US 2011 0097.422A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0097.422 A1 Lopes (43) Pub. Date: Apr. 28, 2011

(54) CLEANING, DISINFECTING AND AOIP3/00 (2006.01) MICROBCIDAL COMPOSITIONS AOIN 4L/04 (2006.01) AOIN 37/10 (2006.01) (76) Inventor: John Alex Lopes, Troy, MI (US) AOIN 37/06 (2006.01) (21) Appl. No.: 12/912,171 (52) U.S. Cl...... 424/637; 514/576; 514/568: 514/557 (22) Filed: Oct. 26, 2010 Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 61/279,726, filed on Oct. A microbicidal disinfecting composition and a method of 26, 2009. preparing the same include the use of an acidifying agent that Publication Classificati comprises at least one of an alkali metal bisulfate, ammonium ublication Classification bisulfate, or a combination thereof. The composition has (51) Int. Cl. broad-spectrum microbicidal properties and does not demon AOIN 59/20 (2006.01) strate cloudiness or precipitation when prepared, diluted, or AOIP I/00 (2006.01) otherwise exposed to hard water. US 2011/0097.422 A1 Apr. 28, 2011

CLEANING, DISINFECTING AND bicidal disinfecting composition. These bisulfates help form MICROBCIDAL COMPOSITIONS an economical, generally non-hazardous, and stable micro bicidal disinfecting composition for use in the food process CROSS-REFERENCE TO RELATED ing, healthcare, personal care, and agricultural industries, to APPLICATION name but a few. The microbicidal disinfecting composition 0001. This application claims the benefit of U.S. Provi may be prepared in the form of a powder, a liquid solution, a sional Application No. 61/279,726 filed Oct. 26, 2009. The gel, a foam, a fog, a mist or as on a wipe. disclosure of the above application is incorporated herein by 0007. A low concentration of the acidifying agent can provide the desired acidity for a wide variety of antimicrobial reference. agents without inducing cloudiness or precipitation when TECHNICAL FIELD exposed to hard water. This dual-functionality of the acidify ing agent may provide a number of economic and product 0002 The technical field of this disclosure generally application advantages. The use of an alkali metal bisulfate relates to microbicidal disinfecting compositions and meth and/or ammonium bisulfate as all or part of the acidifying ods of their preparation. agent, for example, allows for more concentrated microbi cidal disinfecting compositions to be prepared. The presence BACKGROUND of additional chemicals to inhibit cloudiness and precipitation 0003 Microbicidal disinfecting compositions that include may not be needed due to the hardwater tolerance of the alkali one or more microorganism-destroying antimicrobial agents metal bisulfate and ammonium bisulfate. The ability to as an active ingredient are used in a robust array of industrial, achieve high antimicrobial agent concentrations can reduce personal, and agricultural settings. The lethal effect of many storage and transportation costs. As another example, the antimicrobial agents towards microorganisms is generally hazards associated with handling, storing, and transporting enhanced at acidic pH levels. For this reason, the pH of microbicidal disinfecting compositions—both concentrated common antimicrobial agents is typically adjusted downward and ready-for-use—made with corrosive mineral acids can be by an acidifying agent in the preparation of a microbicidal avoided. Alkali metal bisulfates and ammonium bisulfate also disinfecting composition. Anionic Surfactants such as esters cost less than organic acid and some mineral acid acidifying of alkyl and aryl Sulfates and Sulfonates, for example, are agents. This cost difference in conjunction with the low con often combined with mineral acids and/or organic acids to centration effectiveness of the acidifying agent may translate achieve a level of acidity conducive to acceptable microbi into raw material and/or production savings. cidal activity. Mineral acids Such a phosphoric acid, Sulfuric 0008. The acidifying agent may, in one embodiment, com acid, and hydrochloric acid, for example, are often used to prise at least one of sodium bisulfate, potassium bisulfate, adjust the pH of alkyl and arylsulfonated esters to form liquid ammonium bisulfate, or combinations thereof. Each of these microbicidal disinfecting compositions. Organic acids Such bisulfates is available in food grade and technical grade. A as citric acid and lactic acid, for example, are often used to food grade quality may be used when the microbicidal disin adjust the pH of alkyl and aryl sulfated or sulfonated esters fecting composition is meant to disinfect food contact Sur and to form powder or liquid microbicidal disinfecting com faces, or be included in an animal or public health product. A positions. technical grade quality may be used for other appropriate 0004. A microbicidal disinfecting composition prepared purposes. The acidifying agent may be employed with a num with mineral and/or organic acids as the acidifying agent, ber of antimicrobial agents including anionic, cationic, and however, has a tendency become cloudy and show precipitate nonionic Surfactants. A small sampling of exemplary antimi formation in hard water. This problem is often combated by crobial agents include sodium dodecyl Sulfate, sodium dio the addition of chemicals to prevent cloudiness and precipi ctyl SulfoSuccinate, Sodium decyl lactylate, sodium dodecyl tate formation—likely by decreasing the critical micelle con benzene Sulfonate, and a quaternary ammonium compound. centration. But the inclusion of additional chemicals into the Other agents may also be present in the microbicidal disin microbicidal disinfecting composition limits the extent to fecting composition including a fungicidal agent, a preserva which the antimicrobial agent may be concentrated. The reli tive, a flavoring agent, a coloring agent, a freeze-thaw modi ance on organic acid acidifying agents may further impact fying agent, or a sequestering agent. The addition of a this physical constraint. These acids are typically weak acids fungicidal agent, such as a copper or Zinc salt, can afford the and, as such, require larger quantities to achieve the desired microbicidal disinfecting composition with antifungal and acidic pH level when compared to mineral acids. algicidal characteristics. 0005. The use of organic acids and/or mineral acids as the 0009. Other exemplary and more detailed embodiments of primary acidifying agent in the preparation of a microbicidal the invention will become apparent from the detailed descrip disinfecting composition can complicate handling, storage, tion that follows. and transportation concerns. The limits imposed on the extent of antimicrobial agent concentration by these acidifying DETAILED DESCRIPTION agents and, as needed, additional chemicals to alleviate tur 0010. A microbicidal disinfecting composition may bidity, can impact storage and transportation efficiencies. include an antimicrobial agent and an acidifying agent. The Certain mineral acids are also corrosive and may require acidifying agent may include at least one of an alkali metal special handling and disposal procedures. bisulfate or ammonium bisulfate and may be present in an amount effective to provide the microbicidal disinfecting SUMMARY composition with an acidity conducive to the desired micro 0006 An acidifying agent that includes at least one of an bicidal activity of the antimicrobial agent. The pH value of the alkali metal bisulfate or ammonium bisulfate, both of which microbicidal disinfecting composition may range from very exhibit high aqueous solubility, may be used to form a micro low up to 7.0 depending on the current state of the composi US 2011/0097.422 A1 Apr. 28, 2011

tion or its intended use (highly concentrated for shipping/ isethionate, Sulfate, Sulfonate, Sulfoacetate, SulfoSuccinate, storage, less concentrated for end-use application, etc.). The lactate, lactylate, phosphate, phosphonate, or mixtures amount of the acidifying agent needed to achieve this pH thereof. value target can vary quit considerably and may range from 0015. A more specific class ofanionic surfactants that may about 0.1 wt.% to about 99.90 wt.%. The microbicidal be used include a free acid or a salt of (1) a C6-C18 alkyl disinfecting composition may also include, if desired, at least sulfate, (2) a C6-C18 alkenylsulfate, (3) a C6-C18 alkyl ether one of a fungicidal agent, a preservative, a flavoring agent, a sulfate, (4) a C6-C18 alkenyl ether sulfate, (5) a C8-C16 alkyl coloring agent, a freeze-thaw modifying agent, or a seques diphenyl ether disulfonate, (6) a C4-C18 fatty acid isethion tering agent. ate, (7) a C6-C18 alkyl sulfonate, (8) a C6-C18 alkenyl sul 0011. The alkali metal bisulfate and/or ammonium bisul fonate, (9) a dialkyl sulfosuccinate in which the alkyl group fate may, at low concentrations, provide the microbicidal independently contains from 6 to 18 carbon atoms, (10) a disinfecting composition with the acidity needed to Support dialkenyl SulfoSuccinate in which the alkenyl group indepen the effectiveness of the antimicrobial agent. The presence of dently contains from 6 to 18 carbon atoms, (11) a C6-C18 hardwater in the microbicidal disinfecting composition or the alkylbenzene Sulfonate, (12) a naphthalene Sulfonate, (13) an later addition of hard water will not promote turbidity or alkyl naphthalene Sulfonate in which the alkyl group inde precipitate formation. The use of an alkali metal bisulfate pendently contains from 1 to 6 carbon atoms, (14) a mono and/or ammonium bisulfate generally contributes to the for (n-alkyl)acyl ester of a C2-C4 hydroxylated monocarboxylic mation of a clear Solution when the microbicidal disinfecting acid in which the alkyl group independently contains from 6 composition is in a liquid aqueous state. The low concentra to 18 carbon atoms, (15) a mono (n-alkenyl) acyl ester of a tion effacacy of these bisulfates and their hardwater tolerance C2-C4 hydroxylated monocarboxylic acid in which the alkyl can simplify, and reduce the costs associated with, the prepa group independently contains from 6 to 18 carbonatoms, (16) ration of the microbicidal disinfecting composition as com a mono (n-alkyl) acyl ester of a C2-C4 hydroxylated dicar pared to other similar compositions that use mineral acids boxylic acid in which the alkyl group independently contains and/or organic acids as the primary acidifying agent. from 6 to 18 carbon atoms, (17) a mono (n-alkenyl) acyl ester 0012. A method of preparing the microbicidal disinfecting of a C2-C4 hydroxylated dicarboxylic acid in which the alk composition may include adding the acidifying agent to a enyl group independently contains from 6 to 18 carbonatoms, liquid medium that includes an antimicrobial agent. The (18) a mono (n-alkyl)alkyl ester of a C2-C4-dicarboxylic acid acidifying agent may be added in an amount effective to in which the alkyl group independently contains from 6 to 18 considerably lower the pH value of the liquid medium to form carbonatoms, (19) a mono (n-alkenyl)alkyl ester of a C2-C4 an acidic concentrate. The acidic concentrate of the microbi dicarboxylic acid in which the alkenyl group independently cidal disinfecting composition may then be shipped or stored, contains from 6 to 18 carbon atoms, and (20) a C4-C18 fatty either in liquid or powder form. The fact that additional alcohol Sulfoacetate. chemicals do not have to be included in the acidic concentrate 0016 Some preferred exemplary anionic surfactants that to prevent turbidity or precipitation when the microbicidal may be used as the antimicrobial agent include at least one of disinfecting composition is exposed to hard water increases a sulfated alkyl ester, a sulfated aryl ester, a sulfonated alkyl the extent to which the antimicrobial agent may be concen ester, or a sulfonated aryl ester. Some specific examples of trated. Then, at Some later time, the acidic concentrate may be Such anionic Surfactants are sodium dodecyl sulfate, sodium diluted with water to form some intermediate microbial dis dioctyl sulfo Succinate, Sodium decyl lactylate, and Sodium infecting composition or an end-use microbicidal disinfect dodecylbenzene sulfonate. ing composition. 0017. A cationic surfactant that may be employed as the 0013 The alkali metal bisulfate may be sodium bisulfate, antimicrobial agent may comprise, for example, a quaternary potassium bisulfate, or a combination of sodium bisulfate and ammonium compound. Other cationic and nonionic Surfac potassium bisulfate. Each of these alkali metal bisulfates as tants known to skilled artisans may also be used as the anti well as ammonium bisulfate is available in food grade and microbial agent. technical grade. The selection of which grade to select for use 0018. The fungicidal agent may be any material that in preparing the microbicidal disinfecting composition exhibits fungicidal activity Such as copper salts and Zinc salts. depends on the particular use for which the composition is Some specific fungicidal agents that may be included in the intended, as understood by skilled artisans. The antimicrobial microbicidal disinfecting composition include copper Sul agent may be an anionic Surfactant, a cationic Surfactant, a fate, cupric sulfate, and Zinc sulfate. These metal salts can nonionic Surfactant, or any other material that exhibits micro provide the microbicidal disinfecting composition with anti bicidal activity in acidic conditions. The antimicrobial agent fungal and algicidal characteristics in the presence of the may be present in an amount ranging from about 0.0001 wt.% acidifying agent. The fungicidal agent may be present in an to about 50 wt.%. amount ranging up to about 10 wt.%. 0014. An anionic surfactant that may be employed as the 0019. The preservative, flavoring agent, coloring agent, antimicrobial agent may comprise a C4-C18 acid or saltcom freeze-thaw modifying agent, and sequestering agent may be pound selected from the group consisting of: (1) an alkyl any material known to skilled artisans. The preservative may, carboxylate, isethionate, Sulfate, Sulfonate, Sulfoacetate, Sul for example, be a free acid, salt, or ester form of at least one foSuccinate, lactate, lactylate, phosphate, phosphonate, or of benzoic acid, Sorbic acid, ascorbic acid, or erythorbic acid. mixtures thereof (2) analkenyl-carboxylate, isethionate, Sul The flavoring agent may be any known agent that imparts a fate, Sulfonate, Sulfoacetate, SulfoSuccinate, lactate, lactylate, specific flavor (meat flavor, seafood flavor, fruity flavor, phosphate, phosphonate, or mixtures thereof; (3) an alkylben herbal flavor, etc.). These materials are generally commer Zene-carboxylate, isethionate, Sulfate, Sulfonate, Sulfoac cially available. The coloring agent may be any coloring etate, Sulfo Succinate, lactate, lactylate, phosphate, phospho agent suitable for the intended use of the microbicidal disin nate, or mixtures thereof, or (4) a naphthalene-carboxylate, fecting composition. The freeze-thaw agent may be any US 2011/0097.422 A1 Apr. 28, 2011 known organic or inorganic material that can be used to increase or decrease the freezing point of the microbicidal -continued disinfecting composition. Some specific examples of freeze thaw agents include an alcohol, an inorganic salt, and urea. Ingredients % Wiw The sequestering agent may be any material that binds to Lactic acid 33.33% metal or toxic compounds. Specific examples of Suitable Water 33.33% sequestering agents include, for example, Sodium acid pyro phosphate, citric acid, isopropyl citrate, and calcium diac Total Wt 100.00% etate. Each of the preservative, flavoring agent, coloring pH of 0.2% 2.54 agent, freeze-thaw modifying agent, and sequestering agent may be included in the microbicidal disinfecting composition in an amount that independently ranges from about 0.0001 Example 4 wt.% to about 10 wt.%. Composition D EXAMPLES 0024 0020. The Examples in Table 1 detail the preparation of several exemplary microbicidal disinfecting compositions. Ananionic Surfactant was used as the antimicrobial agent and Sodium bisulfate was used as the acidifying agent. The com Ingredients % ww positions were diluted with water for determining their Copper sulfate 10.00% microbicidal efficacy. Sodium bisulfate 90.00% Example 1 Total Wt 100.00% pH of 0.1% 2.54 Composition A 0021 Example 5 Composition E Ingredients % Wiw Sodium dodecylbenzene Sulfonate 33.33% 0025 Sodium bisulfate 66.67%

Total Wt 100.00% pH of 0.1% 2.54 Ingredients % Wiw Copper sulfate O.98% Sodium dodecylbenzene sulfonate 2.44% Example 2 Sodium bisulfate 96.59% Composition B Total Wt 100.00% pH of 0.1% 2.54 0022 0026. The microbicidal efficacy of the microbicidal disin fecting compositions of Examples 1-3 (compositions A-C) Ingredients % Wiw were evaluated with 50 ppm of hypochlorite as a control Sodium dodecylbenzene Sulfonate 26.67% against Staphylococcus aureus and Escherichia coli by the Citric acid 20.00% modified detergent and germicidal sanitizer test of the A.O. Benzoic acid 13.33% A.C. (Lopes, 1986). The results are shown in Table 1. Sodium bisulfate 40.00%

Total Wt 100.00% TABLE 1 pH of 0.1% 2.54 Sanitizing % Kill Composition % Wiw Staph. aureus E. coi Example 3 Example 1 O.10 >99.999 >99.999 Example 2 O.10 >99.999 >99.999 Composition C Example 3 O.20 >99.999 >99.999 Hypochlorite 50 ppm >99.999 >99.999 0023 Control

0027. The microbicidal efficacy of the microbicidal disin Ingredients % Wiw fecting composition of Example 1 (composition A) was fur Sodium dodecylbenzene Sulfonate 13.33% ther tested and proven effective against Salmonella on con Sodium bisulfate 20.00% taminated tomatoes. When Salmonella-contaminated tomatoes were treated with 0.1% solution of composition A, US 2011/0097.422 A1 Apr. 28, 2011 the viable bacterial population was reduced by 2.31 logo food grade freeze-thaw modifying agent, a food grade CFU as compared with 2.11 ogo CFU with 150 ppm of sequestering agent, or combinations thereof. hypochlorite. 13. The microbicidal disinfecting composition of claim 1, What is claimed is: further comprising: 1. A microbicidal disinfecting composition, comprising: a fungicidal agent comprising at least one of copper Sulfate, cupric Sulfate, Zinc sulfate, or combinations thereof; an antimicrobial agent; and a food grade preservative comprising a salt, free acid, or an amount of an acidifying agent effective to provide the ester of at least one of benzoic acid, Sorbic acid, ascorbic microbicidal disinfecting composition with a pH value acid, erythorbic acid, or combinations thereof; of 7.0 or below, wherein the acidifying agent comprises a sequestering agent comprising at least one of Sodium at least one of an alkali metal bisulfate, ammonium pyrophosphate, citric acid, isopropyl citrate, calcium bisulfate, or a combination thereof. diacetate, or combinations thereof. 2. The microbicidal disinfecting composition of claim 1, 14. A microbicidal disinfecting composition, comprising: wherein the alkali metal bisulfate comprises at least one of an antimicrobial agent in an amount ranging from about Sodium bisulfate, potassium bisulfate, or a combination 0.0001 wt.% to about 50 wt.%: thereof. a fungicidal agent in an amount up to about 10 wt.%; and 3. The microbicidal disinfecting composition of claim 1, an amount of sodium bisulfate, potassium bisulfate, wherein the antimicrobial agent is present in an amount that ammonium bisulfate, or combinations thereof effective ranges from about 0.0001 wt.% to about 50 wt.% and the to provide the microbicidal disinfecting composition amount of the acidifying agent ranges from about 0.1 wt.% to with a pH value of 7.0 or below. about 99.90 wt.%. 15. The microbicidal disinfecting composition of claim 14, 4. The microbicidal disinfecting composition of claim 1, wherein the antimicrobial agent comprises at least one of a wherein the antimicrobial agent comprises an anionic Surfac sulfated alkyl ester, a sulfated aryl ester, a sulfonated alkyl tant. ester, or a sulfonated aryl ester, and wherein the fungicidal 5. The microbicidal disinfecting composition of claim 4, agent comprises at least one of a copper salt, a Zinc salt, or wherein the anionic surfactant comprises at least one C4-C18 combinations thereof. acid or salt compound selected from the group consisting of 16. The microbicidal disinfecting composition of claim 15, (1) an alkyl-carboxylate, isethionate, Sulfate, Sulfonate, Sul wherein the antimicrobial agent comprises at least one of foacetate, Sulfo Succinate, lactate, lactylate, phosphate, phos Sodium dodecyl Sulfate, sodium dioctyl SulfoSuccinate, phonate, or mixtures thereof; (2) an alkenyl-carboxylate, sodium decyllactylate, sodium dodecylbenzene sulfonate, or isethionate, Sulfate, Sulfonate, Sulfoacetate, SulfoSuccinate, combinations thereof. lactate, lactylate, phosphate, phosphonate, or mixtures 17. The microbicidal disinfecting composition of claim 15, thereof; (3) an alkylbenzene-carboxylate, isethionate, sulfate, wherein the fungicidal agent comprises at least one of copper Sulfonate, Sulfoacetate, Sulfo Succinate, lactate, lactylate, Sulfate, cupric Sulfate, Zinc sulfate, or combinations thereof. phosphate, phosphonate, or mixtures thereof (4) a naphtha 18. A method for preparing a microbicidal disinfecting lene-carboxylate, isethionate, Sulfate, Sulfonate, Sulfoacetate, composition, the method comprising: SulfoSuccinate, lactate, lactylate, phosphate, phosphonate, or providing a liquid medium that comprises an antimicrobial mixtures thereof; or (5) a combination of any of the C4-C18 agent and having a pH value; organic acid or salt compounds of (1)–(4). adding to the liquid medium an amount of an acidifying 6. The microbicidal disinfecting composition of claim 5, agent effective to lower the pH value of the liquid wherein the anionic Surfactant comprises at least one of a medium to form an acidic concentrate of the microbi sulfated alkyl ester, a sulfated aryl ester, a sulfonated alkyl cidal disinfecting composition, wherein the acidifying ester, or a Sulfonated aryl ester, or combinations thereof. agent comprises at least one of an alkali metal bisulfate, 7. The microbicidal disinfecting composition of claim 6, ammonium bisulfate, or a combination thereof, and wherein the anionic Surfactant comprises at least one of diluting the acidic concentrate of the microbicidal disin Sodium dodecyl Sulfate, sodium dioctyl SulfoSuccinate, fecting composition with water in an amount that does Sodium decyllactylate, sodium dodecylbenzene Sulfonate, or not raise the pH value above 7.0 to form the microbicidal combinations thereof. disinfecting composition. 8. The microbicidal disinfecting composition of claim 1, 19. The method of claim 18, wherein the alkali metal wherein the antimicrobial agent comprises a cationic Surfac bisulfate comprises sodium bisulfate, potassium bisulfate, or tant. a combination thereof. 9. The microbicidal disinfecting composition of claim 8. 20. The method of claim 19, wherein providing a liquid wherein the cationic Surfactant comprises a quaternary medium comprises: ammonium compound. providing an aqueous solution that comprises the antimi 10. The microbicidal disinfecting composition of claim 1, crobial agent and a fungicidal agent, wherein the anti further comprising a fungicidal agent in an amount up to microbial agent comprises at least one of sodium dode about 10 wt.%. cyl Sulfate, sodium dioctyl sulfo Succinate, Sodium decyl 11. The microbicidal disinfecting composition of claim 10, lactylate, Sodium dodecyl benzene Sulfonate, or combi wherein the fungicidal agent comprises at least one of copper nations thereof, and wherein the fungicidal agent com Sulfate, cupric sulfate, Zinc sulfate, or combinations thereof. prises at least one of copper Sulfate, cupric sulfate, Zinc 12. The microbicidal disinfecting composition of claim 1, sulfate, or combinations thereof. further comprising at least one of a food grade preservative, a food grade flavoring agent, a food grade coloring agent, a c c c c c