Copper-containing compounds and compositions for antimicrobial paints and coatings

Abstract

The present disclosure generally relates to polymer emulsion compositions. The polymer emulsion composition includes a latex binder. The polymer emulsion composition further includes an insoluble divalent copper compound. The polymer emulsion composition further includes a complementary pigment. The insoluble divalent copper compound is present in the polymer emulsion composition in an amount of less than about 4000 ppm of Cu.

Description

Technical Field

[0001] Related Applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 357,671, filed on July 1, 2022, which is incorporated herein by reference in its entirety.

Background Art

[0002]

[0002] Paints and coatings are often used to protect surfaces from corrosion, oxidation, or other types of degradation. At all stages of their lifespan, paints and coatings are susceptible to contamination and degradation by various microorganisms, including viruses, bacteria, fungi, and algae. Additionally, the presence of water and nutrients makes these paints, such as latex paints, vulnerable to microbial attack in both wet and dry coating films. Microbial growth on the surface of latex paints can cause staining and degradation, leading to a decrease in the durability of the paint and a poor aesthetic appearance of the surface. Therefore, biocides or antibacterial agents may be incorporated into the paint formulation to reduce or inhibit the growth of microorganisms in the latex paint and maintain the aesthetic appearance of the surface.

Summary of the Invention

Problems to be Solved by the Invention

[0003]

[0003] It is desirable to employ hygienic paints and coatings that have a broad antibacterial effect against viruses and bacteria while minimizing the impact on the color of the dry coating film. Due to government regulations and manufacturing cost considerations, it may be desirable to adopt a combination of antibacterial agents with reduced amounts of each antibacterial agent while still achieving a high antibacterial effect.

[0004]

[0004] Therefore, there is a need to adopt improved antibacterial agent compositions in polymer emulsions.

Means for Solving the Problems

[0005]

[0005] Generally, the present disclosure is directed to polymer emulsion compositions and antimicrobial agent compositions. The compositions disclosed herein may be incorporated into preservatives for latex emulsion compositions, such as latex paint compositions, in a wet state within a container. In particular, the compositions of the present disclosure advantageously exhibit antimicrobial properties. Specifically, it has been found that when an insoluble cupric compound is employed in combination with a complementary colored pigment in a polymer emulsion composition as described by the present disclosure, a polymer emulsion composition exhibiting a wide range of antimicrobial properties while avoiding the effects of undesirable colors can be obtained. Further, the components of the compositions disclosed herein may exhibit beneficial enhancing effects in order to advantageously utilize a reduced amount of the composition while still achieving the desired degree of antimicrobial effect.

[0006]

[0006] In one embodiment, the polymer emulsion composition comprises an insoluble cupric compound. The polymer emulsion composition further comprises a complementary pigment. In particular, the insoluble cupric compound is present in the polymer emulsion composition in an amount of less than about 4,000 ppm of Cu.

[0007]

[0007] In one exemplary embodiment, the insoluble cupric compound may comprise at least one of basic copper(II) carbonate, copper(II) hydroxide, copper 8 - quinolinolate, copper(II) pyrithione, copper acetylacetonate, copper(II) oxide, or combinations thereof.

[0008]

[0008] In another exemplary embodiment, the complementary pigment may comprise a red or white pigment.

[0009] In another exemplary embodiment, the complementary pigment may comprise at least one of iron(III) oxide, diketopyrrolopyrrole, dibromanthranthrone, zinc oxide, or combinations thereof.

[0009]

[0010] In another exemplary embodiment, the complementary pigment may be present in a total amount of about 5000 ppm or less.

[0011] In another exemplary embodiment, the insoluble secondary copper compound may be present in the polymer composition in a total amount of from about 100 ppm to about 1800 ppm.

[0010]

[0012] In another exemplary embodiment, the insoluble secondary copper compound may be micronized insoluble secondary copper compound particles, and at least 50% of the micronized insoluble secondary copper compound particles have a median particle size of less than about 1 micron.

[0011]

[0013] In another exemplary embodiment, the polymer emulsion composition may further comprise a co-biocide such as at least one derivative of quaternary ammonium, isothiazolinone, pyrithione, triazine, haloalkylnyl, hydantoin, urea, or combinations thereof.

[0012]

[0014] In another exemplary embodiment, the co-biocide may comprise at least one of dimethylbenzylammonium chloride, N,N-didecyl-N,N-dimethylammonium chloride, N,N-didecyl-N,N-dimethylammonium carbonate / bicarbonate, zinc pyrithione, sodium pyrithione, or combinations thereof.

[0013]

[0015] In another exemplary embodiment, the co-biocide may be present in a total amount of from about 50 ppm to about 5500 ppm.

[0016] In another exemplary embodiment, an adjuvant may be further included.

[0014]

[0017] In another exemplary embodiment, the adjuvant may comprise at least one of 2-dicyandiamide, zinc trifluoroethyl acetoacetate, or combinations thereof.

[0015]

[0018] In another exemplary embodiment, the latex paint composition may comprise the polymer emulsion composition disclosed herein.

[0019] Each of the exemplary embodiments listed above may be combined with one or more of the other exemplary embodiments listed above in a particular embodiment. For example, all of the exemplary embodiments listed above may be combined with each other in some embodiments. In another example, in some other embodiments, any combination of two, three, four, five, or more of the 20 exemplary embodiments listed above may be combined. Therefore, the exemplary embodiments listed above may be used in combination with each other in some exemplary embodiments. Alternatively, the exemplary embodiments listed above may be implemented individually in other exemplary embodiments. Thus, it will be understood that various exemplary embodiments can be realized by using the exemplary embodiments listed above.

[0016]

[0020] In another exemplary embodiment, the antimicrobial composition comprises an insoluble divalent copper compound comprising basic copper carbonate. The antimicrobial composition further comprises a complementary color pigment. In particular, the insoluble divalent copper compound is present in the antimicrobial composition in an amount of less than about 4,000 ppm.

[0017]

[0021] These and other configurations, embodiments, and advantages of the present invention will be further understood by reference to the following description and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

[0018]

[0022] Reference will now be made in detail to the exemplary embodiments disclosed herein. Those skilled in the art should understand that this disclosure is only an explanation of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0019]

[0023] The present disclosure generally relates to polymer emulsion compositions and antimicrobial compositions. The polymer emulsion composition may comprise an insoluble divalent copper compound. Further, the polymer emulsion composition may comprise a complementary color pigment. In particular, the insoluble divalent copper compound is present in the polymer composition in an amount of less than about 4000 ppm of Cu.

[0020]

[0024] The compositions disclosed herein may advantageously exhibit antiviral and antibacterial properties. Specifically, the polymer emulsion compositions and the antibacterial agent compositions have a broad spectrum of antibacterial activity against various microorganisms. Further, the insoluble cupric compound combined with a complementary pigment may advantageously limit or inhibit the growth of microorganisms without coloring the polymer emulsion composition. It has been conventionally understood that the insoluble cupric compounds described herein impart colors such as green hues to paints and coatings. However, the polymer emulsion compositions and the biocidal compositions of the present disclosure may advantageously exhibit antibacterial properties while surprisingly avoiding the conventionally predicted color effects by the insoluble cupric compounds.

[0021]

[0025] Furthermore, the polymer emulsion compositions and the antibacterial agent compositions disclosed herein may optionally include various other components such as co-biocides, auxiliary compounds, or combinations thereof. Particularly advantageously, the polymer emulsion compositions and the antibacterial agent compositions disclosed herein may exhibit enhanced interactions and a relatively high antibacterial effect against a variety of microorganisms.

[0022]

[0026] As used herein, "enhanced interaction" refers to the insoluble cupric compound combined with a complementary pigment having a combined effect greater than the biocidal or antibacterial properties of the antibacterial agent acting alone. For example, the insoluble cupric compounds and complementary pigments disclosed herein, optionally in combination with one or both of a co-biocide and an auxiliary compound, are made to act together so as to have a higher antibacterial activity against certain microorganisms in the presence of each compared to the antibacterial activity of the insoluble cupric compound alone. Due to this enhancing effect, the amounts of the insoluble cupric compound and the complementary pigment present in the composition can be reduced while still exhibiting the desired effectiveness.

[0023]

[0027] Combinations of biocides and additives combined with each other according to the present disclosure include at least an insoluble cupric compound and a complementary pigment. In some examples, one or more biocides may be present to further enhance the effect. Therefore, the amount of the insoluble cupric compound present in the composition can be reduced or minimized. For example, the polymer emulsion composition and the antibacterial composition may have an equivalent or better effectiveness against one or more microorganisms while containing a total amount of the insoluble cupric compound and the complementary pigment that is less than when only one is present.

[0024]

[0028] According to an exemplary embodiment of the present disclosure, the insoluble cupric compound generally includes a copper compound such as an inorganic copper compound. The cupric compound has a water solubility of less than 50 mg / mL. For example, the insoluble cupric compound may include an inorganic copper salt such as a carbonate, bicarbonate, sulfate, nitrate, chloride, hydroxide, borate, fluoride, or oxide.

[0025]

[0029] Other examples of the insoluble cupric compound 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. Still other examples of copper-containing compounds include copper octoate, copper diammonia diacetate complex, copper ethanolamine complex, copper naphthenate, and copper 8-quinolinolate. 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.

[0026]

[0030] In one exemplary embodiment, the insoluble secondary copper compound comprises at least one of basic copper carbonate (II), copper hydroxide (II), copper 8-quinolinolate, copper (II) pyrithione, copper acetylacetonate, and copper (II) oxide. In a preferred exemplary embodiment, the insoluble secondary copper compound comprises basic copper carbonate.

[0027]

[0031] It has been recognized that the insoluble secondary copper compounds described herein can affect the color of the paint or coating from which the copper compound is obtained and may in some cases completely change the color, and thus are not conventionally employed in paint and coating products. Particularly advantageously, the inventors of the present invention have found that when the insoluble secondary copper compounds herein are employed in a polymer emulsion composition according to an exemplary embodiment of the present disclosure, surprisingly, the effect on the color of the resulting paint or coating is negligible. Therefore, despite the presence of the insoluble secondary copper compound, the latex paint can advantageously be a "pure white" base paint or a paint that may have a desired color tone. In one exemplary embodiment, the insoluble secondary copper compound preferably comprises or is basic copper carbonate.

[0028]

[0032] In one embodiment, the insoluble secondary copper compound may comprise micronized insoluble secondary copper compound particles. The micronized insoluble secondary copper compound particles may have a particle size of from about 0.01 micron to about 25.0 microns, such as from about 0.01 micron to about 10 microns, such as from about 0.05 micron to about 10 microns, such as from about 0.1 micron to about 10.0 microns, such as from about 0.01 micron to about 1.0 micron, such as from about 0.05 micron to about 1.0 micron, such as from about 0.1 micron to about 1.0 micron, such as from about 0.2 micron to about 1.0 micron.

[0029]

[0033] Advantageously, the insoluble secondary copper compound may be present in the compositions of the present disclosure, including the polymer emulsion and the antimicrobial composition, 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.

[0030]

[0034] In one embodiment, the insoluble secondary copper compound disclosed herein may be added directly to the polymer emulsion composition and the antimicrobial composition. Therefore, the insoluble secondary copper compound of the present disclosure substantially does not contain a medium or matrix such as glass. Further, the insoluble secondary copper compound may be present in the form of a dispersion or a solution.

[0031]

[0035] As described above, the polymer emulsion composition and the antimicrobial composition contain a complementary pigment. For example, the complementary pigment may include a red pigment. In one exemplary embodiment, the red pigment includes iron(II) oxide, diketopyrrolopyrrole, or dibromoanthraquinone. Alternatively, the complementary pigment may include a white pigment such as zinc oxide.

[0032]

[0036] The complementary pigment may be present in the form of particles having a particle size of 0.01 microns to 25.0 microns in the compositions of the present disclosure, including the polymer emulsion and the antimicrobial composition. In one embodiment, the particle size of the inorganic oxide compound used in the compositions disclosed herein may be 0.01 to 10 microns, 0.05 to 10 microns, 0.1 to 10.0 microns, 0.01 to 1.0 microns, 0.05 to 1.0 microns, 0.1 to 1.0 microns, 0.2 to 1.0 microns.

[0033]

[0037] The complementary pigment may be present in the compositions disclosed herein at concentrations 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, etc.

[0034]

[0038] In another exemplary embodiment, regardless of the type or amount of pigment employed, the complementary pigment may be present in a micronized form, either alone or in combination with a dispersant. For example, in one embodiment, the complementary 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.

[0039] In one embodiment, the insoluble cupric compound and the complementary pigment may be present in the polymer emulsion composition or the antibacterial agent composition at 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.

[0035]

[0040] In one exemplary embodiment, the insoluble cupric compound and iron oxide are present in the polymer emulsion composition at a weight ratio of about 10:1 to about 30:1, such as about 15:1 to about 25:1.

[0036]

[0041] In another exemplary embodiment, the insoluble cupric compound and zinc oxide are present in the polymer emulsion composition at a weight ratio of about 10:1 to about 1:10, such as about 1:1.

[0037]

[0042] As described above, the polymer emulsion composition and the antibacterial agent composition disclosed in this specification may optionally contain a co-biocide. For example, the co-biocide may include one or more of a quaternary ammonium compound, an isothiazolinone compound, a pyrithione compound, a triazine compound, a haloalkylnile compound, a hydantoin compound, or a urea compound.

[0038]

[0043] In another exemplary embodiment, the biocide includes a quaternary ammonium compound. For example, the biocide may include a quaternary ammonium halide, a quaternary ammonium carbonate / bicarbonate, or a benzylammonium halide.

[0039]

[0044] The quaternary ammonium compound, also known as "quat", typically contains at least one quaternary ammonium cation along with a suitable anion. Quats generally have the following general formula:

[0040]

Chemical formula

[0041] and will have.

[0045] The groups R1, R2, R3, and R4 may vary within wide limits and examples of quaternary ammonium compounds having antibacterial properties will be well known to those skilled in the art. Typically, two of R1, R2, R3, and R4 are lower alkyls meaning having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, or butyl groups. Further, two of R1, R2, R3, and R4 are long-chain alkyl groups having 6 to 24 carbon atoms, or a benzyl group. A - is a monovalent anion of an inorganic or organic acid or a 1-equivalent polyvalent anion. A - Suitable anions for A are in principle all inorganic or organic anions, especially halides such as chloride or bromide, carboxylic acids, sulfonic acids, phosphoric acids, or mixtures thereof.

[0042]

[0046] In another exemplary embodiment, the quaternary ammonium compound 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 (where n = 1 to 20), R3 and R4 are each independently C 1~4 alkyl, R5 is hydrogen or unsubstituted or substituted alkyl or phenyl, and A - is a monovalent anion of an inorganic or organic acid or one equivalent of a polyvalent anion.

[0043]

[0047] In another exemplary embodiment, the quaternary ammonium compound may include a dialkylammonium compound such as a dimethyldialkylammonium compound. In one embodiment, the dimethyldialkylammonium compound may have from about 8 to about 12 carbon atoms, such as from about 8 to about 10 carbon atoms, in each of the alkyl groups.

[0044]

[0048] Examples of dimethyldialkylammonium compounds that may be used as biocides include dimethyldioctylammonium compounds such as dimethyldioctylammonium chloride, dimethyldidecylammonium compounds such as dimethyldidecylammonium chloride, and the like. Mixtures of dimethyldialkylammonium compounds may also be used, and other anions such as those described above may also be used. Commercially available dimethyldialkylammonium compounds include, for example, BARDAC™ LF-80, BARDAC™ 22, and BARDAC™ 208M, available from Arxada, LLC (formerly Lonza Specialty Ingredients).

[0045]

[0049] In another exemplary embodiment, the co-biocide has the following formula:

[0046]

Chemical formula

[0047] It may contain a quaternary ammonium carbonate that can be represented by

[0050] In the formula, R 1 is a C1-C 20 alkyl or aryl-substituted alkyl group, and R 2 is a C8-C 20 alkyl group, preferably R 1 is the same as R 2 and R 1 is a C8-C 20 alkyl group, and at the same time the composition is the corresponding quaternary ammonium bicarbonate

[0048]

Chemical formula

[0049] and further contains

[0051] In the formula, R 1 is the same or different C1-C 20 alkyl or aryl-substituted alkyl group as described above, and R 2 is the same or different C8-C 20 alkyl group as described above, but preferably R 1 is the same as R 2 and R 1 is a C8-C 12 alkyl group.

[0050]

[0052] The quaternary ammonium carbonate / bicarbonate may include a di-C8-C 12 alkylammonium carbonate / bicarbonate. For example, in one specific exemplary embodiment, the composition includes didecyldimethylammonium carbonate and didecyldimethylammonium bicarbonate.

[0051]

[0053] However, in other exemplary embodiments, the carbonate / bicarbonate of the quaternary ammonium cation 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 carbonates.

[0052]

[0054] Preferably, the quaternary ammonium compound may include one or more of didecyldimethylammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, and alkyldimethylbenzylammonium chloride.

[0053]

[0055] In one exemplary embodiment, the co-biocide may include a benzylammonium compound such as an alkyldimethylbenzylammonium compound. Generally, the alkyl group may include from about 10 to about 18 carbon atoms, such as from about 12 to about 16 carbon atoms.

[0054]

[0056] Examples of alkyldimethylbenzylammonium compounds that can be used as biocides include C 12 alkyldimethylbenzylammonium chloride, C 14 alkyldimethylbenzylammonium chloride, and C 16Examples include alkyldimethylbenzylammonium chloride. Furthermore, mixtures of these alkyldimethylbenzylammonium compounds can be used. Commercially available alkyldimethylbenzylammonium compounds include, for example, BARQUAT® DM-80 and BARQUAT® 50-65B, which are available from Arxada, LLC (formerly Lonza Specialty Ingredients). These commercially available alkyldimethylbenzylammonium compounds are blends of C 12 、C 14 、and C 16 alkyldimethylbenzylammonium chloride. Generally, alkyldimethylbenzylammonium compounds, when in blend, preferably contain a higher concentration of C 16 alkyl than the C 12 alkyl and C 14 alkyl components. Note that other anions, including those described above, may also be used.

[0055]

[0057] In another exemplary embodiment, the co-biocide comprises an isothiazolone compound. Suitable isothiazolinones are represented by the following general formula:

[0056] [Chemical Formula]

[0057] as represented by.

[0058] In the formula, 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 each independently represent hydrogen, halogen, or C1-C4 alkyl; or R 2 and R 3may combine together to give a 1,2 - benzisothiazolin - 3 - one group (i.e., R 2 and R 3 may combine to form -(CH)4 -).

[0058]

[0059] In one exemplary embodiment, R 2 and R 3 each independently represents chloro or hydrogen, or R 2 and R 3 may combine together to provide a 1,2 - benzisothiazolin - 3 - one group.

[0059]

[0060] Thus, in one exemplary embodiment, the R 1 substituent is 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.

[0060]

[0061] In one such exemplary embodiment, the R 1 substituent in the compound of the above formula represents hydrogen, optionally substituted C1 - C 18 alkyl, optionally substituted aralkyl having up to 10 carbon atoms, or optionally substituted aryl having up to 10 carbon atoms. In a further embodiment, R 1 represents hydrogen or optionally substituted C1 - C 18 alkyl. Further or alternatively, R 1 is hydrogen or C1 - C8 alkyl, and hydrogen, methyl, butyl, and octyl are the most preferred R 1 substituents.

[0061]

[0062] Accordingly, in one aspect, the isothiazolinone used in the polymer emulsion composition and / or the antibacterial agent composition according to the present disclosure is represented by the above general formula, wherein R 1 represents hydrogen or C1-C8 alkyl, and R 2 and R 3 each independently represents chloro or hydrogen, or R 2 and R 3 may together form a 1,2-benzisothiazolin-3-one group.

[0062]

[0063] In one exemplary aspect, the isothiazolinone used in the polymer emulsion composition and / or the antibacterial agent 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 each independently represents chloro or hydrogen, or R 2 and R 3 may together form a 1,2-benzisothiazolin-3-one group.

[0063]

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

[0064]

Chemical formula

[0065] is benzisothiazolinone.

[0065] In the formula, R is hydroxy, halogen (especially chlorine), C 1~4 alkyl, or C 1~4 alkoxy; R 1 is as defined above herein; 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 benzisothiazolinone. However, in a further aspect, n is zero.

[0066]

[0066] In one exemplary embodiment, the benzisothiazolinone has R 1 being H or C 1~5 alkyl, or R 1 being H or C 3~5 alkyl. 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. Thus, in one embodiment, the benzisothiazolinone is 1,2-benzisothiazolin-3-one.

[0067]

[0067] For example, in one exemplary embodiment, the isothiazolone includes, but is not limited to, methyl isothiazol-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), octyl isothiazol-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). Particularly preferred isothiazolones include, but are not limited to, methyl isothiazol-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), octyl isothiazol-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), octyl isothiazolone (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), and N-(n-butyl)-1,2-benzisothiazol-3-one (BBIT), more preferably octyl isothiazolone (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), and N-(n-butyl)-1,2-benzisothiazol-3-one (BBIT), or a combination thereof.

[0068] 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), 1,2-benzothiazolin-3-one (BIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), and 2-butyl-1,2-benzisothiazolin-3(2H)-one (BBIT).

[0069]

[0069] In another exemplary embodiment, the biocide includes a pyrithione compound. For example, the pyrithione compound may include sodium pyrithione, zinc pyrithione, copper pyrithione, 1-hydroxy-2-pyridone, and pyrithione disulfide.

[0070]

[0070] In another exemplary embodiment, the biocide includes a triazine compound. For example, the triazine compound may include 1,3,5-triazine.

[0071] In another exemplary embodiment, the biocide includes a haloalkyl nitrile compound such as haloalkyl nitrile carbamate. For example, the haloalkyl nitrile carbamate has the following general formula:

[0071]

Chemical formula

[0072] It may include iodoalkynyl carbamate having the formula:

[0072] In the formula, m is 1, 2, or 3; n is 1, 2, or 3; R is hydrogen (H); unsubstituted or substituted alkyl, aryl, aralkyl, alkylaryl, alkenyl, cycloalkyl, or cycloalkenyl, or alkoxyaryl all have from 1 to 20 carbon atoms, and m and n may be the same or different.

[0073]

[0073] Suitable R substituents for the iodoalkynyl carbamate compounds include alkyl such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, etc., cycloalkyl such as cyclohexyl, etc., aryl, alkaryl, and aralkyl such as phenyl, benzyl, tolyl, cumyl, etc., halogenated alkyl and aryl such as chlorobutyl and chlorophenyl, etc., and alkoxyaryl such as ethoxyphenyl, etc. Accordingly, 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-chlorophenyl carbamate (IPCI PhC), 3-iodo-2-propynyl-4-chlorobutyl carbamate (IPCI BC), and mixtures thereof.

[0074]

[0074] Preferably, the haloalkynyl compound may contain 3-iodo-2-propynyl butyl carbamate (IPBC).

[0075] In another exemplary embodiment, the biocide includes a hydantoin compound such as an aldehyde. For example, the aldehyde may include formaldehyde and paraformaldehyde. The aldehyde forming the compound includes an imidazolidine compound such as a hydantoin such as dimethylol dimethyl hydantoin (DMDMH).

[0075]

[0076] In another exemplary embodiment, the co-biocide includes urea derivatives such as aryl urea compounds. For example, the aryl urea compound may include (3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron).

[0076]

[0077] The complementary pigment may be present in the compositions disclosed herein at concentrations 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.

[0077]

[0078] Optionally, the compositions disclosed herein may further include an auxiliary compound. For example, the auxiliary compound may include a guanidine accelerator having the structure of Compound I, and Compound I has the formula: HR2N-(C=NHR3)-NR1H

[0078]

Chemical formula

[0079] wherein it has the following structure.

[0079] In the formula, 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 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 12It is aryl; at least one of R3, R1, or R2 is C.

[0080]

[0080] In one exemplary embodiment, the auxiliary compound and the insoluble divalent copper compound are present in the polymer emulsion composition in a weight ratio of about 1:1 to about 1000:1.

[0081] In another exemplary embodiment, the auxiliary compound is present in the polymer emulsion composition at a concentration of about 100 ppm Cu to about 10,000 ppm Cu, such as, for example, about 200 ppm Cu to about 10,000 ppm Cu, such as, for example, about 1,000 ppm Cu to about 10,000 ppm Cu.

[0081]

[0082] As used herein, the description of chemical formulas uses standard element symbols according to the periodic table (e.g., C represents carbon, N represents nitrogen, etc.). Further, since the description of chemical formulas is based on standard bonds, unless otherwise specified, carbon can form four bonds and nitrogen can form three bonds. Thus, the description of CN should be understood to represent a cyano group, where carbon contains a triple bond with nitrogen and the remaining carbon bonds can represent the attachment of the cyano group to the chemical structure.

[0082]

[0083] The guanidine accelerator contains one or more of 1-cyanoguanidine, salts of 1-cyanoguanidine, 2-cyanoguanidine (also called dicyandiamide), and salts of 2-cyanoguanidine. Both 1-cyanoguanidine and 2-cyanoguanidine are derivatives of Compound I, wherein in each case, R2 or R1 is CN, R3 is H, and R1 and R2 are H, and R3 is CN. As should be understood, the conversion between 1-cyanoguanidine and 2-cyanoguanidine occurs by tautomerization in an aqueous solution or exposure to other proton-donating solvents, and thus a composition containing only one tautomer may show conversion to a mixture of both over time. Further, when exemplified using 1-cyanoguanidine and 2-cyanoguanidine, generally, tautomers of species derived from Compound I may be included as the guanidine accelerator according to the examples of the present disclosure. The tautomers of Compound I include structures (a) and (b), which have the formula:

[0083]

Chemical formula

[0084] and are as follows.

[0084] In the formula, 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 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 at least one of R3, R1, or R2 is CN.

[0085]

[0085] Generally, guanidine compounds can react with proton donors to form salts having a guanidinium cation with a positive charge paired with an anion having a negative charge. Therefore, in a specific polymer emulsion composition or antibacterial agent composition, the guanidine promoter may be a salt of Compound I, such as a salt of 1-cyanoguanidine and / or a salt of 2-cyanoguanidine.

[0086]

[0086] Some examples of anions that may be included as a salt of 1-cyanoguanidine or a salt of 2-cyanoguanidine include inorganic anions such as halides (e.g., chloride, bromide, fluoride, iodide, etc.), nitric acid, and sulfuric acid. Alternatively or additionally, the anion may include an organic anion such as an acetate anion or a carboxylic acid anion derived from a fatty acid such as octanoic acid, decanoic acid, or dodecanoic acid. Preferably, the guanidine promoter contains 2-dicyandiamide.

[0087]

[0087] In another exemplary embodiment, the auxiliary compound may include trifluoroacetic acid or a salt thereof. For example, the auxiliary compound may include zinc ethyltrifluoroacetate.

[0088] In another exemplary embodiment, the auxiliary compound may include tetramethylguanidine (TMG) such as 1,1,3,3-tetramethylguanidine and / or 2-tert-butyl-1,1,3,3-tetramethylguanidine.

[0088]

[0089] In another exemplary embodiment, the auxiliary compound may include a cystamine promoter such as cystamine dihydrochloride.

[0090] In one exemplary embodiment, the pH of the polymer emulsion composition or antibacterial agent composition is from about 8.0 to about 9.5. As is known in the art, pH builders, pH buffers, and other pH adjusters may be used to obtain and stabilize the above pH values.

[0089]

[0091] The polymer emulsion composition of the present disclosure further comprises a solvent. In the polymer emulsion of the present disclosure, the solvent may include various suitable organic and / or inorganic solvents. In one exemplary embodiment, the solvent includes water.

[0090]

[0092] In another exemplary embodiment, the polymer emulsion composition of the present disclosure may be a latex paint composition. Generally, a latex paint composition further comprises a latex binder (e.g., a polymer containing one or more acrylate, vinyl acetate, vinyl chloride, and / or styrene-butadiene monomers). Optionally, the latex paint may further comprise an emulsifier and / or surfactant to improve the distribution of the latex binder throughout the polymer emulsion composition. Thus, the emulsifier and / or surfactant can be used to create a more homogeneous mixture that can result in a smoother coating of the resulting latex paint coating. Optionally, the latex paint composition may include a thickener to adjust the viscosity of the latex paint and improve the wet paint adhesion to an application tool (e.g., a brush or roller). Optionally, the latex paint composition may include a co-solvent (e.g., ethylene glycol) that can improve the solubility of the components of the latex paint composition.

[0091]

[0093] In one exemplary embodiment, the polymer emulsion composition may constitute about 5 wt.% to about 40 wt.% of the latex paint composition, such as about 20 wt.% to about 30 wt.% of the latex paint composition.

[0092]

[0094] Another aspect of the embodiments may include certain latex binders. The latex binder may include various polymers suitable for latex paints, such as acrylates (e.g., polymethyl methacrylate) that may be formed as homopolymers or copolymers. For example, the copolymer may incorporate another monomer (e.g., butadiene styrene). In some implementations, the acrylate can be modified to include one or more nitrile groups. Thus, the latex binder may include various acrylates, acrylate butadiene styrene copolymers, and acrylonitrile butadiene styrene copolymers. Further, these latex binders are shown for illustrative purposes, and additional latex binders may be used alone or in combination with the disclosed embodiments.

[0093]

[0095] As an example for illustration, embodiments of the present disclosure may include a latex paint including a latex binder having an acrylate. The acrylate may include a polymer or copolymer including one or more acrylate monomers. Example embodiments of the acrylate polymer or copolymer may include a certain mass fraction of acrylate monomers. For example, the acrylate may include a copolymer including 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 about 20 wt% or more and about 100 wt% or less, such as about 30 wt% or more and about 80 wt% or less, about 40 wt% or more and about 70 wt% or less, or about 45 wt% or more and about 60 wt% or less, etc. (e.g., 100 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt%, or 50 wt%). In particular, certain embodiments may include acrylates having a mass fraction of acrylate monomer exceeding 50 wt% relative to the total weight of the acrylate.

[0094]

[0096] In the practice of the present disclosure, the latex paint may contain an amount of pigment or may be formulated to contain an amount of pigment. For example, an exemplary latex paint may contain pigment, and the pigment may contain titanium dioxide (TiO2) at a concentration of 5 wt% or more and 60 wt% or less of TiO2 based on the total weight of the latex paint. TiO2 can be used to impart whiteness and / or opacity to the examples and may also be included to increase viscosity. Generally, the examples may contain 5 wt% or more and 60 wt% or less of TiO2, such as 15 wt% or more and 55 wt% or less of TiO2, 20 wt% or more and 50 wt% or less of TiO2, or 25 wt% or more and 45 wt% or less of TiO2.

[0095]

[0097] In another exemplary embodiment, the polymer emulsion composition of the present disclosure may be an adhesive.

[0098] In one exemplary aspect, the antimicrobial composition according to the present disclosure may be manufactured and sold as a biocide additive composition containing an insoluble cupric compound, a complementary pigment, and one or both of a co-biocide and an auxiliary compound, and the additive composition may substantially contain no other materials. Thus, the additive composition may be a three-component additive composition or a four-component additive composition in such exemplary embodiments. The three-component or four-component additive composition may be provided as a component for forming a latex paint composition or a polymer emulsion composition. Further, the three-component additive composition or the four-component additive composition may be added to other components to form a latex paint composition or a polymer emulsion composition. As described above, the polymer emulsion composition and / or the latex paint composition can advantageously achieve a wide range of antimicrobial control in the composition.

[0096]

[0099] As evidence of the enhancing effect of the insoluble cupric compound and the complementary pigment, the inhibitory concentration of the complementary pigment is lower in the presence of the insoluble cupric compound when tested against the target microorganism.

[0100] The foregoing description is, in essence, merely exemplary and is not intended to limit the scope of the disclosure, its applicability, or its configuration in any way. Without departing from the scope of the disclosure, various changes may be made to the functions and arrangements of the elements described herein with respect to the embodiments described.

[0097]

[0101] Unless otherwise defined, 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 pertains.

[0098]

[0102] As used in this application and the claims thereof, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Further, the term "includes" means "comprises." The methods and compositions of the present disclosure that include a component may include, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as additional or optional components, elements, or limitations described herein or useful in a biocidal composition.

[0099]

[0103] Unless otherwise specified, any numerical values, such as molecular weights, percentages, etc., representing amounts or properties of components used herein in the specification or claims are to be understood as being modified by the term "about." Accordingly, unless otherwise specified, the numerical parameters shown, whether implicitly or explicitly, are approximations that may depend upon the desired properties and / or the detection limits under standard test conditions / methods. When distinguishing an embodiment directly and explicitly from the prior art discussed, the numbers of the embodiment are not approximations unless the term "about" is recited.

[0100]

[0104] As used herein, "optional" or "optionally" means that the subsequently recited material, event, or circumstance may or may not be present or occur, and the description includes instances where the material, event, or circumstance is present or occurs and instances where they are not present or do not occur. As used herein, "w / w%" and "wt%" mean the relative weight to another component or the percentage of the total weight in a composition.

[0101]

[0105] The term "about" is intended to mean approximately, around, roughly, or nearly. When the term "about" is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the stated numerical values. It should be understood that the numerical parameters set forth in the following specification and the appended claims are approximate values unless otherwise specified. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents of the claims, the numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[0102]

[0106] When the term "substantially free of" is used to describe the amount of a substance in a material, it should not be limited to meaning completely free of or entirely without, but may correspond to the absence of a recognizable or detectable amount of the listed 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 accuracy of the test for measuring the amount of the substance in an accepted device or material in the industry. In certain exemplary embodiments, a material may be considered "substantially free of" a substance when the amount of the substance in the material is less than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.1% by weight of the material.

[0103]

[0107] The expression "effective amount" means the amount of a compound that promotes, improves, stimulates, or induces a response to a particular disease or disorder, or a particular symptom of a disease or disorder.

[0108] As used herein, the terms "enhancer" and "adjuvant" refer to additives that, when used in combination with an active compound, can affect the performance of the active compound but do not themselves exhibit biocidal activity and / or do not themselves exhibit biocidal activity in the compositions of the present invention.

[0104]

[0109] As used herein, the term "antibacterial agent" refers to any chemical compound that inhibits the growth of organisms on a coated surface and / or inhibits the growth of organisms "in the container" in a paint or coating before application to the surface.

[0105]

[0110] The terms "antifouling paint" and "antifouling coating" are used interchangeably herein.

[0111] 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 location or importance of individual members.

[0106]

[0112] Here, and throughout the specification and claims, the limits of a range are combined and interchanged, and such range is defined and includes any sub-ranges included therein, unless otherwise indicated in context or by the expression. For example, any range disclosed herein includes endpoints, and the endpoints can be combined independently of each other.

[0107]

[0113] As used herein, the term "D50" or "D50 particle size" refers to the volume median particle size, where 50% of the sample volume has particles with a size below that range or value.

[0114] Similarly, as used herein, the term "D95" or "D95 particle size" refers to a value where 95% of the particles in the sample volume have a size below that range or value.

[0108]

[0115] As used herein, the term "particle size", unless specifically stated otherwise, 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.

[0109]

[0116] The terms "median particle size", "average particle size", and D50 are used interchangeably herein.

[0117] As used herein, the term "miniaturization" means a median particle size (D50) within the range of 0.01 to 25 microns.

[0110]

[0118] This specification uses examples to disclose the present disclosure, including the best mode, and also includes the fabrication and use of any device or system and the implementation of any incorporated method, enabling any person skilled in the art to practice the disclosure. The patentable scope of the disclosure is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments 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 that differ only slightly from the literal language of the claims.

[0111]

[0119] Furthermore, certain aspects of the present disclosure can be better understood in accordance with the following examples, which are intended to be non-limiting and are essentially exemplary. Further, it is understood that the compositions described in the examples may not substantially contain any substances not explicitly described.

Examples

[0112] Example 1

[0120] The compatibility of the copper compounds in the paint was evaluated by visual inspection of the dried paint film appearance of a flat wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1). To obtain a Cu level of 600 ppm, a micronized basic copper carbonate (μBCC containing Cu: Cu) dispersion or an aqueous copper sulfate (CuSO4) solution (for the 5 wt% solution, 2 grams of soluble CuSO4 was dissolved in 38 g of water) was added to the flat wall paint. The test paint was mixed at 1500 rpm for 10 minutes and then equilibrated overnight. The test paint was applied onto a sealed Leneta chart to obtain a wet film thickness of 5 mils and then air-dried for 24 hours. The coating appearance was visually inspected for defects such as particles formed due to incompatibility.

[0113]

Table 1

[0114]

Table 2

[0115]

[0121] As shown in Table 2, the water-insoluble μBCC is compatible but the water-soluble CuSO4 is incompatible in this acrylic paint. In the latter case, the soluble copper cations react with acrylic acid in the acrylic latex to form an insoluble copper acrylate compound, which results in the formation of particles in the dried paint film.

[0116] Example 2. Influence of the Color of the Copper Compound

[0122] The effect of copper compounds on the color of the dry coating film was investigated in a matte wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1). 5 grams of an insoluble copper compound was dispersed in a mixture of 44.5 g of water and 0.5 g of Tamol 731A dispersant and then mixed at 1500 rpm for 10 minutes. 2 grams of a soluble copper compound was dissolved in 38 g of water. The resulting dispersion of the insoluble copper compound (10 wt%) and the solution of the soluble copper compound (5 wt%) were added to the paint to obtain Cu levels of 300 and 600 ppm. The test paint was mixed at 1500 rpm for 10 minutes and then equilibrated overnight. The test paint was applied onto a sealed Leneta chart to obtain a wet film thickness of 5 mils and then air-dried for 24 hours. The color of the dry coating film was measured with a BYK SpectroGuide colorimeter, and the color change (ΔE, ΔE’) was calculated as follows.

[0117] - L: Lightness of color (L* = 0 gives black and L* = 100 indicates diffused white; specular white can be even higher); - a: Position between red / magenta and green (a*, negative values indicate green while positive values indicate magenta); - b: Position between yellow and blue (b*, negative values indicate blue and positive values indicate yellow).

[0118] - 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.

[0119]

Table 3

[0120]

[0123] As shown in Table 3, the μBCC dispersion results in less color change than other colored cupric compounds, excluding cupric oxide, at Cu levels of 300 and 600 ppm. Without wishing to be bound by any particular theory, the reduced color change by cupric oxide is thought to possibly be mainly due to the insufficient dispersibility of cupric oxide in the paint.

[0121] Example 3

[0124] The color change of the matte wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1) containing μBCC (green) can be reduced by incorporating iron oxide pigment (red: complementary color) and zinc oxide (ZnO). 10 grams of ZnO was dispersed in a mixture of 29.5 g of water and 0.5 g of Tamol 731A dispersant, and then mixed at 1500 rpm for 10 minutes. μBCC, Colanyl Oxide Red B130, and the above ZnO dispersion (25 wt%) were added to the matte wall paint to obtain the desired levels of Cu, Oxide Red, and ZnO. The test paint was mixed at 1500 rpm for 10 minutes and then equilibrated overnight. The test paint was applied onto a sealed Leneta chart to obtain a 5 mil wet film thickness and then air-dried for 24 hours. The color of the dry paint film was measured by a BYK Spectro Guide colorimeter, and the color change (ΔE, ΔE’) was calculated.

[0122]

Table 4

[0123]

[0125] As shown in Table 4, the color change of the dry paint film containing μBCC is visually perceptible at 1150 ppm of Cu (ΔE and ΔE’ > 2.0). The color change can be reduced to a level where it is not visually perceptible (ΔE and ΔE’ < 2.0) by adding a combination of Colanyl Oxide Red B130 (100 ppm) or Colanyl Oxide Red B130 (50 ppm) and ZnO (2000 ppm).

[0124] Example 4

[0126] The contact time was shortened from 24 hours to 2 hours, and Pseudomonas aeruginosa was added as an additional bacterium. The antibacterial effect of the copper-containing composition in the dry coating film was evaluated using the modified JIS Z2801 method (Antibacterial products - Test for antibacterial activity and efficacy: 2000). Briefly, the μBCC dispersion and an optional ZnO dispersion (25 wt%) were added to a flat wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1) to achieve the desired Cu and ZnO levels, respectively. The paint was applied with a brush onto sterilized plastic filter paper. The filter paper was coated twice on each side, and the resulting coated filter paper was dried under ambient conditions for 3 days. The dried coating was then leached in 10 L of water for 24 hours (changing the water 4 times in the first 8 hours). Each of the inocula (0.4 mL) of three bacterial species: Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), and Pseudomonas aeruginosa (ATCC 15442) was used to inoculate the dry coating film (40 mm × 40 mm) of the test paint to obtain an inoculum concentration of 1.0 - 4.0×10 5 cfm / mL for each bacterium on the dry surface of each test paint. The test paints were incubated at 35 ± 1 °C and 90% relative humidity (RH) for 2 hours. The degree of bacterial contamination of all samples was determined relatively by comparing the viable cell count of the bacteria by the agar plate culture method with that of the blank paint.

[0125]

Table 5

[0126]

[0127] Table 5 shows the antibacterial effect of the copper-containing composition in the dry coating film of the flat paint. When μBCC is used alone, at 1650 ppm of Cu, or when μBCC is used in combination with ZnO, at 825 ppm of Cu and 825 ppm of ZnO, a >3 Log 10 or >99.9% reduction in the number of bacteria is obtained.

[0127] Example 5

[0128] The contact time was shortened from 24 hours to 2 hours, Pseudomonas aeruginosa was added as an additional bacterium, and the inoculum strength was increased to 5.0 - 10.0×10 7 cfm / mL. Then, using the modified JIS Z2801 method (Antibacterial products - Test for antibacterial activity and efficacy: 2000), the antibacterial effect of the copper-containing composition in the dry coating film was evaluated. Briefly, the μBCC dispersion was added to a quat-containing matte wall paint (41.5% solid volume, <50 g / L VOC, 0.52% alkyl (50% C 14 10% C 16 40% C 12 ) dimethylbenzylammonium chloride) to achieve the desired Cu and quat levels respectively. The paint was applied with a brush onto sterilized plastic filter paper. It was applied twice to each side of the filter paper, and the resulting coated filter paper was dried under ambient conditions for 3 days. The dried coating was then leached in 10 L of water for 24 hours (changing the water 4 times in the first 8 hours). Each of the inocula (0.4 mL) of three bacteria: Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), and Pseudomonas aeruginosa (ATCC 15442) was used to inoculate the dry coating film (40 mm × 40 mm) of the test paint to obtain an inoculum concentration of 5.0 - 10.0×10 7 cfm / mL on the dry surface of each test paint. The test paints were incubated at 35 ± 1 °C and 90% RH for 2 hours. The degree of bacterial contamination was determined relatively by comparing the viable cell count of the bacteria by the agar plate culture method with that of the blank paint.

[0128]

[0129] The antibacterial effect of the copper-containing composition in the dry coating film of this matte paint is shown in Table 6, which demonstrates the improvement in efficacy by the addition of μBCC into the quat-containing paint. In particular, for Pseudomonas, when 330 ppm of Cu was combined with 5200 ppm of quat, a further >3 Log 10 or >99.9% reduction in the number of bacteria was obtained.

[0129]

Table 6

[0130] Example 6

[0130] The antibacterial effect of the copper-containing composition in the dry coating film was evaluated using the Provisional EPA Method (<Provisional method for evaluating the effectiveness of antibacterial surface coatings: 10-02-2020>). Briefly, the μBCC dispersion was added to a flat wall paint (38% solids volume, <50 g / L VOC) to achieve the desired Cu level. The paint was applied onto a sterilized steel substrate (2.54 cm (1 inch) × 2.54 cm (1 inch) AISI type 304 stainless steel). The resulting coated substrate was dried at ambient conditions for at least 24 hours. Each of two bacterial inocula: Staphylococcus aureus (ATCC 6538) and Pseudomonas aeruginosa (ATCC 15442) (20 mL each) was used to inoculate the dry coating film of the test paint to obtain each bacterium at 104-105 cfu / carrier on the dry surface of each test paint. The test paint was incubated at 22 °C and 30-40% RH for 2 hours. The degree of bacterial contamination was determined by the number of viable cells relative to the substrate without coating with respect to the antibacterial effect.

[0131]

Table 7

[0132]

[0131] The antibacterial effect of the copper-containing composition in the dry coating film of this flat paint is shown in Table 7. Compared to the blank paint, the addition of μBCC (1670 ppm Cu) achieves a >3 Log 10 or >99.9% reduction in the number of bacteria to meet the EPA criteria for supplemental antibacterial products.

[0133] Example 7

[0132] The antibacterial effect of the copper-containing composition in the dry coating film was evaluated using the Provisional EPA Method (Provisional Method for Evaluating the Efficacy of Antimicrobial Surfaces Coatings: 10-02-2020). Briefly, the μBCC dispersion was added to a matte wall paint (41.5% solid volume, <50 g / L VOC, 0.52% alkyl (50% C 14 , 10% C 16 , 40% C 12 ) dimethylbenzylammonium chloride) to achieve the desired Cu and quat levels, respectively. The paint was applied onto a sterilized steel substrate (2.54 cm (1 inch) × 2.54 cm (1 inch) AISI type 304 stainless steel). The resulting coated substrate was dried at ambient conditions for at least 24 hours. For the claim of one-week residual efficacy, some of the dried coated substrates were further subjected to dry abrasion and chemical abrasion. For dry abrasion, a BYK Gardner-Scrub apparatus was used to perform 10 cycles of dry abrasion on the coated substrate with a Scotch-Brite non-scratching scrub sponge, each of which included 16 single passes. For chemical abrasion, the scrub sponge was immersed in a sodium hypochlorite (2000 ppm NaOCl) solution and an EPA-registered quat-containing Nugen™ MB 5 N-256 (256-fold dilution) bactericide before abrasion. The coated substrate was subjected to 10 cycles of chemical abrasion with the immersed scrub sponge, each of which included 8 single passes. After rinsing and drying to remove the NaOCl and quat, each of two bacterial inocula: Staphylococcus aureus (ATCC 6538) and Pseudomonas aeruginosa (ATCC 15442) (20 mL) was used to inoculate the dry coating film of the test paint to obtain 104 - 105 cfu / carrier of bacteria on the dry surface of each test paint. The test paint was incubated at 22 °C and 30 - 40% RH for 2 hours. The degree of bacterial contamination was determined by the number of viable cells regarding the antibacterial effect relative to the substrate without coating.

[0134]

Table 8

[0135]

[0133] The antibacterial effect of the copper-containing composition in the dry coating film of this matting paint is shown in Table 8, which demonstrates the improvement in effectiveness by the addition of μBCC to the quat-containing paint. In particular, the combination of μBCC (1670 ppm) and quat (5200 ppm) achieves > 3 Log 10 or > 99.9% reduction of both Staphylococcus and Pseudomonas after dry abrasion and NaOCl / quat abrasion to enable a 1-week residual claim according to EPA standards.

[0136] Example 8

[0134] The antifungal effect of the copper-containing composition in the dry coating film was evaluated using the ASTM method (standard test method for resistance to mold growth on the surface of interior coatings in an environmental chamber). Briefly, μBCC dispersion and optional quat (quaternary ammonium compound) were added to a matting wall paint (50% PVC, 35% solid volume, 45 g / L VOC, Table 1) to the respective target Cu and quat levels. The coating was applied twice to both sides and all edges of a wooden panel (leave for 1 day between coatings). The resulting coated panels were dried at 23 ± 2 °C and 50 ± 5% relative humidity for 4 days. Greenhouse soil was inoculated with Aspergillus niger (ATCC 6275), Aureobasidium pullulans (ATCC 9348), and Penicillium citrinum (ATCC 9849). Inside the environmental chamber, the dried coated panels were hung vertically, approximately 7.62 cm (3 inches) above the surface of the inoculated soil at the bottom, with sufficient spacing to allow free air circulation and prevent contact between the panels or with the wall surface. The coated panels were exposed in the environmental chamber at 32.5 ± 1 °C and 95 ± 3% relative humidity for 4 weeks. The degree of fungal contamination was evaluated using the evaluation scale in Table 9.

[0137]

Table 9

[0138]

[0135] Table 10 shows the antifungal effects of the copper-containing additives in the dry coating film of this matte wall paint. μBCC passes the test at 333 ppm of Cu but fails at the 167 ppm Cu level, while the two quats fail the test at the 2000 ppm level. The combination of μBCC (167 ppm of Cu) and quat (2000 ppm) passes the test, while each individual component fails the test at these levels.

[0139]

Table 10

[0140]

[0136] Those skilled in the art may make these and other modifications and changes to the present invention without departing from the spirit and scope of the present invention as more particularly set forth in the appended claims. Furthermore, it should be understood that aspects of various embodiments may be exchanged, both in whole or in part. Furthermore, those skilled in the art will recognize that the foregoing description is by way of example only and is not intended to limit the present invention as further described in such appended claims.

Claims

1. a latex binder; an insoluble cupric compound; a complementary color pigment and a polymer emulsion composition comprising: the polymer emulsion composition, wherein the insoluble cupric compound is present in the polymer emulsion composition in an amount of less than about 4000 ppm Cu.

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

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, dibromoanthrone, 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 compound in an amount of about 5000 ppm or less.

7. The polymer emulsion composition according to any one of claims 1 to 6, wherein the insoluble cupric compound is present in the polymer emulsion composition in an amount of 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 cupric compound comprises micronized insoluble cupric compound particles, and 50% or more of the micronized insoluble cupric 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, pyrithione, triazine, haloalkylnil, hydantoin, and urea.

11. The polymer emulsion composition according to claim 9, wherein the biocide comprises one or more of dimethylbenzylammonium 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 biocide is present in the polymer emulsion composition in an amount of about 50 ppm of Cu to about 5500 ppm of Cu.

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

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

15. A latex paint composition comprising the polymer emulsion composition according to claim 1.

16. An insoluble divalent copper compound; A complementary pigment An antibacterial agent composition comprising: The antibacterial agent composition, wherein the insoluble divalent copper compound is present in the polymer composition in an amount of less than about 4000 ppm of Cu.

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