paints to Bacterial Growth in the Wet State, Apr. 2016) by extending three (3) inoculation cycles to four (4) inoculation cycles. In brief, a matt wall paint (85% PVC) was prepared following the composition listed in Table 1. Micronized basic copper carbonate dispersion (pBCC containing copper: expressed as Cu) or copper sulfate solution (CuSCU), Proxel BD-20 (containing l,2-benzisothiazolin-3-one: expressed as BIT), Vanquish 100 (containing 2-butyl-l,2-benzisothiazolin-3-one: expressed as BBIT), Isocil WT (containing 2- octyl-l,2-isothiazolin-3-one: expressed as OIT) and Proxel 101 (containing 5-chloro-2- methyl-l,2-thiazol-3-one: expressed as CMIT and 2-methyl-l,2-isothiazolin-3-one: expressed as MIT) were added into the matt wall paint for target Cu, BIT, BBIT, OIT and CMIT/MIT level, respectively. A standard consortium of six (6) bacterial populations: Alcaligenes faecalis (BAM 487 NCIMB 13147), Enterobacter aerogenes (BAM 594 NCIMB 10102), Escherichia coli (BAM 590 NCIMB 12793), Flavobacterium odoratum (BAM 657 NCIMB 13294), Pseudomonas vesicularis (BAM 592 NCIMB 13293), Providencia rettgeri (BAM 488 NCIMB 10842) was used to inoculate an aliquot (e.g., 30 gram) of test paint (Table 1) at 1% (v/w) to achieve 5 x 10⁶ to 5 x 10⁷ cfm/mL of inoculum concentration in each test paint. The test paints were incubated at 30 ± 2°C for 7 days. The degrees of microbial contamination of all samples were determined by carrying out streak inoculation onto the appropriate growth medium (Nutrient Agar for Bacteria) following 7 day incubation and prior to the next inoculation. The microbial growth on streak plates was assessed using the rating scale given in Table 2. The above steps were repeated to re-inoculate the samples for the 2^nd, 3^rd and 4^th cycle, and the microbial growths were re-assessed accordingly.

[00156] Table 1. Matt Wall Paint Composition

[00157] Table 2. Rating Scale of Microbial Growth

[00158] The antibacterial efficacies of copper-containing additives in this wet matt wall paint are given in Table 3. When pBCC or CuSC (at 50 ppm Cu) was added into the paint, the BIT level for passing the tests was significantly lower (from 150 ppm to 15 ppm) while pBCC itself does not show antibacterial efficacy up to 200 ppm Cu level. Furthermore, the combinations of pBCC (at 50 ppm Cu) with BIT (15 ppm), further combined with BBIT (15 ppm), or OIT (15 ppm), or CMIT/MIT (7.5 and 15 ppm) pass the test while BBIT, OIT, or CMIT/MIT alone fails the test at 15 ppm.

[00159] Table 3. Antibacterial Efficacies of Emulsion Compositions in Paint

EXAMPLE 2

[00160] The antifungal and anti -yeast efficacies of emulsion compositions were evaluated by an Arxada (formerly Lonza Specialty Ingredients) Standard 5 “Fungal/ Yeast Wet State Preservation Test”. In brief, a matt wall paint (85% PVC) was prepared following the composition listed in Table 1. pBCC dispersion (containing Cu) or copper sulfate solution (CuSC ), Proxel BD-20 (containing BIT), Vanquish 100 (containing BBIT), Isocil WT (containing OIT) and Proxel 101 (containing CMIT/MIT) were added into the matt wall paint for target Cu, BIT, BBIT, OIT and CMIT/MIT level, respectively. A standard consortium of three (3) fungi populations: Aspergillus brasiliensis (ATCC 9642), Geotrichum candidum (IMI 321760), Penicillium funiculosum (IMI 211742), and two (2) yeast populations: Candida albicans (NCYC 1363), Saccharomyces cerevisiae (ATCC 9763) was used to inoculate an aliquot (e.g., 30 gram) of test paint to achieve 10⁵ cfm/mL of fungi/yeast concentration in each test paint. The test paints were incubated at 25°C. After a contact time of 7 days, the degrees of microbial contamination of all samples were determined by carrying out streak inoculation onto the surface of Sabouraud dextrose agar. Plates were stored at 25°C for fungi/yeast and incubated for at least 120 hour prior to examining the surface for viable colonies. The inoculation and assessment procedure was repeated at 7 day intervals for a period of 4 weeks. The microbial growth on streak plates was assessed using the rating scale given in Table 4. [00161] Table 4. Rating Scale of Microbial Growth

[00162] The antifungal/yeast efficacies of copper-containing additives in this wet matt wall paint are given in Table 5. The combinations of pBCC (at 200 ppm Cu) or CuSO4 (at 100 ppm Cu) and BIT (at 15 ppm) pass the test while each individual component fails the test at these levels. Furthermore, the combination of pBCC (at 20 ppm Cu) and BIT (at 15 ppm) with CMIT/MIT (both 7.5 and 15 ppm) further reduces the respective Cu and CMIT/MIT level from 200 and 15 ppm to 20 and 7.5 ppm for passing the test. In addition, when the pBCC (at 20 ppm Cu) in combination with BIT (at 15 ppm) and OIT (at 15 ppm) has more efficient control than pBCC plus BIT or OIT alone.

[00163] Table 5. Antifungal/Yeast Efficacies of Emulsion Compositions in Paint

EXAMPLE 3

[00164] A flat wall paint (50% PVC, 35% Solid Vol, 45 g/L VOC) was prepared following the composition listed in Table 6. Aliquots of 200 gram flat wall paint were weighed out and treated with Proxel CMC-E (containing CMIT/MIT) or Proxel BC (containing BIT and CMIT/MIT) to achieve an active level of 20 ppm of CMIT/MIT. The treated paints were split into 2 parts. One part was left as a CMIT only treatment and the other part was treated with pBCC to achieve an active level of 100 ppm Cu. All samples were further split into 2 parts. One part was submitted for time zero analysis, while the other one was aged in at 30°C in an oven. The 30°C-aged samples were submitted for analysis at 2 and 4 weeks. The quantitative levels of CMIT in paints was analysed by Liquid Chromatography-Mass Spectroscopy (LC-MS).

[00165] Table 6. Flat Wall Paint Composition

[00166] The CMIT/MIT levels in flat wall paint after 30°C aging are given in Table 7. The presence of 100 ppm Cu gives better CMIT/MIT stability as indicated by the higher percent of CMIT/MIT retained in the paint after 2 and 4 week aging (70-75% vs. 55-60%/45-50% vs. 30-35%).

[00167] Table 7. CMIT Level in Flat Wall Paint

EXAMPLE 4

[00168] The compatibilities of copper compounds in paint were evaluated via visual assessment of dry film appearance of the flat wall paint (50% PVC, 35% Solid Vol, 45 g/L VOC, Table 6). pBCC dispersion or CuSC aqueous solution (5%) were added into the flat wall paint to achieve 600 ppm level of Cu. The test paints were mixed at 1500 rpm for 10 minute and then equilibrated overnight. Test paints were drawn down on sealed Leneta chart to achieve 5 mil wet film thickness and then air dried for 24 hours. The coating appearance was visually inspected for any defects such as grits formed due to incompatibility. As shown in Table 8, water-insoluble pBCC is compatible but water-soluble CuSC is incompatible in this acrylic paint.

[00169] Table 8. Compatibilities of Copper Compounds in Paint

EXAMPLE 5 [00170] The impacts of copper compounds on the color of dried paint film were studied in a flat wall paint (50% PVC, 35% Solid Vol, 45 g/L VOC, Table 7). 5 gram of insoluble copper compound was dispersed into a mixture of 44.5 g water and 0.5 g Tamol 731 A dispersant and then mixed at 1500 rpm for 10 minutes. 2 gram of soluble copper compound was dissolved into 38 g water. The resulting dispersion of insoluble copper compound (10%) and solution of soluble copper compound (5%) were added into the paint to achieve 300 and 600 ppm level of Cu. The test paints were mixed at 1500 rpm for 10 minute and then equilibrated overnight. The test paints were drawn down on sealed Leneta chart to achieve 5 mil wet film thickness and then air dried for 24 hours. The colors of dry films were measured by a BYK spectro-guide colorimeter and the color changes (DE, DE’) were calculated as follow.

[00171] L: the lightness of the color (L = 0 yields black and L = 100 indicates diffuse white; specular white may be higher)

[00172] a: its position between red/magenta and green (a, negative values indicate green while positive values indicate magenta)

[00173] b: its position between yellow and blue (b, negative values indicate blue and positive values indicate yellow)

[00174] AE = (AL2 + Aa2 + Ab2)0.5 (overall) and AE’ = (Aa2 + Ab2)0.5 (color only); DE and DE’ < 1.0-2.0: color change is not visually perceivable.

[00175] As shown in Table 9, mBCC dispersion is one of the copper (II) compounds that give the least color change at 300 and 600 ppm Cu level.

[00176] Table 9. Impact of Copper Compound on Color of Dry Paint Film

EXAMPLE 6

[00177] The color change of the flat wall paint (50% PVC, 35% Solid Vol, 45 g/L VOC, Table 6) comprising pBCC (green) can be minimized by incorporation of complementary colored pigment (red) and zinc oxide (ZnO). 10 gram of ZnO was dispersed into a mixture of 29.5 g water and 0.5 g Tamol 731 A dispersant and then mixed at 1500 rpm for 10 minutes. pBCC, Colanyl Oxide Red B130 and the above ZnO dispersions were added into the flat wall paint to achieve the target level of Cu, Oxide Red and ZnO. The test paints were mixed at 1500 rpm for 10 minute and then equilibrated overnight. The test paints were drawn down on sealed Leneta chart to achieve 5 mil wet film thickness and then air dried for 24 hours. The colors of dry films were measured by a BYK spectro-guide colorimeter and the color changes (AE, AE’) were calculated.

[00178] As shown in Table 10, the color changes in pBCC-containing dry paint films are not visually perceivable (AE and AE’ < 1.0) at low Cu level (< 100 ppm Cu in wet paint). The color change can be further reduced by addition of Colanyl Oxide Red B130 or combination of Colanyl Oxide Red B 130 and ZnO.

[00179] Table 10. Reduction of Color Change in |jBCC-containing Dry Paint Films at Low Cu Level

[00180] As shown in Table 11, the color change in pBCC-containing dry paint films is visually perceivable (AE and AE’ > 2.0) at high Cu level (1150 ppm Cu in wet paint). The color change can be reduced to visually unperceivable (AE and AE’ < 2.0) by addition of Colanyl Oxide Red Bl 30 (at 100 ppm) or the combination of Colanyl Oxide Red B 130 (at 50 ppm) and ZnO (at 2000 ppm).

[00181] Table 11. Reduction of Color Change in p,BCC-containing Dry Paint

Films at High Cu Level

Claims

WE CLAIM:

1. A polymer emulsion composition comprising: a copper containing compound, and a biocide comprising one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol; and a solvent; wherein the copper containing compound is present in the polymer emulsion composition in an amount of less than about 10,000 ppm and the biocide is present in the polymer emulsion composition in an amount of less than about 10,000 ppm, and wherein the polymer emulsion composition is substantially free of glass.

2. The polymer emulsion composition of claim 1, wherein the copper containing compound comprises at least one of basic copper carbonate, copper naphthenate, cupric oxide, copper thiocyanate, copper hydroxide, copper 8- quinolinolate, copper sulphate, copper nitrate, and copper bis(5-oxo-L-prolinato).

3. The polymer emulsion composition of claim 2, wherein the copper containing compound comprises basic copper carbonate.

4. The polymer emulsion composition of claim 1, wherein the copper containing compound and the biocide are present in the polymer emulsion composition at a weight ratio of from about 1 :0.001 to about 1 : 1000.

5. The polymer emulsion composition of claim 1, wherein the copper containing compound comprises micronized copper compound particles, wherein 50% or more of the micronized copper compound particles have a median particle size of less than about 1 micron.

6. The polymer emulsion composition of claim 1, wherein the biocide comprises the quaternary ammonium compound, and the quaternary ammonium compound comprises one or more of dialkyl dimethyl ammonium chloride, dialkyl dimethyl ammonium carbonate, dialkyl dimethyl ammonium bicarbonate, alkyl dimethyl benzyl ammonium chloride, and dialkyl methyl poly(oxyethyl) ammonium propionate.

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7. The polymer emulsion composition of claim 1, wherein the biocide comprises the isothiazolone compound, and the isothiazolone compound comprises one or more of 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4- isothiazolin-3-one (CMIT), 4,5-dichloro-2-w-octylisothiazolin-3-one (DCOIT), 5- chloro-2-w-octyl-4-isothiazolin-3-one (COIT), 2-octyl-2H-isothiazolin-3-one (OIT), l,2-benzothiazolin-3-one (BIT), N-methyl-l,2-benzisothiazolin-3-one (MBIT), and 2- butyl-l,2-benzisothiazolin-3(2H)-one (BBIT).

8. The polymer emulsion composition of claim 1, wherein the biocide comprises the haloalkylnyl compound, and the haloalkylnyl compound comprises 3- iodo-2-propynyl butyl carbamate (IPBC).

9. The polymer emulsion composition of claim 1, wherein the biocide comprises the triazine compound, and the triazine compound comprises 1,3,5-triazine.

10. The polymer emulsion composition of claim 1, wherein the biocide comprises the azole compound, and the azole compound comprises a 1,2,4-triazole compound, the 1,2,4-triazole compound comprising one or more of cy proconazole, fenbuconazole, propiconazole, tebuconazole, triadimefon, triticonazole, and difenoconazole.

11. The polymer emulsion composition of claim 10, wherein the azole compound is complexed with the copper containing compound.

12. The polymer emulsion composition of claim 10, wherein the azole compound comprises micronized azole particles, wherein 50% or more of the micronized azole particles have a median particle size of less than about 1 micron.

13. The polymer emulsion composition of claim 1, wherein the biocide comprises the aryl urea compound, and the aryl urea compound comprises (3-(3,4- di chlorophenyl)- 1 , 1 -dimethylurea.

14. The polymer emulsion composition of claim 1, wherein the biocide comprises the succinate dehydrogenase inhibitor, and the succinate dehydrogenase inhibitor comprises a carboxamide compound.

15. The polymer emulsion composition of claim 1, wherein the pH of the polymer emulsion composition is from about 8.0 to about 9.5.

16. The polymer emulsion composition of claim 1, wherein the polymer emulsion composition further comprises an inorganic oxide compound.

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17. The polymer emulsion composition of claim 16, wherein the inorganic oxide compound comprises one or more of zinc oxide and iron oxide.

18. The polymer emulsion composition of claim 1, wherein the polymer emulsion composition further comprises an adjuvant compound.

19. The polymer emulsion composition of claim 18, wherein the adjuvant compound comprises one or more of 2-dicyandiamide and zinc ethyltrifluoroacetate.

20. The polymer emulsion composition of claim 1, wherein the solvent comprises water.

21. A latex paint composition comprising the polymer emulsion composition of claim 1.

22. A biocidal composition comprising: a copper containing compound comprising basic copper carbonate; a biocide comprising one or more of a quaternary ammonium compound, an isothiazolone compound, a haloalkylnyl compound, a triazine compound, an azole compound, an aryl urea compound, a succinate dehydrogenase inhibitor, and bronopol; and one or both of an inorganic oxide compound and an adjuvant compound, wherein the inorganic oxide compound comprises one or both of zinc oxide and iron oxide, the adjuvant compound comprises one or both of 2-dicyandiamide and zinc ethyltrifluoroacetate, and the biocidal composition is substantially free of glass.

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