Copper-containing compounds and compositions for antibacterial coatings and coatings

Abstract

The present disclosure generally relates to a polymer emulsion composition. The polymer emulsion composition comprises a latex binder. The polymer emulsion composition also includes an insoluble copper compound. The polymer emulsion composition also includes a color complementing pigment. The insoluble copper compound is present in the polymer emulsion composition in an amount of less than about 4000 ppm Cu.

Description

[0001] Related Applications

[0002] This application is based upon and claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 357,671, filed on July 1, 2022, which is incorporated herein by reference. Background Art

[0003] Paints and coatings are often used to protect surfaces from corrosion, oxidation or other types of deterioration. At every stage of their service life, paints and coatings are susceptible to contamination and degradation by various microorganisms (including viruses, bacteria, fungi and algae). In addition, the presence of water and nutrients makes these coatings (e.g., latex paints) susceptible to microbial attack both in wet state and in dry film. Microbial growth on the surface of latex paints may cause stains and degradation, resulting in reduced durability of the paint and poor aesthetic quality of the surface. Therefore, biocides or antimicrobial agents can be incorporated into paint formulations to reduce or inhibit the growth of microorganisms in latex paints and maintain the aesthetic quality of the surface.

[0004] It is desirable to use sanitary paints and coatings that have broad spectrum antimicrobial efficacy against viruses and bacteria with minimal effect on the color of the dried film. Due to government regulations and production costs, it may be desirable to use antimicrobial combinations with reduced amounts of each antimicrobial while still achieving high antimicrobial efficacy.

[0005] Therefore, there is a need for improved antimicrobial compositions for use in polymer emulsions.

[0006] Brief description of the invention

[0007] Generally, the present invention relates to polymer emulsion compositions and antimicrobial (antimicrobial) compositions. The compositions disclosed herein can be incorporated into in-can wet preservative additives for latex emulsion compositions (e.g., latex coating compositions). Notably, the compositions disclosed herein advantageously exhibit antimicrobial properties. In particular, it has been found that the use of an insoluble copper compound in combination with a complementary color pigment in a polymer emulsion composition as described herein results in the polymer emulsion composition exhibiting a wide range of antimicrobial properties while surprisingly avoiding undesirable color effects. In addition, the components of the compositions disclosed herein may also exhibit beneficial enhancements so that a reduced amount of the composition may be advantageously used while still achieving a desired degree of antimicrobial efficacy.

[0008] In one embodiment, the polymer emulsion composition includes an insoluble copper compound. The polymer emulsion composition further includes a complementary color pigment. Notably, the insoluble copper compound is present in the polymer emulsion composition in an amount of less than about 4,000 ppm Cu.

[0009] In an exemplary aspect, the insoluble copper compound may include at least one of basic copper (II) carbonate, copper (II) hydroxide, 8-hydroxyquinoline copper, copper (II) pyrithione, copper acetylacetonate, copper (II) oxide, or a combination thereof.

[0010] In another exemplary aspect, the complementary color pigment can include a red or white pigment.

[0011] In another exemplary aspect, the complementary color pigment can include at least one of iron (III) oxide, diketopyrrolopyrrole, dibromanthranthrone, zinc oxide, or a combination thereof.

[0012] In another exemplary aspect, the complementary color pigments can be present in a total amount of less than or equal to about 5000 ppm.

[0013] In another exemplary aspect, the insoluble copper compound can be present in the polymer composition in a total amount of about 100 ppm to about 1800 ppm.

[0014] In another exemplary aspect, the insoluble copper compound can be micronized insoluble copper compound particles, and 50% or more of the micronized insoluble copper compound particles have a median particle size of less than about 1 micron.

[0015] In another exemplary aspect, the polymer emulsion composition can further include a co-biocide, such as at least one derivative of a quaternary ammonium, an isothiazolinone, a pyridinethione, a triazine, a haloalkynyl, a hydantoin, a urea, or a combination thereof.

[0016] In another exemplary aspect, the co-biocide can include at least one of dimethylbenzyl ammonium chloride, N,N-didecyl-N,N-dimethylammonium chloride, N,N-didecyl-N,N-dimethylammonium carbonate / bicarbonate, zinc pyrithione, sodium pyrithione, or a combination thereof.

[0017] In another exemplary aspect, the co-biocide may be present in a total amount of about 50 ppm to about 5500 ppm.

[0018] In another exemplary aspect, an adjuvant may be further included.

[0019] In another exemplary aspect, the adjuvant may include at least one of 2-dicyandiamide, zinc trifluoroethylacetoacetate, or a combination thereof.

[0020] In another exemplary aspect, a latex coating composition can include the polymer emulsion composition disclosed herein.

[0021] In certain embodiments, each of the exemplary aspects described above can be combined with one or more other exemplary aspects described above. For example, in some embodiments, all of the exemplary aspects described above can be combined with each other. As another example, any combination of two, three, four, five or more of the twenty exemplary aspects described above can be combined in other embodiments. Therefore, in some exemplary embodiments, the exemplary aspects described above can be used in combination with each other. Alternatively, the exemplary aspects described above can be implemented separately in other exemplary embodiments. Therefore, it should be understood that the exemplary aspects described above can be utilized to realize various exemplary embodiments.

[0022] In another exemplary embodiment, the antimicrobial composition includes an insoluble copper compound (including basic copper carbonate). The antimicrobial composition also includes a complementary color pigment. It is noteworthy that the insoluble copper compound is present in the antimicrobial composition in an amount of less than about 4,000 ppm.

[0023]

[0013] These and other features and aspects, embodiments and advantages of the present invention will become better understood with reference to the following description and appended claims.

[0024] Detailed description

[0025] Reference will now be made in detail to exemplary embodiments of the present disclosure. It should be appreciated by those skilled in the art that the present disclosure is merely illustrative of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0026] The present invention generally relates to polymer emulsion compositions and antimicrobial compositions. The polymer emulsion composition may include an insoluble copper compound. In addition, the polymer emulsion composition may include a complementary color pigment. It is noteworthy that the insoluble copper compound is present in the polymer composition in an amount of less than about 4000 ppm Cu.

[0027] The compositions disclosed herein can advantageously exhibit antiviral and antibacterial properties. In particular, the polymer emulsion compositions and antimicrobial compositions have broad-spectrum antimicrobial activity against a variety of microorganisms. In addition, the combination of insoluble copper compounds with complementary color pigments can advantageously limit or inhibit the growth of microorganisms without dyeing the polymer emulsion composition. Insoluble copper compounds as described herein are generally understood to impart color, such as a green hue, to coatings and coatings. However, the polymer emulsion compositions and biocides disclosed herein can advantageously exhibit antimicrobial properties while surprisingly avoiding the conventional expected color effects of insoluble copper compounds.

[0028] In addition, the polymer emulsion compositions and antimicrobial compositions disclosed herein may optionally include various other components, such as co-biocides, adjuvant compounds, or combinations thereof. Particularly advantageously, the polymer emulsion compositions and antimicrobial compositions disclosed herein may exhibit enhanced interactions and relatively high antimicrobial efficacy against a variety of microorganisms.

[0029] As used herein, "enhancing interaction" refers to the biocidal or antimicrobial properties of the combination of the insoluble copper compound and the complementary color pigment having a total effect greater than that of the antimicrobial agent acting alone. For example, the insoluble copper compound and complementary color pigment disclosed herein, optionally in combination with one or both of a co-biocide and an adjuvant compound, act together to have an antimicrobial activity against certain microorganisms in the presence of each greater than the antimicrobial activity of the insoluble copper compound alone. Due to this enhancing effect, the amount of the insoluble copper compound and complementary color pigment present in the composition can be reduced while still producing the desired efficacy.

[0030] The combination of co-biocides and additives combined together according to the present invention includes at least an insoluble copper compound and a complementary color pigment. In some examples, one or more co-biocides can be present to further enhance the effect. Therefore, the amount of insoluble copper compounds present in the composition can be reduced or minimized. For example, the polymer emulsion composition and the antimicrobial composition can include less than the total amount of insoluble copper compounds and complementary color pigments present in only one, while still having the same or better efficacy against one or more microorganisms.

[0031] According to embodiments of the present disclosure, the insoluble copper compound generally includes a copper compound, such as an inorganic copper compound. The copper compound has a water solubility of less than 50 mg / mL. For example, the insoluble copper compound may include an inorganic copper salt, such as a carbonate, bicarbonate, sulfate, nitrate, chloride, hydroxide, borate, fluoride or oxide.

[0032] Other examples of insoluble copper compounds include copper oxides, such as cuprous oxide and cupric oxide, and copper salts, such as copper salts of fatty acids and rosin acids, copper ethylenediamine complexes, copper triethanolamine complexes, copper ethylenediaminetetraacetate, and copper thiocyanate. Other examples of copper-containing compounds include copper octoate, copper diamine diacetate complexes, copper ethanolamine complexes, copper naphthenate, and copper 8-quinolinate. In one embodiment, the solubility of basic copper carbonate is 2×10 -3 mg / mL. The solubility of copper hydroxide is 2.9 mg / mL. The solubility of copper pyrithione is 3.0×10 -5 mg / mL. The solubility of copper acetylacetonate is 0.2 mg / mL.

[0033] In one exemplary aspect, the insoluble copper compound comprises at least one of basic copper (II) carbonate, copper (II) hydroxide, 8-hydroxyquinoline copper, copper (II) pyrithione, copper acetylacetonate, and copper (II) oxide. In a preferred exemplary aspect, the insoluble copper compound comprises basic copper carbonate.

[0034] The insoluble copper compounds described herein are not typically used in coating and coating products due to the perceived ability of copper compounds to affect and in some cases completely change the color of the resulting coating or coating. Particularly advantageously, the inventors have found that the use of the insoluble copper compounds herein in polymer emulsion compositions according to exemplary aspects of the present disclosure surprisingly has little effect on the color of the resulting coating or coating. Thus, despite the presence of the insoluble copper compound, the latex coating can advantageously be a "pure white" base coating or a coating that can be tinted to a desired color. In an exemplary aspect, the insoluble copper compound preferably comprises basic copper carbonate or is basic copper carbonate.

[0035] In one embodiment, the insoluble copper compound may include micronized insoluble copper compound particles. The micronized insoluble copper compound particles may have a particle size of about 0.01 micron to about 25.0 microns, such as about 0.01 micron to about 10 microns, such as about 0.05 micron to about 10 microns, such as about 0.1 micron to about 10.0 microns, such as about 0.01 micron to about 1.0 micron, such as about 0.05 micron to about 1.0 micron, such as about 0.1 micron to about 1.0 micron, such as about 0.2 micron to about 1.0 micron.

[0036] Advantageously, the insoluble copper compound can be present in the compositions of the present disclosure (including polymer emulsions and antimicrobial compositions) in an amount of less than about 4000 ppm Cu, such as less than about 2,500 ppm Cu, such as less than about 1,000 ppm Cu, such as less than about 600 ppm Cu, such as less than about 500 ppm Cu, such as less than about 400 ppm Cu, such as less than about 300 ppm Cu, such as less than about 200 ppm Cu, such as less than about 100 ppm Cu, such as less than about 75 ppm Cu, such as less than about 50 ppm Cu, such as less than about 25 ppm Cu, such as about 10 ppm Cu.

[0037] In one embodiment, the insoluble copper compounds disclosed herein can be added directly to the polymer emulsion composition and the antimicrobial composition. Therefore, the insoluble copper compounds disclosed herein are substantially free of a medium or matrix, such as glass. In addition, the insoluble copper compounds can be present in the form of a dispersion or a solution.

[0038] As described above, the polymer emulsion composition and the antimicrobial composition include a complementary color pigment. For example, the complementary color pigment may include a red pigment. In an exemplary aspect, the red pigment includes iron (II) oxide, diketopyrrolopyrrole or dibromanthranthrone. Alternatively, the complementary color pigment may include a white pigment, such as zinc oxide.

[0039] The complementary color pigment may be present in the compositions of the present disclosure in the form of particles having a particle size of 0.01 microns to 25.0 microns, including polymer emulsions and antimicrobial compositions. In one embodiment, the particle size of the inorganic oxide compound used in the compositions disclosed herein may be between 0.01 and 10 microns, between 0.05 and 10 microns, between 0.1 and 10.0 microns, between 0.01 and 1.0 microns, between 0.05 and 1.0 microns, between 0.1 and 1.0 microns, between 0.2 and 1.0 microns.

[0040] The complementary color pigment may be present in the compositions disclosed herein at a concentration of about 10 ppm Cu to about 4,000 ppm Cu, such as about 15 ppm Cu to about 900 ppm Cu, such as about 50 ppm Cu to about 500 ppm Cu.

[0041] In another exemplary aspect, the complementary color pigment may be present in a micronized form alone or in combination with a dispersant, although the type or amount of pigment used is different. For example, in one embodiment, the complementary color pigment 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.

[0042] In one embodiment, the insoluble copper compound and the complementary color pigment may be present in the polymer emulsion composition or the antibacterial composition in a weight ratio of about 1000:1 to about 1:1000, such as about 500:1 to about 1:500, such as about 20:1 to about 1:20, such as about 15:1 to about 1:15, such as about 5:1 to about 1:5, such as about 3:1 to about 1:3, such as about 2:1 to about 1:2, such as about 1:1.

[0043] In an exemplary aspect, the insoluble copper compound and the iron oxide are present in the polymer emulsion composition in a weight ratio of about 10:1 to about 30:1, such as about 15:1 to about 25:1.

[0044] In another exemplary aspect, the insoluble copper compound and zinc oxide are present in the polymer emulsion composition in a weight ratio of about 10:1 to about 1:10, such as about 1:1.

[0045] As described above, the polymer emulsion composition and antimicrobial composition disclosed herein may optionally include a co-biocidal agent. For example, the co-biocidal agent may include one or more of a quaternary ammonium salt, an isothiazolinone compound, a pyridinethione compound, a triazine compound, a haloalkynyl compound, a hydantoin compound, or a urea compound.

[0046] In another exemplary aspect, the biocide comprises a quaternary ammonium salt. For example, the biocide can comprise a quaternary ammonium halide, a quaternary ammonium carbonate / quaternary ammonium bicarbonate, or a benzyl ammonium halide.

[0047] Quaternary ammonium salts, also known as "quats", generally include at least one quaternary ammonium cation with a suitable anion. Quaternary ammonium salts generally have the following general formula:

[0048]

[0049] The groups R1, R2, R3 and R4 can vary over a wide range, and examples of quaternary ammonium salts having antimicrobial properties will be well known to those of ordinary skill in the art. Typically, two of R1, R2, R3 and R4 are low alkyl groups, meaning having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl. Additionally, two of R1, R2, R3 and R4 are long chain alkyl groups of 6 to 24 carbon atoms or benzyl groups. - It is a monovalent anion or a monovalent polyvalent anion of an inorganic or organic acid. - Suitable anions are in principle all inorganic or organic anions, in particular halides (eg chloride or bromide), carboxylates, sulfonates, phosphates or mixtures thereof.

[0050] In another exemplary aspect, the quaternary ammonium salt may have the following R groups: R1 is benzyl or C 6-18 -alkyl, R2 is C 1-18 -alkyl or -[(CH2)2-O] n R5, wherein n=1-20, R3 and R4 are independently C 1-4 -alkyl, R5 is hydrogen or unsubstituted or substituted alkyl or phenyl, and A - It is a monovalent anion or a monovalent polyvalent anion of an inorganic acid or an organic acid.

[0051] In another exemplary aspect, the quaternary ammonium salt can include a dialkylammonium compound, such as a dimethyldialkylammonium compound. In one embodiment, the dimethyldialkylammonium compound can have from about 8 to about 12 carbon atoms, such as from about 8 to about 10 carbon atoms in each alkyl group.

[0052] Examples of dimethyldialkylammonium compounds that can be used as biocides include dimethyldioctylammonium compounds, such as dimethyldioctylammonium chloride, dimethyldidecylammonium compounds, such as dimethyldidecylammonium chloride, and the like. Mixtures of dimethyldialkylammonium compounds can also be used, and other anions, such as those described above, can also be used. Commercially available dimethyldialkylammonium compounds include, for example, BARDAC TM LF-80、BARDAC TM 22 and BARDAC TM 208M, which is available from Arxada, LLC (formerly Lonza Specialty Ingredients).

[0053] In another exemplary aspect, the co-biocide can include a quaternary ammonium carbonate, which can be represented by the formula:

[0054]

[0055] Where R 1 C1-C 20 Alkyl or aryl substituted alkyl, and R 2 For C8-C 20 alkyl, and preferably wherein R 1 With R 2 Same, R 1 For C8-C 12 Alkyl, and further comprising a composition of a corresponding quaternary ammonium bicarbonate

[0056]

[0057] Where R 1 As above C1-C 20 The alkyl or aryl-substituted alkyl groups are the same or different, and R 2 As above C8-C 20 The alkyl groups are the same or different, but preferably R 1 With R 2 Same, R 1 For C8-C 12 alkyl.

[0058] Quaternary ammonium carbonate / bicarbonate may include di-C8-C 12 Alkyl ammonium carbonates / bicarbonates. For example, in one particular exemplary embodiment, the composition comprises didecyl dimethyl ammonium carbonate and didecyl dimethyl ammonium bicarbonate.

[0059] However, in other exemplary embodiments, the carbonate / bicarbonate of the quaternary ammonium cation can be selected from dioctyldimethylammonium carbonate, decyloctyldimethylammonium carbonate, benzalkonium carbonate, benzethonium carbonate, stearalkonium carbonate, cetrimonium carbonate, behentrimonium carbonate, dioctyldimethylammonium bicarbonate, decyloctyldimethylammonium bicarbonate, benzalkonium bicarbonate, phenethylammonium bicarbonate, stearalkonium carbonate, cetrimonium carbonate, behentrimonium carbonate, and mixtures of one or more such carbonates.

[0060] Preferably, the quaternary ammonium salt may include one or more of didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium hydrogencarbonate and alkyldimethylbenzylammonium chloride.

[0061] In an exemplary embodiment, the co-biocide can include a benzyl ammonium compound, such as an alkyl dimethyl benzyl ammonium compound. Typically, the alkyl group can include from about 10 to about 18 carbon atoms, such as from about 12 to about 16 carbon atoms.

[0062] Examples of alkyl dimethyl benzyl ammonium compounds that can be used as biocides include C 12 Alkyl dimethyl benzyl ammonium chloride, C 14 Alkyl dimethyl benzyl ammonium chloride and C 16 Alkyl dimethyl benzyl ammonium chloride. In addition, mixtures of these alkyl dimethyl benzyl ammonium compounds may be used. Commercially available alkyl dimethyl benzyl ammonium compounds include, for example DM-80 and 50-65B, which are available from Arxada, LLC (formerly known as Lonza Specialty Ingredients). These commercially available alkyl dimethyl benzyl ammonium compounds are C 12 , C 14 and C 16 Generally, it is preferred that when it is a blend, the alkyl dimethyl benzyl ammonium compound comprises more than C 16 The higher concentration of alkyl components in C 12 Alkyl and C 14 Alkyl component. It should be noted that other anions, including those mentioned above, may also be used.

[0063] In another exemplary aspect, the co-biocide comprises an isothiazolinone compound. Suitable isothiazolinones are represented by the following general formula:

[0064]

[0065] Where: R 1 represents hydrogen, optionally substituted C1-C 18 alkyl, C2-C8 alkenyl or alkynyl, C2-C8 haloalkynyl, optionally substituted C3-C 12 cycloalkyl, optionally substituted aralkyl having up to 10 carbon atoms, or optionally substituted aryl having up to 10 carbon atoms; R 2 and R 3 independently represent hydrogen, halogen or C1-C4 alkyl; or R 2 and R 3 Together, they can provide a 1,2-benzisothiazolin-3-one group (ie, R 2 and R 3 Can combine to form -(CH)4-).

[0066] In one exemplary aspect, R 2 and R 3 independently represents chlorine or hydrogen, or R 2 and R 3 Together they can provide a 1,2-benzisothiazolin-3-one group.

[0067] Thus, in one exemplary aspect, R 1 The substituents are selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, cyclohexyl, 4-methoxyphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, benzyl, 4-methoxybenzyl, 4-chlorobenzyl, 3,4-dichlorobenzyl, phenethyl, 2-(4-methoxyphenyl)ethyl, 2-(4-chlorophenyl)ethyl, 2-(3,4-dichlorophenyl)ethyl, hydroxymethyl, chloromethyl and chloropropyl.

[0068] In one such exemplary aspect, R in the compound of the above formula 1 The substituents represent hydrogen, optionally substituted C1-C 18 In another aspect, R 1 represents hydrogen or an optionally substituted C1-C 18 Additionally or alternatively, R 1 R is hydrogen or C1-C8 alkyl, of which hydrogen, methyl, butyl and octyl are the most preferred 1 Substituent.

[0069] Therefore, in one aspect, the isothiazolinone used in the polymer emulsion composition and / or antimicrobial composition according to the present disclosure is those represented by the above general formula, wherein R 1 represents hydrogen or C1-C8 alkyl, and R 2 and R 3 independently represents chlorine or hydrogen, or R 2 and R 3 Together they can provide a 1,2-benzisothiazolin-3-one group.

[0070] In one exemplary aspect, the isothiazolinone used in the polymer emulsion composition and / or antimicrobial composition according to the present disclosure is represented by the above general formula, wherein R 1 represents hydrogen, methyl, butyl or octyl, and R 2 and R 3 independently represents chlorine or hydrogen, or R 2 and R 3 Together they can provide a 1,2-benzisothiazolin-3-one group.

[0071] Furthermore, as described above, in one exemplary aspect, the isothiazolinone of the above formula is a benzisothiazolinone of the following general formula:

[0072]

[0073] Wherein R is hydroxyl, halogen (especially chlorine), C 1-4 -alkyl or C 1-4 -alkoxy; R 1 is as defined above; and n is 0 to 4. When present in one aspect, R is located at one or both of the 5 and 6 positions of the phenyl ring of the benzisothiazolinone. However, in another aspect, n is 0.

[0074] In an exemplary aspect, a benzisothiazolinone is wherein R 1 H or C 1-5 -alkyl, or wherein R 1 H or C 3-5 Examples of these compounds include, for example, 1,2-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. Therefore, in one aspect, benzisothiazolinone is 1,2-benzisothiazolin-3-one.

[0075] For example, in one exemplary aspect, isothiazolinones include, but are not limited to, methylisothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), octylisothiazolin-3-one (OIT), 1,2-benzisothiazolin-3(2H)-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), and N-(n-butyl)-1,2-benzisothiazolin-3-one (BBIT). Particularly preferred isothiazolinones include, but are not limited to, methylisothiazol-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), octylisothiazolin-3-one (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), N-methyl-1,2-benzisothiazol-3-one (MBIT), and N-(n-butyl)-1,2-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)-1,2-benzisothiazol-3-one (BBIT), more preferably octylisothiazolone (OIT), 1,2-benzisothiazol-3(2H)-one (BIT) and N-(n-butyl)-1,2-benzisothiazol-3-one (BBIT), or a combination thereof.

[0076] Preferably, the isothiazolinone 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), 1,2-benzothiazolin-3-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT) and 2-butyl-1,2-benzisothiazolin-3(2H)-one (BBIT).

[0077] In another exemplary aspect, the co-biocide comprises a pyrithione compound. For example, the pyrithione compound can include sodium pyrithione, zinc pyrithione, copper pyrithione, 1-hydroxy-2-pyridone, and pyrithione disulfide.

[0078] In another exemplary aspect, the co-biocide comprises a triazine compound. For example, the triazine compound can comprise 1,3,5-triazine.

[0079] In another exemplary aspect, the co-biocidal agent includes a haloalkynyl compound, such as a haloalkynyl carbamate. For example, the haloalkynyl carbamate can include an iodoalkynyl carbamate having the general formula:

[0080]

[0081] wherein m is 1, 2 or 3; n is 1, 2 or 3; and R is hydrogen (H); unsubstituted or substituted alkyl, aryl, aralkyl, alkylaryl, alkenyl, cycloalkyl or cycloalkenyl or alkoxyaryl, all having 1 to no more than 20 carbon atoms, and m and n may be the same or different.

[0082] Suitable R substituents for iodoalkynyl carbamate compounds include alkyl groups such as methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl (pentyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cycloalkyl groups such as cyclohexyl, aryl, alkaryl and aralkyl groups such as phenyl, benzyl, tolyl, cumyl, haloalkyl and aryl groups such as chlorobutyl and chlorophenyl, and alkoxyaryl groups such as ethoxyphenyl, and the like. Therefore, suitable carbamate compounds are selected from: 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-chlorophenyl carbamate (IPCIPhC), 3-iodo-2-propynyl 4-chlorobutyl carbamate (IPCI BC) and mixtures thereof.

[0083] Preferably, the haloalkynyl compound may include 3-iodo-2-propynylbutyl carbamate (IPBC).

[0084] In another exemplary aspect, the co-biocides include hydantoin compounds, such as aldehydes. For example, the aldehydes may include formaldehyde and paraformaldehyde. Aldehyde-forming compounds include imidazolidine compounds, such as hydantoins, such as dimethylol dimethyl hydantoin (DMDMH).

[0085] In another exemplary aspect, the co-biocide comprises a urea derivative, such as an aryl urea compound. For example, the aryl urea compound can include (3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron).

[0086] The complementary color pigment may be present in the compositions disclosed herein at a concentration of about 10 ppm Cu to about 5,500 ppm Cu, such as about 100 ppm Cu to about 5,000 ppm Cu, such as about 500 ppm Cu to about 4,500 ppm Cu, such as about 1,000 ppm Cu to about 3,500 ppm Cu.

[0087] Optionally, the compositions disclosed herein may further include an adjuvant compound. For example, the adjuvant compound may include a guanidine enhancer having the structure of Compound I, which has the following formula:

[0088] HR2N-(C=NHR3)-NR1H

[0089]

[0090] Wherein, R3 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -Alkynyl, C7-C 30 -alkylaryl or C6-C 12 -aryl; R1 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -Alkynyl, C7-C 30 --Alkyl aryl or C6-C 12 -aryl; R2 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -Alkynyl, C7-C 30 -alkylaryl or C6-C 12 -aryl; and wherein at least one of R3, R1 or R2 is C.

[0091] In another exemplary aspect, the adjuvant compound and the insoluble copper compound are present in the polymer emulsion composition in a weight ratio of about 1:1 to about 1000:1.

[0092] In another exemplary aspect, the adjuvant compound is present in the polymer emulsion composition at a concentration of about 100 ppm Cu to about 10,000 ppm Cu, such as about 200 ppm Cu to about 10,000 ppm Cu, such as about 1,000 ppm Cu to about 10,000 ppm Cu.

[0093] As used herein, references to chemical formulae use standard element symbols according to the periodic table (e.g., C for carbon, N for nitrogen, etc.). Furthermore, unless otherwise indicated, references to chemical formulae are based on standard bonding, such that carbon can form up to four (4) bonds and nitrogen can form up to three (3) bonds. Thus, references to CN should be understood to refer to a cyano group, wherein the carbon includes a triple bond to the nitrogen, and the remaining carbon bonds may represent the attachment of the cyano group to the chemical structure.

[0094] Guanidine enhancers include one or more of the following: 1-cyanoguanidine, salts of 1-cyanoguanidine, 2-cyanoguanidine (also known as dicyandiamide) and salts of 2-cyanoguanidine. Both 1-cyanoguanidine and 2-cyanoguanidine are derivatives of compound I, wherein each R2 or R1 is CN and R3 is H, and R1 and R2 are H and R3 is CN. It should be understood that the conversion between 1-cyanoguanidine and 2-cyanoguanidine can occur by tautomerization in aqueous solution or exposure to other proton donor solvents, so a composition containing only one tautomer can be shown to be converted to a mixture of the two over time. In addition, although 1-cyanoguanidine and 2-cyanoguanidine are used for illustration, according to exemplary embodiments of the present disclosure, tautomeric forms of substances derived from compound I can generally be included as guanidine enhancers. Tautomeric forms of compound I include structures (a) and (b), which have the following formula:

[0095]

[0096] Wherein, R3 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -Alkynyl, C7-C 30 --Alkyl aryl or C6-C 12 -aryl; R1 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -Alkynyl, C7-C 30 -alkylaryl or C6-C 12 -aryl; R2 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -Alkynyl, C7-C 30 -alkylaryl or C6-C 12 -aryl; and wherein at least one of R3, R1 or R2 is CN.

[0097] Generally, the guanidine compound can react with a proton donor to form a salt having a positively charged guanidinium cation that is paired with a negatively charged anion. Therefore, in certain polymer emulsion compositions or antimicrobial 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.

[0098] Some examples of anions that can be included as a salt of 1-cyanoguanidine or a salt of 2-cyanoguanidine can include inorganic anions, such as halides (e.g., chloride, bromide, fluoride, iodide, etc.), nitrates, sulfates, etc. Alternatively or in addition, the anions can include organic anions, 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.

[0099] In another exemplary aspect, the adjuvant compound can include trifluoroacetic acid or a salt thereof. For example, the adjuvant compound can include ethyl zinc trifluoroacetate.

[0100] In another exemplary aspect, the adjuvant compound can include tetramethylguanidine (TMG), such as 1,1,3,3-tetramethylguanidine and / or 2-tert-butyl-1,1,3,3-tetramethylguanidine.

[0101] In another exemplary aspect, the adjuvant compound can include a cystamine enhancer, such as cystamine dihydrochloride.

[0102] In an exemplary aspect, the pH of the polymer emulsion composition or antimicrobial composition is from about 8.0 to about 9.5. As known in the art, pH builders, pH buffers, and other pH adjusters can be used to obtain and stabilize the above pH values.

[0103] The polymer emulsion composition of the present disclosure also includes a solvent. In the polymer emulsion of the present disclosure, the solvent may include a variety of suitable organic and / or inorganic solvents. In an exemplary aspect, the solvent includes water.

[0104] In another exemplary aspect, the polymer emulsion composition of the present disclosure can be a latex paint composition. Typically, the latex paint composition also includes a latex binder (e.g., a polymer comprising one or more acrylates, vinyl acetate, vinyl chloride and / or styrene butadiene monomers). Optionally, the latex paint can also include an emulsifier and / or a surfactant to improve the distribution of the latex binder throughout the polymer emulsion composition. In this way, an emulsifier and / or a surfactant can be used to produce a more uniform mixture, which can provide a more uniform coating of the resulting latex paint coating. Optionally, the latex paint composition can include a thickener to adjust the viscosity of the latex paint, thereby improving the adhesion of the wet paint to an applicator (e.g., a brush or roller). Optionally, the latex paint composition can include a cosolvent (e.g., ethylene glycol), which can improve the solubility of the components of the latex paint composition.

[0105] In an exemplary aspect, the polymer emulsion composition can comprise from about 5 wt.% to about 40 wt.% of the latex coating composition, such as from about 20 wt.% to about 30 wt.% of the latex coating composition.

[0106] Another aspect of the exemplary embodiments may include a latex binder. The latex binder may include various polymers suitable for latex coatings, such as acrylates (e.g., polymethyl methacrylate), which may be formed as homopolymers or copolymers. For example, the copolymer may include another monomer (e.g., butadiene styrene) incorporated. In some embodiments, the acrylate may be modified to include one or more nitrile groups. Therefore, the latex binder may include various acrylates, acrylate butadiene styrene copolymers, and acrylonitrile butadiene styrene copolymers. In addition, these latex binders are provided for exemplary purposes, and other latex binders may be used alone or in combination with embodiments of the present disclosure.

[0107] As an example of illustration, embodiments of the present disclosure may include a latex coating containing a latex binder and an acrylate. The acrylate may include a polymer or copolymer comprising one or more acrylate monomers. Exemplary aspects of an acrylate polymer or copolymer may include a certain mass fraction of acrylate monomers. For example, the acrylate may include a copolymer comprising an acrylate monomer (e.g., methyl methacrylate) and a second monomer (e.g., butadiene styrene). The mass fraction of the acrylate monomer relative to the total weight of the copolymer may define the mass fraction. In some acrylates, the mass fraction of the acrylate monomer relative to the total weight of the copolymer may be not less than about twenty (20) wt% and not more than about one hundred (100) wt%, such as not less than about thirty (30) wt% and not more than about eighty (80) wt%, not less than about forty (40) wt% and not more than about seventy (70) wt%, or not less than about forty-five (45) wt% and not more 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, some embodiments may include acrylates having a mass fraction of the acrylate monomer relative to the total weight of the acrylate greater than fifty (50) wt%.

[0108] In embodiments of the present disclosure, a latex paint may include or may be formulated to include a certain amount of pigment. For example, certain exemplary latex paints may include a pigment comprising titanium dioxide (TiO2) at a concentration of not less than five (5) wt% TiO2 and not more than sixty (60) wt% TiO2 based on the total weight of the latex paint. TiO2 may be used to impart whiteness and / or opacity to the exemplary embodiments, and may also be included to build viscosity. Typically, exemplary embodiments may include not less than five (5) wt% and not more than sixty (60) wt% TiO2, such as not less than fifteen (15) wt% and not more than fifty-five (55) wt% TiO2, not less than twenty (20) wt% and not more than fifty (50) wt% TiO2, or not less than twenty-five (25) wt% and not more than forty-five (45) wt% TiO2.

[0109] In other exemplary embodiments, the polymer emulsion composition of the present disclosure may be an adhesive.

[0110] In an exemplary aspect, the antimicrobial composition according to the present disclosure can be manufactured and sold as a biocidal additive composition, the biocidal additive composition includes an insoluble copper compound, a complementary color pigment, and one or both of a co-biocide and an adjuvant compound, and the additive composition can be substantially free of other materials. Therefore, in such exemplary embodiments, the additive composition can be a three-part additive composition or a four-part additive composition. The three-part or four-part additive composition can be provided as an ingredient for forming a latex coating composition or a polymer emulsion composition. In addition, the three-part additive composition or the four-part additive composition can be added to other components to form a latex coating composition or a polymer emulsion composition. As described above, the polymer emulsion composition and / or the latex coating composition can advantageously provide broad-spectrum antimicrobial control in the composition.

[0111] As evidence of the enhancing effect of the insoluble copper compound and the complementary color pigment, the inhibitory concentration of the complementary color pigment was lower in the presence of the insoluble copper compound when tested against the target microorganism.

[0112] The foregoing description is exemplary in nature and is not intended to limit the scope, applicability, or configuration of the disclosure in any way. Various changes may be made to the described embodiments in the function and arrangement of elements described herein without departing from the scope of the disclosure.

[0113] 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 belongs.

[0114] As used in this application and claims, the singular forms "a", "an", and "the" include the plural forms unless the context clearly dictates otherwise. In addition, the term "comprising" means "including". The methods and compositions of the present disclosure (including components thereof) may comprise, consist of, or consist essentially of the basic elements and definitions of the embodiments described herein, as well as any additional or optional ingredients, components, or definitions described herein or otherwise useful in biocidal compositions.

[0115] Unless otherwise indicated, all numbers used in the specification or claims indicating the quantity of ingredients, properties such as molecular weight, percentages, etc. should be understood as being modified by the term "about". Therefore, unless otherwise implicitly or explicitly indicated, the numerical parameters listed are approximate values, which may depend on the desired properties sought and / or the detection limits under standard test conditions / methods. When directly and unambiguously distinguishing an embodiment from the prior art in question, the numerical values ​​of the embodiments are not approximate values ​​unless the word "about" is cited.

[0116] As used herein, "optional" or "optionally" means that the subsequently described material, event or circumstance may or may not exist or occur, and that the description includes instances where the material, event or circumstance exists or occurs, and instances where the material, event or circumstance does not exist or does not occur. As used herein, "w / w%" and "wt%" refer to the weight relative to another component or the percentage of the total weight in a composition.

[0117] The term "about" is intended to mean approximately, within the range of, roughly, or approximately. 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. Unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and the appended claims are approximate. At the very least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, the numerical parameters should be interpreted in light of the number of reported significant digits and applying ordinary rounding techniques.

[0118] When used to describe the amount of a substance in a material, the term "substantially free" is not limited to being completely or completely free, and may correspond to the absence of any appreciable or detectable amount of the substance in the material. Thus, for example, a material is "substantially free" of a substance when the amount of the substance in the material is less than the precision of an industrially acceptable instrument or test for measuring the amount of the substance in the material. In certain exemplary embodiments, a material may be "substantially free" of a substance when the amount of the substance in the material is less than 10% by weight, less than 9% by weight, less than 8% by weight, less than 7% by weight, less than 6% by weight, less than 5% by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight.

[0119] The phrase "effective amount" refers to an amount of a compound that promotes, ameliorates, stimulates or encourages a response to a particular condition or disorder or a particular symptom of a condition or disorder.

[0120] The terms "synergist" and "adjuvant" as used herein refer to additives that may affect the performance of the active compound when used in combination with the active compound, but do not exhibit any biocidal activity and / or do not exhibit significant biocidal activity themselves in the composition of the present invention.

[0121] As used herein, the term "antimicrobial agent" refers to any compound that prevents the growth of organisms on the surface of a coating prior to surface application and / or prevents the growth of organisms "in the can" in a coating or coating.

[0122] The terms "antifouling paint" and "antifouling coating" are used interchangeably herein.

[0123] As used herein, the terms “first,” “second,” and “third” may be used interchangeably to distinguish one component from another, and are not intended to indicate the position or importance of each component.

[0124] Unless context or language indicates otherwise, here and throughout the specification and claims, range limitations are combined and interchanged, such ranges are identified and include all sub-ranges contained therein. For example, all ranges disclosed herein include the endpoints, and the endpoints are independently combinable with each other.

[0125] As used herein, the term "D50" or "D50 particle size" refers to the volume median particle size, wherein 50% of the particles by volume of a sample have a size below that range or value.

[0126] Similarly, the term "D95" or "D95 particle size" as used herein refers to the value at which 95% of the particles by volume of a sample have a size below the range or value.

[0127] Unless specifically stated otherwise, the term "particle size" as used herein refers to the median particle size D50. The particle size can be measured using a laser scattering particle size analyzer, such as a HORIBA LA 910 particle size analyzer.

[0128] The terms "median particle size" and "average particle size" and D50 are used interchangeably herein.

[0129] The term "micronized" as used herein refers to a median particle size (D50) in the range of 0.01-25 microns.

[0130] This written description uses embodiments to disclose the present disclosure, including the best mode, and also enables any person skilled in the art to practice the present disclosure, including making and using any device or system and performing any combined method. The patent scope of the present disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. If these other examples include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims, these other examples are intended to fall within the scope of the claims.

[0131] In addition, certain aspects of the present disclosure may be better understood from the following examples, which are non-limiting and exemplary in nature. In addition, it should be understood that the compositions described in the examples may be substantially free of any substance not explicitly described. Example

[0132] Example 1

[0133] The compatibility of copper compounds in coatings was evaluated by visually evaluating the dry film appearance of flat wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1). A dispersion of micronized basic copper carbonate (μBCC containing copper: Cu) or an aqueous solution of copper sulfate (CuSO4) (2 grams of soluble CuSO4 dissolved in 38 grams of water to form a 5 wt% solution) was added to the flat wall paint to obtain a 600 ppm level of Cu. The test paints were mixed at 1500 rpm for 10 minutes and then equilibrated overnight. The test paints were drawn down onto sealed Leneta cards to obtain a 5 mil wet film thickness and then air dried for 24 hours. The coating appearance was visually inspected for any defects, such as sand particles formed due to incompatibility.

[0134] Table 1. Matt wall coating compositions

[0135] Material Weight(g) water 350.5 Defoaming agent 4.6 Dispersants 10.6 Surfactants 1.1 Ethylene glycol 29.3 Coagulant 3.8 Cellulose 3.0 Attapulgite 5.9 pH Adjusters As needed Kaolin 87.8 Nepheline syenite 146.3 Titanium Dioxide 152.1 100% acrylic emulsion 205.0 gross weight 1000.0

[0136] Table 2. Compatibility of copper compounds in coatings

[0137]

[0138] As shown in Table 2, water-insoluble μBCC is compatible in this acrylic coating, but water-soluble CuSO4 is not. In the latter case, the soluble copper cations react with the acrylic acid in the acrylic latex to form insoluble acrylated copper compounds, which lead to coarse particle formation in the dried film.

[0139] Example 2. Effect of the color of copper compounds

[0140] The effect of copper compounds on the color of dry paint films was studied in matte wall paint (50% PVC, 35% solid volume, 45g / L VOC, Table 1). 5 grams of insoluble copper compound were dispersed in a mixture of 44.5g water and 0.5g Tamol 731A dispersant and then mixed at 1500rpm for 10 minutes. 2 grams of soluble copper compound were dissolved in 38g water. The resulting dispersion of insoluble copper compound (10wt%) and solution of soluble copper compound (5wt%) were added to the paint to obtain 300 and 600ppm levels of Cu. The test paint was mixed at 1500rpm for 10 minutes and then balanced overnight. The test paint was scraped onto a sealed Leneta card to obtain a 5 mil wet film thickness and then air dried for 24 hours. The color of the dry film was measured by a BYK spectro-guide colorimeter and the color change (ΔE, ΔE') was calculated as follows.

[0141] L: lightness of the color (L*=0 produces black, L*=100 indicates diffuse white; specular white may be higher);

[0142] ■a: the position between red / magenta and green (a*, negative values ​​represent green, while positive values ​​represent magenta); and

[0143] ■b: The position between yellow and blue (b*, negative values ​​represent blue, positive values ​​represent yellow).

[0144] ■ΔE=(ΔL 2 +Δa 2 +Δb 2 ) 0.5 (overall) and ΔE'=(Δa 2 +Δb 2 ) 0.5 (color only); ΔE and ΔE' < 1.0-2.0: color change is not visually perceptible.

[0145] Table 3. Effect of copper compounds on dry paint film color

[0146]

[0147] As shown in Table 3, the μBCC dispersion produced less color change than other colored copper compounds at 300 and 600 ppm Cu levels, except for copper oxide. While not wishing to be bound by any particular theory, it is believed that the reduced color change of copper oxide may be primarily due to poor dispersibility of copper oxide in the coating.

[0148] Example 3

[0149] The color change of the matte wall paint (50% PVC, 35% solid volume, 45g / L VOC, Table 1) containing μBCC (green) can be slowed down by adding iron oxide pigment (red: complementary color) and zinc oxide (ZnO). 10 grams of ZnO are dispersed in a mixture of 29.5g water and 0.5g Tamol 731A dispersant, and then mixed at 1500rpm for 10 minutes. μBCC, Colanyl Oxide Red B130 and the above ZnO dispersion (25wt%) are added to the matte wall paint to obtain the target level of Cu, OxideRed and ZnO. The test paint is mixed at 1500rpm for 10 minutes and then balanced overnight. The test paint is scraped on a sealed Leneta card to obtain a 5 mil wet film thickness and then air dried for 24 hours. The color of the dry film is measured by a BYK spectrum-pointing colorimeter, and the color change (ΔE, ΔE') is calculated.

[0150] Table 4. Reduction in color change of dried coating films containing μBCC at high Cu

[0151]

[0152] As shown in Table 4, at 1150 ppm Cu, the color change in the dried coating film containing μBCC was visually noticeable (ΔE and ΔE'>2.0). The color change could be reduced to visually unnoticeable (ΔE and ΔE'<2.0) by adding Colanyl Oxide Red B130 (100 ppm) or a combination of Colanyl Oxide Red B130 (50 ppm) and ZnO (2000 ppm).

[0153] Example 4

[0154] The antimicrobial efficacy of the copper-containing composition in dry paint films was evaluated using a modified JIS Z2801 method (Antimicrobial Product - Test for Antimicrobial Activity and Efficacy: 2000) by reducing the contact time from 24 hours to 2 hours and including Pseudomonas aeruginosa as an additional bacteria. Briefly, μBCC dispersions and optional ZnO dispersions (25 wt %) were added to matte wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1) for target Cu and ZnO levels, respectively. The paint was brushed onto sterilized plastic filter paper. Each side of the filter paper was painted twice, and the resulting coated paper was dried under ambient conditions for 3 days. The dried coating was then leached with 10 L of water for 24 hours (the water was changed 4 times in the first 8 hours). Dry films (40 mm x 40 mm) of the test coatings were inoculated with each of three (3) bacterial inocula (0.4 ml): Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 15442) to obtain 1.0 to 4.0 x 10 of each bacterium on the dry surface of each test coating. 5 The inoculum concentration was 1.3 cfm / mL. The test coatings were incubated at 35±1°C and 90% relative humidity (RH) for 2 hours. The degree of bacterial contamination of all samples was determined by agar plate culture method via bacterial viable cell counts relative to blank coatings.

[0155] Table 5. Summary of the antimicrobial efficacy of μBCC and ZnO in coatings

[0156]

[0157]

[0158] The antimicrobial efficacy of the copper containing compositions in dry films of matte paint is given in Table 5. Bacterial counts >3 Log were obtained at 1650 ppm Cu when μBCC was used alone or at 825 ppm Cu and 825 ppm ZnO when μBCC was used in combination with ZnO. 10 or >99.9% reduction.

[0159] Example 5

[0160] A modified JIS Z2801 method (Antimicrobial Product-Test for Antimicrobial Activity and Efficacy: 2000) was used by reducing the contact time from 24 h to 2 h, including Pseudomonas aeruginosa as an additional bacterium, and increasing the inoculum strength to 5.0-10.0 × 10 7 cfm / mL, to evaluate the antimicrobial efficacy of copper-containing compositions in dry paint films. Briefly, μBCC dispersions were added to matte wall paint containing quaternary ammonium salts (41.5% solid volume, <50 g / L VOC, 0.52% alkyl (50% C14, 10% C16, 40% C12) dimethylbenzyl ammonium chloride) for target Cu and quaternary ammonium salt levels, respectively. The paint was applied to sterilized plastic filter paper. Each side of the filter paper was painted twice, and the resulting coated paper was dried under ambient conditions for 3 days. The dried coating was then leached with 10 L of water for 24 hours (the water was changed 4 times in the first 8 hours). Dry films (40 mm x 40 mm) of the test coatings were inoculated with each of three (3) bacterial inocula (0.4 ml): Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 15442) to obtain 5.0 to 10.0 x 10 of each bacterium on the dry surface of each test coating. 7 Inoculum concentration of cfm / mL. The test coatings were incubated at 35±1°C and 90% relative humidity (RH) for 2 hours. The degree of bacterial contamination was determined by agar plate culture method via viable cell counts of bacteria relative to blank coatings.

[0161] The antimicrobial efficacy of the copper-containing composition in the dry film of the matte paint is given in Table 6, which demonstrates the improved efficacy by adding μBCC to the quaternary ammonium salt-containing paint. In particular, when 330 ppm Cu was combined with 5200 ppm quaternary ammonium salt, an additional >3 Log increase in bacterial count was achieved for Pseudomonas. 10 or >99.9% reduction.

[0162] Table 6. Summary of the antimicrobial efficacy of μBCC and quaternary ammonium salts in coatings

[0163]

[0164] Example 6

[0165] The antimicrobial efficacy of copper-containing compositions in dry paint films was evaluated using an interim EPA method (Interim Method for Evaluating the Efficacy of Antimicrobial Surface Coatings: 10-02-2020). Briefly, μBCC dispersions were added to matte wall paint (38% solid volume, <50 g / L VOC) for target Cu levels. The paints were drawn-down onto sterilized steel substrates (1 inch x 1 inch AISI type 304 stainless steel). The resulting coated substrates were dried at ambient conditions for at least 24 hours. Dry films of the test paints were inoculated with each of two (2) bacterial inocula (20 ml): Staphylococcus aureus (ATCC 6538) and Pseudomonas aeruginosa (ATCC 15442) to obtain 10 on the dry surface of each test paint. 4 Up to 10 5 cfm / carrier for each bacteria. The test coatings were incubated for 2 hours at 22°C and 30-40% RH. The extent of bacterial contamination was determined by viable cell counts for antimicrobial efficacy relative to uncoated substrates.

[0166] Table 7. Summary of the antimicrobial efficacy of μBCC in coatings

[0167]

[0168] The antimicrobial efficacy of the copper-containing composition in the dry film of the matte paint is given in Table 7. The addition of μBCC (1670 ppm Cu) resulted in a >3 Log increase in bacterial counts compared to the blank paint. 10 or >99.9% reduction to pass EPA standards for supplemental antimicrobial products.

[0169] Example 7

[0170] The antimicrobial efficacy of copper-containing compositions in dry paint films was evaluated using a transitional EPA method (Transitional Method for Evaluating the Efficacy of Antimicrobial Surface Coatings: 10-02-2020). In brief, μBCC dispersions were added to matte wall paint (41.5% solid volume, <50 g / L VOC, 0.52% alkyl (50% C14, 10% C16, 40% C12) dimethylbenzyl ammonium chloride) for target Cu and quaternary ammonium salt levels, respectively. The coating was scraped onto a sterilized steel substrate (1 inch × 1 inch AISI type 304 stainless steel). The resulting coated substrate was dried at ambient conditions for at least 24 hours. Some dried coated substrates were further subjected to residual efficacy requirements for drying and chemical abrasion for 1 week. As for dry abrasion, the coated substrate was exposed to 10 cycles of dry abrasion using a BYK Gardner-Scrub machine, with Scotch Brite Non-Scratch scrubbing sponges, each cycle including 16 single passes. For chemical abrasion, soak the scrubbing sponge in a solution of sodium hypochlorite (2000 ppm NaOCl) and EPA registered Nugen quaternary ammonium salts prior to abrasion. TM MB 5 N-256 (256-fold dilution) disinfectant. The coated substrates were exposed to 10 chemical abrasion cycles, each consisting of 8 single passes, by means of a soaked scrubbing sponge. After rinsing and drying to remove residual NaOCl and quaternary ammonium salts, the dry films of the test coatings were inoculated with each of two (2) bacterial inocula (20 ml): Staphylococcus aureus (ATCC 6538) and Pseudomonas aeruginosa (ATCC 15442) to obtain 10 on the dry surface of each test coating. 4 Up to 10 5 The test coatings were incubated at 22°C and 30-40% RH for 2 hours. The degree of bacterial contamination was determined by viable cell counts for antimicrobial efficacy relative to uncoated substrates.

[0171] Table 8. Summary of the antimicrobial efficacy of μBCC and quaternary ammonium salts in coatings

[0172]

[0173]

[0174] The antimicrobial efficacy of the copper-containing composition in the matte paint dry film is given in Table 8, which demonstrates the improved efficacy by adding μBCC to the quat-containing paint. In particular, after drying and NaOCl / quat abrasion, the combination of μBCC (1670 ppm) and quat (5200 ppm) achieved >3 Log for both Staphylococcus and Pseudomonas. 10or >99.9% reduction to achieve the 1-week residual efficacy requirement per EPA standards.

[0175] Example 8

[0176] The antifungal efficacy of copper-containing compositions in dry paint films was evaluated using the ASTM method (Standard Test Method for Resistance to Mold Growth on Interior Coating Surfaces in Environmental Chambers). In brief, μBCC dispersions and optional quaternary ammonium salts (quaternary ammonium compounds) were added to matte wall paint (50% PVC, 35% solid volume, 45 g / LVOC, Table 1) for target Cu and quaternary ammonium salt levels, respectively. Two coats were brushed onto both faces and all edges of the wood panel. Panels (1 day allowed between coats). The resulting coated panels were dried for 4 days at 23 ± 2 ° C and 50 ± 5% relative humidity. Greenhouse soil was inoculated with Aspergillus niger (ATCC 6275), budding short stalk mold (ATCC 9348) and Penicillium citrinum (ATCC 9849). In the environmental chamber, the dried coated panels were hung vertically, with the bottom about 3 inches above the inoculated soil surface, and with sufficient spacing to allow air to circulate freely and prevent contact between the panels or with the wall surface. The coated panels were exposed to 32.5±1°C and 95±3% relative humidity in an environmental chamber for 4 weeks. The degree of fungal contamination was assessed using the scoring scale in Table 9.

[0177] Table 9. Fungal growth scoring scale

[0178] score describe Notes 10 0% damage pass 9 1-10% damage pass 8 11-20% damage pass 7 21-30% damaged Failed 6 31-40% damaged Failed 5 41-50% destroyed Failed 4 51-60% destroyed Failed 3 61-70% destroyed Failed 2 71-80% destroyed Failed 1 81-90% destroyed Failed 0 91-100% destroyed Failed

[0179] The antifungal efficacy of the copper-containing additives in the matte wall paint dry film is given in Table 10. μBCC passed the test at the 333 ppm Cu level, but failed at the 167 ppm Cu level, while the two quaternary ammonium salts failed the test at the 2000 ppm level. The combination of μBCC (167 ppm Cu) and quaternary ammonium salts (2000 ppm) passed the test, while each individual component failed the test at these levels.

[0180] Table 10. Summary of the antifungal efficacy of μBCC and quaternary ammonium salts in coatings

[0181]

[0182] Without departing from the spirit and scope of the present invention, those of ordinary skill in the art may implement these and other modifications and variations of the present invention, which are more specifically set forth in the appended claims. In addition, it should be understood that the aspects of the various embodiments may be interchangeable in whole or in part. In addition, those of ordinary skill in the art will appreciate that the foregoing description is exemplary only and is not intended to limit the present invention as further described in the appended claims.

Claims

1. A polymer emulsion composition, comprising: latex adhesive; Insoluble copper compounds; and Complementary color pigments, wherein the insoluble copper compound is present in the polymer emulsion composition in an amount of less than about 4000 ppm Cu.

2. The polymer emulsion composition of claim 1, wherein the insoluble copper compound comprises one or more of basic copper (II) carbonate, copper (II) hydroxide, 8-hydroxyquinoline copper, copper (II) pyrithione, copper (II) acetylacetonate, and copper (II) oxide.

3. The polymer emulsion composition according to claim 1 or 2, wherein the complementary color pigment is a red pigment.

4. The polymer emulsion composition according to claim 1 or 2, wherein the complementary color pigment is a white pigment.

5. The polymer emulsion composition according to any one of claims 1 to 4, wherein the complementary color pigment comprises one or more of iron (III) oxide, diketopyrrolopyrrole, dibromanthranthrone and zinc oxide.

6. The polymer emulsion composition according to any one of claims 1 to 5, wherein the complementary color pigment is present in the polymer emulsion composition in an amount of less than or equal to about 5000 ppm.

7. The polymer emulsion composition according to any one of claims 1 to 6, wherein the insoluble copper compound is present in the polymer emulsion composition in an amount from about 100 ppm to about 1800 ppm Cu.

8. The polymer emulsion composition according to any one of claims 1 to 7, wherein the insoluble copper compound comprises micronized insoluble copper compound particles, and wherein 50% or more of the micronized insoluble copper compound particles have a median particle size of less than about 1 micron.

9. The polymer emulsion composition according to any one of claims 1 to 8, further comprising a co-biocide.

10. The polymer emulsion composition according to claim 9, wherein the co-biocide comprises one or more derivatives of quaternary ammonium, isothiazolinone, pyridinethione, triazine, haloalkynyl, hydantoin and urea.

11. The polymer emulsion composition according to claim 9, wherein the co-biocide comprises one or more of dimethylbenzyl ammonium chloride, N,N-didecyl-N,N-dimethylammonium chloride, N,N-didecyl-N,N-dimethylammonium carbonate / bicarbonate, zinc pyrithione, and sodium pyrithione.

12. The polymer emulsion composition according to claim 9, wherein the co-biocide is present in the polymer emulsion composition in an amount of from about 50 ppm Cu to about 5500 ppm Cu.

13. The polymer emulsion composition according to any one of claims 1 to 12, further comprising an adjuvant.

14. The polymer emulsion composition according to claim 13, wherein the adjuvant comprises one or more of 2-dicyandiamide and zinc trifluoroethylacetoacetate.

15. A latex coating composition comprising the polymer emulsion composition of claim 1.

16. An antimicrobial composition comprising: Insoluble copper compounds; and Complementary color pigments, wherein the insoluble copper compound is present in the polymer composition in an amount less than about 4000 ppm Cu.

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