Compositions with residual antimicrobial activity

Abstract

The present disclosure is directed to a germicide composition comprising a quaternary ammonium biocide in combination with a polyethyleneimine film former. The germicide composition forms a film on a surface that is abrasion resistant and provides antimicrobial activity over an extended period of time.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to the benefit of U.S. Provisional Application No. 63 / 325,823, filed March 31, 2022, the entire contents of which are expressly incorporated by reference herein. [Background technology]

[0002] Pathogenic organisms, such as bacteria, fungi, and viruses, continue to cause infectious diseases in humans as well as livestock and pets. Antiseptic formulations have been developed over the last few decades to reduce or destroy pathogenic organisms, thus lowering infection rates. Since any hard surface can be contaminated, particular focus has been directed to hard surfaces, including floors, walls, countertops, windows, window sills, sinks, faucets, waste containers, electrical appliances, and cabinet surfaces. Although antiseptics have been developed to treat hard surfaces for use in hospitals, nursing homes, schools, and homes, existing antiseptic compositions do not provide sufficient residual antimicrobial activity between cleanings, and therefore sanitization must be repeated or the antiseptic composition must be reapplied. That is, the effectiveness of many antiseptic compositions decreases rapidly after application. In particular, existing antiseptic compositions cannot remain on a surface for any period of time to provide sustained effectiveness, since the antiseptic composition tends to rapidly decompose, evaporate, or be physically removed from the surface by repeated touching or wiping with a cloth. As a result, if the surface is recontaminated, the germicide composition must be reapplied to kill the newly deposited microorganisms. Thus, many existing germicide compositions are unable to maintain their antimicrobial properties on high wear surfaces and are easily removed by friction or frequent contact.

[0003] For example, a particular class of antimicrobial compositions includes quaternary ammonium compounds, also known as "quats," as microbial control agents. The use of quats as biocides is well known, but germicide compositions containing quaternary ammonium compounds fail to provide long-term antimicrobial activity. Furthermore, most cationic formulations, such as quat-based wipe germicide formulations, fail to provide long-term antimicrobial protection for high-touch or high-abrasion surfaces and leave significant residues that are particularly noticeable on smooth, shiny surfaces.

[0004]

[0004] Efforts to create germicidal compositions with long-lasting antimicrobial activity have included embedding germicidal metals into various surfaces. Unfortunately, such compositions are expensive and require concentrations above regulatory limits for many areas to provide sufficient antimicrobial activity. Summary of the Invention [Problem to be solved by the invention]

[0005]

[0005] It would therefore be an advantage to provide a germicide composition that exhibits good antimicrobial activity over an extended period of time. It would also be an advantage to provide a germicide composition that provides a period of antimicrobial activity, even on surfaces that are subject to high contact or friction. It would also be an advantage to provide one or more of the above advantages using a germicide composition that is substantially free of germicidal metals. [Means for solving the problem]

[0006]

[0006] The present disclosure is generally directed to a disinfectant composition that provides hard surfaces with residual antimicrobial activity. The disinfectant composition includes a quaternary ammonium biocide and a film former, the film former including polyethyleneimine. Further, the composition provides a log reduction of about 2 or greater against S. aureus after abrasion resistance testing according to EPA 01-1A.

[0007] In one embodiment, the disinfectant composition has a basic pH, for example, about 9 or more, or even about 9.5 or more. Additionally, in one embodiment, the disinfectant composition can include a nonionic surfactant, a strengthening agent, which in one embodiment can be a strengthening surfactant, or a combination thereof. In yet another embodiment, the strengthening agent is a C12-C24 fatty alkyl quaternary ammonium compound or a silane quaternary ammonium, different from the quaternary ammonium biocide. Additionally or alternatively, in one embodiment, the strengthening agent is a cetyltrimethylammonium compound, a lauryltrimethylammonium compound, a stearyldimethylbenzylammonium compound, a soyatrimethylammonium compound, a behentrimethylammonium compound, a dimethylditallow quaternary ammonium compound, or a combination thereof. In one embodiment, the non-ionic surfactant is an alkyl polyglucoside, an alcohol polyglycol ether, an amine ethoxylate, a fatty alcohol alkoxylate, a polyethylene glycol (PEG), an alcohol PEG-ether, a fatty acid ethoxylate, a glycerol ester, or a combination thereof, and in one embodiment is an alkyl polyglucoside.

[0008]

[0008] In yet another embodiment, the quaternary ammonium biocide is a dialkyldimethylammonium compound, an alkyldimethylbenzylammonium compound, an alkyltrimethylammonium compound, or a combination thereof. For example, in one embodiment, the quaternary ammonium biocide is a C8 dialkyldimethylammonium compound, a C10 dialkyldimethylammonium compound, a C12-C16 alkyldimethylbenzylammonium compound, a C8-C18 alkyltrimethylammonium compound, or a combination thereof.

[0009]

[0009] In yet another embodiment, the germicide composition can be a ready-to-use composition. In one such embodiment, the quaternary ammonium biocide can be present in the ready-to-use composition in an amount of about 0.01% to about 5% by weight, such as about 0.05% to about 4% by weight, such as about 0.1 to about 3% by weight, or even about 0.15% to about 2% by weight, based on the weight of the composition. Additionally or alternatively, the film-forming agent is present in the ready-to-use composition in an amount of about 0.1 to about 10% by weight, such as about 0.5% to about 9.5% by weight, such as about 1% to about 9% by weight.

[0010]

[0010] Furthermore, in one embodiment, the disinfectant composition can be in a concentrated form. In one such embodiment, the quaternary ammonium biocide is present in the concentrated composition in an amount of about 0.1% to about 30% by weight, for example, about 0.5% to about 25% by weight, for example, about 1 to about 20% by weight, or even about 1.5% to about 15% by weight, based on the weight of the composition. Additionally or alternatively, in one embodiment, the film-forming agent is present in the concentrated composition in an amount of 0.1% to about 50% by weight, for example, about 0.5% to about 40% by weight, for example, about 1 to about 35% by weight, or even about 1.5% to about 32.5% by weight, based on the weight of the composition.

[0011] In one embodiment, the quaternary ammonium biocide, the enhancer, or both, can be a quaternary ammonium carbonate, a quaternary ammonium bicarbonate, a quaternary ammonium halide, a quaternary ammonium phosphate, a quaternary ammonium sulfate, or a combination thereof.

[0012]

[0012] Furthermore, in one embodiment, the disinfectant composition can include a chelating agent, a second surfactant, a pH adjuster, a drying agent, an aqueous carrier, or a combination thereof. In a particular embodiment, the chelating agent is a C1-C10 carboxylic acid, preferably the carboxylic acid is citric acid, sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, or a mixture thereof. Furthermore, in one embodiment, the second surfactant is a zwitterionic surfactant, which in one embodiment can be cocamidopropyl betaine, cocamidopropyl hydroxyl sultaine, or a combination thereof.

[0013] Additionally or alternatively, in one embodiment, the germicide composition does not include any film-forming agents other than polyethyleneimine.

[0014] The present disclosure is also generally directed to a method of providing residual sanitization to a hard surface. The method includes applying a germicidal composition to a hard surface and subjecting the hard surface to a rub cycle using a GardCo Washability and Wear Tester set between 2.25 and 2.5, where the composition provides about a 2 or greater log reduction against Staphylococcus aureus after being subjected to at least 2 seconds of rub. Additionally, the germicidal composition includes a quaternary ammonium biocide and a film former including polyethyleneimine.

[0014]

[0015] In one aspect, the method exhibits a log reduction after subjecting the hard surface to 2 to 12 abrasion cycles of about 2 to about 5 seconds. Additionally, in one aspect, the composition further provides a log reduction of about 2 or greater against K. aerogenes.

[0015]

[0016] Additionally or alternatively, in one embodiment, the germicide composition applied to the surface further has a pH greater than about 9, or even greater than about 9.5. In another embodiment, the germicide composition applied to the surface further comprises a non-ionic surfactant. In one embodiment, the hard surface to which the germicide composition is applied is a non-porous and / or inanimate surface.

[0016]

[0017] In a further embodiment, the germicide composition applied to the surface further comprises a potentiator, which in one embodiment is a C12-C24 aliphatic alkyl quaternary ammonium compound or a silane quaternary ammonium, different from the quaternary ammonium biocide. In one such embodiment, the potentiator is a cetyltrimethylammonium compound, a lauryltrimethylammonium compound, a stearyldimethylbenzylammonium compound, a soyatrimethylammonium compound, a behentrimethylammonium compound, a dimethylditarod quaternary ammonium compound, or a combination thereof. Further, in one embodiment, the quaternary ammonium biocide included in the germicide composition of the present method is a dialkyldimethylammonium compound, an alkyldimethylbenzylammonium compound, an alkyltrimethylammonium compound, or a combination thereof. In one such embodiment, the quaternary ammonium biocide is a C8 dialkyldimethylammonium compound, a C10 dialkyldimethylammonium compound, a C12-C16 alkyldimethylbenzylammonium compound, a C8-C18 alkyltrimethylammonium compound, or a combination thereof.

[0017]

[0018] Other features and aspects of the present disclosure are discussed in more detail below, and it should be understood that any one or more of the above aspects can be utilized alone or in combination with any of the other aspects noted above or discussed elsewhere herein. definition

[0019] As used herein, the terms "about," "approximately," or "generally," when used to modify a value, indicate that the value can be up or down by 10% and remain within the scope of the disclosed embodiments, e.g., 7.5%, e.g., 5%, e.g., 4%, e.g., 3%, e.g., 2%, e.g., 1%, or any range or value therebetween. Furthermore, the term "substantially free," when used to describe the amount of a substance in a material, is not limited to total or complete absence, but can correspond to the absence of any appreciable or detectable amount of the recited substance in the material. Thus, for example, a material is "substantially free" of a substance if the amount of the substance in the material is less than the precision of an art-accepted device or test for measuring the amount of the substance in the material. In certain exemplary embodiments, a material can be "substantially free" of a substance if the amount of the substance within the material is less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1% by weight of the material.

[0018]

[0020] Quaternary ammonium compounds, also known as "quats", typically contain at least one quaternary ammonium cation with a suitable anion. Quats generally have the general formula (1):

[0019] [ka]

[0020]

[0021] The R1, R2, R3 and R4 groups can vary within wide limits, and examples of quaternary ammonium compounds with antibacterial properties are well known to those skilled in the art. Usually, one or more of R1, R2, R3 and R4 is a lower alkyl, which means that it has 1 to 4 carbon atoms, for example, a methyl, ethyl, propyl or butyl group. In addition, one or more of R1, R2, R3 and R4 is a longer chain alkyl group of 6 to 24 carbon atoms, or a benzyl group. A" is equivalent to a monovalent anion or a polyvalent anion of an inorganic or organic acid. Suitable anions for A" are, in principle, all inorganic or organic anions, in particular halides, for example chloride or bromide, carbonate, bicarbonate, carboxylate, sulfonate, phosphate or mixtures thereof. The carboxylate can be derived from a lower carboxylic acid or a fatty acid.

[0021]

[0022] Alkyl is hereinafter taken to mean in each case an unbranched or branched alkyl group of the specified number of carbons. In particular, it is also taken to mean the homologue mixtures derived from natural sources, such as "cocoalkyl".

[0022]

[0023] Substituted phenyl is in particular a phenyl group having one or more C 1~18 It is understood to mean a phenyl group substituted with alkyl and / or halogen atoms. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023]

[0024] Those skilled in the art will appreciate that the discussion of the present invention is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0025] The present disclosure is generally directed to a composition for disinfecting surfaces that not only delivers fast and effective antimicrobial properties against a broad range of microorganisms, but also provides residual antimicrobial activity over a longer period of time.That is, the present disclosure has surprisingly found that a combination of a quaternary ammonium biocide and a film former comprising polyethyleneimine forms a synergistic composition that not only provides good initial antimicrobial activity against a broad range of microorganisms, but also forms a coating or film on the surface to provide extremely abrasion-resistant and contact-resistant antimicrobial properties over a longer period of time.Among certain advantages, the coating or film formed on the surface is transparent, non-sticky, and relatively invisible.

[0024]

[0026] For example, the present disclosure has surprisingly found that a disinfectant composition according to the present disclosure, even after being subjected to a rub resistance test according to EPA 01-1A, can exhibit a log reduction of about 2 or more, such as a log reduction of about 2.5 or more, such as a log reduction of about 3 or more, such as a log reduction of about 3.5 or more, or any range or value therebetween, against one or more microorganisms, e.g., as discussed in more detail below against Staphylococcus aureus, Klebsiella aerogenes, or a combination thereof. That is, such behavior surprisingly exhibits, for example, after about 2 rub cycles according to EPA 01-1A, about 3 or more rub cycles according to EPA 01-1A, for example, about 4 or more rub cycles, for example, about 5 or more rub cycles, for example, about 6 or more rub cycles, for example, about 7 or more rub cycles, for example, about 8 or more rub cycles, for example, about 9 or more rub cycles, for example, about 10 or more rub cycles, for example, about 11 or more rub cycles, up to about 12 rub cycles, or any range or value therebetween, where each rub cycle lasts from about 2 seconds to about 5 seconds. As is known in the art and discussed in more detail in the Examples below, EPA Protocol 01-1A requires a series of wet and dry rubs and reinoculation of the test substrate, which is extremely difficult to pass. Thus, in accordance with the above, the germicide composition may exhibit the above log reduction on a surface for a period of about 1 hour or more, such as about 2 hours or more, such as about 4 hours or more, such as about 6 hours or more, such as about 12 hours or more, such as about 18 hours or more, even up to about 24 hours. Thus, as noted above, it was surprising that the synergistic composition of this pending claim was able to pass EPA 01-1A while exhibiting excellent antimicrobial activity.

[0025]

[0027] Furthermore, after being subjected to testing according to EPA 01-1A, even if following any one or more of the above cycles or time periods, an amount of the germicide composition (shown in the examples below as percent weight retention) of about 5% by weight or more, such as about 7.5% by weight or more, such as about 8% by weight or more, such as about 10% by weight or more, such as about 12.5% ​​by weight or more, up to about 95% by weight or less, or any range or value therebetween, based on the weight of the film or coating formed by the germicide composition before the rub test, can remain on the surface. Of course, as discussed in more detail below, a greater amount of weight may be removed by wet testing than by dry testing, but the germicide compositions discussed herein still provide superior rub-resistant and contact-resistant coatings even when subjected to repeated wet rub conditions.

[0026]

[0028] Nonetheless, examples of specific microorganisms that may be killed or controlled in accordance with the present disclosure and that may exhibit the above log reductions before or after the friction test include Staphylococcus aureus, Streptococcus pneumoniae, Pseudomonas aeruginosa, Serratia marcescens, Salmonella enteritidis, Neisseria gonorrhoeae, Escherichia coli, Enterococcus hirae, Acinetobacter baumannii, Listeria monocytogenes, Enterobacter gergoviae, Klebsiella pneumoniae, Burkholderia cepacia, and the like. cepacia, Pseudomonas putida, Kocuria rhizophila, Candida albicans, Saccharomyces cerevisiae, Aspergillus brasiliensis, Penicillium funiculosum, Eupenicillium levitum, Bacillus cereus, Bacillus subtilis, Clostridium difficile, Clostridium perfringens, Mycobacterium tuberculosis, Mycobacterium terrae terrae, Mycobacterium avium, Poliovirus, Adenovirus, Norovirus, Vaccinia virusvirus, Influenza virus, Hepatitis B virus, Human Immunodeficiency virus, Human papilloma virus, or a mixture thereof.

[0027]

[0029] Regardless of the microorganism selected, in one embodiment, the quaternary ammonium biocide includes a dialkyldimethylammonium compound, an alkyldimethylbenzylammonium compound, an alkyltrimethylammonium compound, or a combination thereof.

[0028]

[0030] In one embodiment, the dimethyldialkylammonium compound can have between about 8 and about 12 carbon atoms in each of the alkyl groups, such as about 8 to about 10 carbon atoms. Examples of dimethyldialkylammonium compounds include dimethyldioctylammonium compounds, dimethyldidecylammonium compounds, or combinations thereof.

[0029]

[0031] Examples of alkyl dimethyl benzyl ammonium compounds include quaternary ammonium compounds containing an alkyl group having from about 10 to about 18 carbon atoms, such as from about 12 to about 16 carbon atoms. For example, the quaternary ammonium biocide can be a C12 alkyl dimethyl benzyl ammonium compound, a C14 alkyl dimethyl benzyl ammonium compound, a C16 alkyl dimethyl benzyl ammonium compound, or a combination thereof.

[0030]

[0032] Further examples of alkyltrimethylammonium compounds include quaternary ammonium compounds containing an alkyl group having from about 8 to about 18 carbon atoms. For example, the quaternary ammonium biocide can be a C8 alkyltrimethylammonium compound, a C10 alkyltrimethylammonium compound, a C12 alkyltrimethylammonium compound, a C14 alkyltrimethylammonium compound, a C16 alkyltrimethylammonium compound, or combinations thereof.

[0031]

[0033] However, although examples of dialkyldimethylammonium compounds, alkyldimethylbenzylammonium compounds, and alkyltrimethylammonium compounds have been discussed separately, it should be understood that the quaternary ammonium biocide can include more than one specific quaternary ammonium compound, and in one embodiment, includes any combination of the quaternary ammonium compounds listed above.

[0032]

[0034] As discussed in more detail below, the germicide composition according to the present pending claims can be formulated as a concentrated composition or diluted into a ready-to-use composition. When formulated as a concentrated composition, the quaternary ammonium biocide is present in the composition in an amount of about 0.1% to about 30% by weight, based on the weight of the composition, such as about 0.5% to about 25% by weight, based on the weight of the germicide composition, such as about 1 to about 20% by weight, such as about 1.5% to about 15% by weight, or any range or value therebetween. When formulated as a ready-to-use composition, the quaternary ammonium biocide is present in the composition in an amount of about 0.01% to about 5% by weight, based on the weight of the germicide composition, such as about 0.05% to about 4% by weight, based on the weight of the composition, such as about 0.1 to about 3% by weight, such as about 0.15% to about 2% by weight, or any range or value therebetween.

[0033]

[0035] Nevertheless, as mentioned above, the present disclosure has surprisingly found that a germicide composition having good antimicrobial properties and abrasion resistance can be formed by utilizing a quaternary ammonium biocide in combination with a film former including polyethyleneimine. In one aspect, the germicide can include a second film former, such as polyvinyl alcohol, polyvinylpyrrolidone, silane, siloxane, or a combination thereof. However, in one aspect, the synergistic properties of the polyethyleneimine and the quaternary ammonium biocide allow the formation of a germicide composition that is generally free of a second film former(s).

[0034]

[0036] When formulated as a concentrated composition, the film-forming agent is present in the composition in an amount of 0.1% to about 50% by weight, based on the weight of the composition, for example, about 0.5% to about 40% by weight, based on the weight of the fungicide composition, for example, about 1 to about 35% by weight, for example, about 1.5% to about 32.5% by weight, or any range therebetween. When formulated as a ready-to-use composition, the film-forming agent is present in the composition in an amount of about 0.1 to about 10% by weight, based on the weight of the fungicide composition, for example, about 0.5% to about 9.5% by weight, for example, about 1% to about 9% by weight, or any range or value therebetween.

[0035]

[0037] Regardless of the amount selected, or whether the disinfectant composition is present as a concentrate or a ready-to-use formulation, the disinfectant composition can include a film-forming agent in an amount greater than the amount of quaternary ammonium biocide, thereby allowing the amount of biocide to be reduced. For example, in one embodiment, the ratio of the amount of film-forming agent to the amount of quaternary ammonium biocide is at least about 1.1:1 or more, such as about 1.25:1 or more, such as about 1.5:1 or more, such as about 1.75:1 or more, such as about 2:1 or more, such as about 2.5:1 or more, such as about 3:1 or more, up to about 20:1 or less, or any range or value therebetween.

[0036]

[0038] Furthermore, the present disclosure has also surprisingly found that the above antibacterial properties and abrasion resistance can be exhibited or even improved when the composition has a relatively high pH, ​​for example, about 9 or more, for example, about 9.25 or more, for example, about 9.5 or more, for example, about 9.75 or more, for example, about 10 or more, for example, about 10.25 or more, or any range or value therebetween. That is, without wishing to be bound by theory, it is believed that polyethyleneimine can exhibit lower solubility at higher pH values ​​while still remaining stable in the composition, allowing for the formation of a stronger film.

[0037]

[0039] Additionally, the disinfectant composition according to the present disclosure may also include a non-ionic surfactant, which in one aspect may improve the spreading and / or wetting of the disinfectant composition, allowing for the formation of a more uniform film with better rub resistance. If present in the composition, the non-ionic surfactant may be an alkoxylated alcohol, polyoxyethylene glycol alkyl ether, octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, alkyl polyglucoside, glucoside alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, polyoxyethylene glycol octylphenol ether, polyoxyethylene glycol alkylphenol ether, glycerol alkyl ester, polyglycerol ester, glyceryl laurate, polyoxyethylene glycol sorbitan alkyl ester, sorbitan alkyl ester, dodecyl dimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol, poloxamer and polyethoxylated tallowamine (POEA), and mixtures thereof. Nevertheless, in one embodiment, the non-ionic surfactant is an alkyl polyglucoside, an alcohol polyglycol ether, an amine ethoxylate, a fatty alcohol alkoxylate, a polyethylene glycol, an alcohol PEG-ether, a fatty acid ethoxylate, a glycerol ester, or a combination thereof. Further, in one embodiment, the non-ionic surfactant is an alkyl polyglucoside.

[0038]

[0040] The amount of nonionic surfactant in the ready-to-use composition can be from about 0.01% to about 5%, for example, from about 0.05% to about 3% nonionic surfactant, for example, from about 0.1% to about 1.5%, or any range or value therebetween, based on the weight of the composition. When present in a concentrated formulation, the nonionic surfactant can be present in the disinfectant composition in an amount of from about 0.1% to about 10%, for example, from about 0.5 to about 7.5%, for example, from about 1% to about 5%, or any range or value therebetween, based on the weight of the disinfectant composition.

[0039]

[0041] Regardless of the amount selected, or whether the germicide composition is present as a concentrate or a ready-to-use formulation, the film-forming agent, if present, can be present in an amount greater than the amount of nonionic surfactant. For example, in one embodiment, the ratio of the amount of film-forming agent to the amount of nonionic surfactant is at least about 1.1:1 or more, such as about 1.25:1 or more, such as about 1.5:1 or more, such as about 1.75:1 or more, such as about 2:1 or more, such as about 2.5:1 or more, such as about 3:1 or more, such as about 4:1 or more, up to about 50:1 or less, such as about 40:1 or less, such as about 30:1 or less, or any value or range therebetween.

[0040]

[0042] Further, in one embodiment, the germicide composition can also include a strengthening agent, which in some cases can provide the germicide composition with additional abrasion resistance. Thus, in one embodiment, the germicide can also include a strengthening agent, which is a C12-C24 fatty alkyl quaternary ammonium compound or a silane quaternary ammonium compound different from the quaternary ammonium biocide, such as, in one embodiment, a cetyltrimethylammonium compound, a lauryltrimethylammonium compound, a stearyldimethylbenzylammonium compound, a soyatrimethylammonium compound, a behentrimethylammonium compound, a dimethylditallow quaternary ammonium compound and / or a di(partially hydrogenated tallow)dimethylammonium compound, a tricetylmethylammonium chloride, or a combination thereof.

[0041]

[0043] When formulated as a concentrated composition, the fortifying agent can be present in the composition in an amount of about 0.1% to about 30% by weight based on the weight of the fungicide composition, for example, about 0.5% to about 25% by weight based on the weight of the composition, for example, about 1 to about 20% by weight, for example, about 1.5% to about 15% by weight, or any range or value therebetween. When formulated as a ready-to-use composition, the fortifying agent can be present in the composition in an amount of about 0.01% to about 5% by weight based on the weight of the fungicide composition, for example, about 0.05% to about 4% by weight based on the weight of the composition, for example, about 0.1 to about 3% by weight, for example, about 0.15% to about 2% by weight, or any range or value therebetween.

[0042]

[0044] Regardless of the enhancer selected, if any, the quaternary ammonium compound contained in the microbicidal composition, e.g., the quaternary ammonium biocide, enhancer, or combination thereof, is a quaternary ammonium carbonate, a quaternary ammonium bicarbonate, a quaternary ammonium halide, a quaternary ammonium phosphate, a quaternary ammonium sulfate, or a combination thereof.

[0043]

[0045] Additionally or alternatively, the disinfectant composition may further comprise a second surfactant. In one embodiment, the second surfactant may be a zwitterionic surfactant, such as a betaine surfactant. The betaine surfactant may be a betaine or sulfobetaine surfactant. The betaine surfactant may include betaines and sulfobetaines of formula (2):

[0044] [ka]

[0045] (Wherein, R is alkyl or (3)

[0046] [ka]

[0047]

[0046] , where Z" is COO" or SO3 - where R1 is alkyl or hydroxyalkyl, R2 is alkyl of up to about 20 carbon atoms, preferably from about 6 to about 16 carbon atoms, and R3 is alkyl.

[0048] Additionally, betaine surfactants may be of the formula:

[0049] [ka]

[0050] (In the formula, R 2 can have up to about 20 carbon atoms, including, for example, alkyl groups having from about 6 carbon atoms to about 16 carbon atoms.

[0048] Examples of betaines useful herein include decyl betaine or 2-(N-decyl-N,N-dimethylammonio)acetate, myristyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, stearyl betaine, coconut dimethyl carboxymethyl betaine ("coco betaine"), cocamidoethyl betaine, cocamidopropyl betaine, lauramidopropyl betaine, myristylamidopropyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl) carboxymethyl betaine, stearyl bis-(2-hydroxy-propyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl) alpha-carboxyethyl betaine, cocamidopropyl dimethyl betaine, and mixtures thereof.

[0051]

[0049] An example of a sulfobetaine surfactant is 3-(N,N-dimethyl-N-acylamidopropylammonio)-2-hydroxy-propane-1-sulfonate, where the acyl group is derived from tallow fatty alcohol or coconut fatty alcohol, with coconut fatty alcohol being preferred. It is recognized by those skilled in the art that in the standard preparation of these derivatives of tallow or coconut fatty alcohol, a mixture of sulfobetaines with different carbon chain lengths for the acyl group is produced. These fatty alcohols contain, for the most part, carbon chain lengths that result in acyl groups with the desired number of carbon atoms, i.e., from about 8 to about 18 carbon atoms. Thus, these mixtures obtained from tallow or coconut fatty alcohol are useful in providing sulfobetaine surfactants for the reagents of the present disclosure. A material of this type for use in the compositions of the present disclosure is N-cocamidopropyl-N,N-dimethyl-N-2-hydroxypropyl sulfobetaine. An example of this is LONZAINE CS, available commercially from Lonza, Inc.

[0052]

[0050] Betaines can also include betaine polymers, such as amphiphilic betaine polymers. Polymeric betaines can include, for example, complexes of dialkyldialkoxylated quaternary ammonium salts with boric acid. Other similar compounds can also include quaternary amine salts formed by protonation of monoalkylamines, dialkylamines, trialkylamines, and monobisalkoxylated amines. In one particular embodiment, the polymeric betaine can include didecylbis(hydroxyethyl)ammonium borate. The polymeric betaine can have the following formula:

[0053] [ka]

[0054] may have the following structure:

[0051] Nevertheless, in one embodiment, the zwitterionic surfactant is a betaine surfactant, such as cocamidopropyl betaine, cocamidopropyl hydroxyl sultaine, or a combination thereof. The disinfectant composition of the present disclosure can contain a single betaine or a combination of betaines as described above as all portions of the zwitterionic surfactant.

[0055]

[0052] The disinfectant composition according to the present disclosure may also include a chelating agent. That is, without wishing to be bound by theory, it is believed that the chelating agent, e.g., a carboxylic acid chelating agent, may provide a complex with the quaternary ammonium biocide at high pH levels to further stabilize the composition. Thus, in one embodiment, any chelating agent known in the art may be suitable, e.g., ethylenediaminetetraacetic acid (EDTA) and its salts (e.g., tetrasodium EDTA), diammonium ethylenediaminetetraacetate, amino carboxylic acids, aminophosphonic acids, fatty acid salts, mixtures thereof, and the like, while in a further embodiment, the chelating agent is a C1-C10 carboxylic acid. Thus, in one embodiment, the chelating agent is citric acid, sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, or mixtures thereof. The chelating agent can be present in the composition in an amount of about 0.01% to about 10%, such as about 0.05% to about 6%, such as about 0.1% to about 5%, or any range or value therebetween, based on the weight of the ready-to-use composition. Additionally, the chelating agent can be present in a concentrated formulation in an amount of about 0.1% to about 20%, such as about 0.5% to about 15%, such as about 1% to about 10%, or any range or value therebetween.

[0056] The compositions may further contain additional ingredients including solvents, pH adjusters, drying agents, aqueous carriers, dyes, fragrances, preservatives, etc. Each of the additives may be present alone or in combination with the other additives.

[0057] For example, the antimicrobial composition can also contain a pH builder. Suitable pH builders include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium citrate, sodium carbonate, silicates such as sodium metasilicate, alkanolamines, and other similar compounds. In one embodiment, the pH builder is sodium metasilicate pentahydrate, monoethanolamine, or a combination thereof. The pH builder can be present in the ready-to-use composition in an amount of about 0.01% to about 2%, for example, about 0.02% to about 1%, or any range or value therebetween, based on the weight of the composition.

[0058] As discussed above, the germicidal compositions of the present disclosure may be supplied as concentrates, which are diluted to use levels prior to use. Alternatively, the germicidal compositions may be provided as ready-to-use (RTU) compositions. In either case, the compositions contain a solvent.

[0059]

[0056] Generally, the solvent is a polar solvent, such as water, or an organic solvent, such as an alcohol and / or a glycol ether. In one embodiment, the only solvent present in the composition is water. Alternatively, the composition may contain water in combination with an organic solvent.

[0060]

[0057] Examples of organic solvents include ethanol, propanol, benzyl alcohol, phenoxyethanol, isopropanol, diethylene glycol propyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, tripropylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, dipropylene glycol n-propyl ether, ethylene glycol hexyl ether and combinations thereof.

[0061]

[0058] Water may be present in the ready-to-use composition generally in an amount greater than about 60% by weight, such as greater than about 70% by weight, such as greater than about 80% by weight, such as greater than about 90% by weight. For example, water may be present in the composition in an amount greater than about 92% by weight, such as greater than about 94% by weight, such as greater than about 96% by weight, such as greater than about 98% by weight. Water may be present generally in an amount less than about 99.5% by weight, such as less than about 99% by weight, such as less than about 95% by weight, or any range or value therebetween. However, water can also be present in concentrated formulations in an amount of, for example, about 85% or less, such as about 75% or less, such as about 65% or less, such as about 60% or less, or, for example, from about 2.5% to about 95%, such as from about 3% to about 90%, such as from about 5% to about 85%, or any range or value therebetween, based on the weight of the disinfectant composition.

[0062] In one embodiment, the solvent comprises water and an additional organic solvent, such as isopropanol, propylene glycol n-propyl ether, or propylene glycol n-butyl ether. When a solvent is present in addition to water, the solvent is preferably present in the concentrate in an amount of about 0.1% to about 20%, such as about 0.25% to about 15%, such as about 0.5% to about 10% by weight, or any range or value therebetween, based on the weight of the composition. In addition to water, the organic solvent can be present in the ready-to-use composition in an amount of about 0.01% to about 2%, such as about 0.05% to about 1.5%, such as about 0.1% to about 1%, such as about 0.25% to about 0.75%, based on the weight of the composition.

[0063]

[0060] The disinfectant composition of the present disclosure may further contain corrosion inhibitors, auxiliaries, preservatives, fragrances, colorants, and the like, as the case may be. Exemplary corrosion inhibitors include, for example, organophosphorus compounds and blends of organophosphorus compounds with polymeric components. Colorants and fragrances can be added, provided they do not interfere with the function of the composition and can function to distinguish the composition. Generally, the optional additional components make up less than about 20% by weight of the composition. For example, each of the ingredients or components identified above can be present in the ready-to-use or concentrated composition in an amount generally between about 0.01% and about 5% by weight. For example, each of the components above can be present in the composition in an amount between about 0.1% and about 2% by weight, such as between about 0.3% and about 1% by weight, or any range or value therebetween. The optional additives are added in amounts conventionally used in sanitizing and disinfecting compositions.

[0064] Advantageously, the addition of fragrance has been found not to alter the streaking and film-forming performance of the composition.

[0062] Nevertheless, the present disclosure is also directed to providing residual sanitization to hard surfaces generally, and / or cleaning and / or sterilizing equipment. Thus, in one aspect, the germicide composition can be delivered to the surface to be cleaned, sanitized, or sterilized by conventional methods, such as by pouring the composition onto the surface; spraying the surface (including, for example, but not limited to, spraying with a pump spray applicator, a pressurized spray applicator, etc.); soaked wipes; rags and buckets; mops and buckets; sponges and buckets; or automated cleaning equipment and other similar and conventional methods for applying antimicrobial or germicide compositions to a surface for the purpose of sanitizing or sterilizing the surface.

[0065] To use the germicide composition of the present disclosure, a surface is treated with a substrate by spraying, pouring, wiping, or otherwise applying the antimicrobial composition to the surface. Once applied to the surface, the germicide composition is allowed to remain on the surface for a period of time. The germicide composition may be applied to the surface and allowed to dry, or alternatively, may be dried by wiping the surface with a dry wipe or wiping device.

[0066]

[0064] Surfaces that can be disinfected with the disinfectant composition include, but are not limited to, surfaces installed in dairies, homes, health care facilities, swimming pools, canneries, food processing plants, restaurants, hospitals, facilities, and industries including secondary oil recovery. Any suitable hard surface, especially hard surfaces that are frequently touched, can be treated according to the present disclosure. Hard surfaces may be made of, for example, glass, metal, such as aluminum or stainless steel, ceramic, stone, such as granite or marble, plastic or polymeric materials, and the like. Specific targeted areas of application include hard surfaces in the home, such as kitchen countertops, cabinets, appliances, cans, laundry areas, trash cans, bathroom fixtures, toilets, water tanks, faucets, mirrors, sinks, bathtubs, and showers. The composition can also be used to sanitize floors, walls, furniture, mirrors, toilet fixtures, windows, and wood surfaces, such as fence rails, porch rails, decks, roofing, siding, window frames, and door frames. The composition is particularly well suited for application on surfaces that indirectly come into contact with food, such as cutting boards, household items, containers, petri dishes, washbasins, electrical appliances, and countertops.Areas in hospitals include floors, gurneys, tables, canisters, toilets, empty cans, stands, cabinets, shower rooms, floors, doorknobs, floor rails, walls, or any other non-porous surfaces.In particular, in one embodiment, the surface can be any inanimate, non-porous, hard surface.

[0067]

[0065] One particularly useful application method is to impregnate the disinfectant composition into a wipe substrate. In such an embodiment, the wipe can be a disposable wipe that is impregnated with the disinfectant composition and stored in a container that dispenses the wipe to the user. The container that holds the wipe may contain single-use wipes or multi-use wipes. Suitable containers include pouches that contain single-use wipes, such as wet wipes that are torn open by the user, or may be pouches with resealable openings that contain multi-use wipes in stacks, rolls, or other suitable configurations that allow the single-use wipes to be removed from the opening one at a time. The pouches are generally prepared from fluid-impermeable materials, such as films, coated paper or foils, or other similar fluid-impermeable materials. Another way of dispensing the wipes of the present disclosure is to place them in a fluid-impermeable container with an opening that allows access to the wipes in the container. The container may be a molded plastic container with a lid that is fluid-impermeable. Typically, the lid has an opening to allow access to the wipes in the container. The wipes in the container may be stacked in an interleaved manner such that when a wipe is removed from the container, the next wipe is placed in the opening of the container to allow the user to remove the next wipe. Alternatively, the wipes may be a continuous material with perforations between the individual wipes in the continuous material. The perforated continuous wipe material may be in a folded or rolled form. Typically, in a rolled form, the wipe material is dispensed from the center of the rolled material. As with an interleaved stack, when a wipe is removed from the container, the next wipe is placed in the opening for use such that the next wipe can be removed when needed.

[0068] The germicidal composition can be impregnated into the wipe so that the wipe is pre-moistened and develops or releases the germicidal composition onto the surface as the wipe moves across the surface to be treated. Typically, the germicidal composition is impregnated into the wipe so that the wipe releases the germicidal composition onto the surface through the wiping action. Depending on the wipe substrate, wetting is typically achieved using about 3 parts by weight of germicidal composition per part by weight of wipe substrate to be wetting. Typically, about 4 to 6 parts by weight of germicidal composition is used per part by weight of wiper substrate. In these ranges, complete wetting of the substrate can be achieved. It is stated that the amount of germicidal solution can be increased or decreased to achieve complete wetting of the wipe substrate, depending on the particular wipe substrate.

[0069]

[0067] Suitable wipe substrates include woven and nonwoven materials. Essentially any nonwoven web material can be used. Exemplary nonwoven materials include, but are not limited to, meltblown, coform, spunbond, airlaid, hydroentangled nonwovens, spunlace, bonded carded webs, and laminates thereof. In some cases, the nonwoven may be laminated with a film material. The fibers used to prepare the wipe substrate may be cellulosic, thermoplastic, and mixtures thereof. The fibers may also be continuous, discontinuous, staple, and mixtures thereof. The basis weight of the nonwoven web may vary from about 12 grams per square meter to more than 200 grams per square meter.

[0070] The following examples are intended to provide a more complete understanding of the invention, but are not intended to limit the invention. EXAMPLES

[0071] Test methods and conditions

[0070] Test conditions Organism: Staphylococcus aureus ATCC 6538 Klebsiella aerogenes ATCC 13048 Culture medium: Nutrient broth was used for test culture against Staphylococcus aureus. Tryptic soy broth was used for test culture of Klebsiella aerogenes. Organic soil: 5% fetal bovine serum (FBS) Dilution: Ready to use Temperature: 20℃ Residual time: 24 hours Contact time (sanitizer test): 5 minutes Neutralizer: D / E Broth Support: 1" (2.5 cm) x 1" (2.5 cm) glass microscope slide, decontaminated by soaking in ethanol and allowed to dry. Product Application: The product was applied by spraying onto the test surface at a distance of 6 inches (15.2 cm) to 8 inches (20.3 cm) for 2 seconds. Friction speed: 2.0-2.5, total surface contact time approximately 5 seconds per friction cycle Inoculation process: Inoculation was performed according to EPA #01-1A with incubation at 35+2° C. using a 10 μl micropipette with at least three consecutive daily transfers.

[0072] Test Method

[0072] Micro-efficacy tests (shown as log reduction in Table 1) were performed according to EPA protocol #01-1A (2022) by applying 10 μL aliquots of the initial inoculum (48-54 hour incubation, serially diluted by two 0.1 mL to 9.9 mL stepwise dilutions) to the glass slide supports discussed above and drying at 35+2°C with the lid open until visually dry. Each sample was then applied to the support and allowed to dry.

[0073] The dried samples were then subjected to abrasion testing at a speed of 2.0-2.5 for a total surface contact time of approximately 5 seconds per abrasion cycle (each cycle including the first and return passes). The carriers were then subjected to an abrasion and reinoculation regime by repeating the initial inoculation described above for 24 hours at room temperature and 45-55% relative humidity. This 24 hour reinoculation was prepared by vortexing the 18-24 hour culture and making two serial dilutions from 0.1 mL to 9.9 mL and one final dilution from 5.0 mL to 5.0 in sterile distilled water. In addition, a volume of serum equivalent to a 5% organic soil loading was added to the dilutions, applied to the carriers and allowed to dry until visually dry (at least 30 minutes).

[0074] For each cycle, alternating wet and dry abrasion was performed for a total of 6 wet abrasion and 6 dry abrasion cycles, where the wet abrasion cycles were performed by spraying the cloth with sterile distilled water as specified in EPA 01-1A. After the 12th cycle, the log reduction of organisms remaining on the carrier was determined and recorded as shown in Table 1.

[0075] For the friction screening data for Samples 1-6 (shown as weight retention in Table 1), the above test procedure was modified by utilizing only seed medium with no live cultures present, and weight retention was determined based on the remaining quaternary ammonium biocide(s) compared to the initial amount of quaternary ammonium biocide(s) via liquid chromatography-mass spectrometry (LC-MS) method.

[0076]

[0076] In addition, Samples 9-15 were formed as discussed with respect to the friction screening of Samples 1-6, except that all 12 cycles were wet-abrasion cycles, and weight retention was determined based on the loss in weight of the film on the glass carrier compared to the initial weight after the sample was allowed to dry overnight.

[0077]

[0077] Formulation details for the disinfectant samples are provided in Table 1, where water was used to make up to 100% to form the ready-to-use compositions. Antimicrobial activity after rub resistance test data is also provided in Table 1 using the test method and conditions set forth above. As shown in Table 1, the compositions according to the present disclosure exhibited excellent antimicrobial activity even after vigorous rub testing.

[0078] [Table 1-1]

[0079] [Table 1-2]

[0080]

[0078] These and other modifications and variations to the present invention may be implemented by those skilled in the art without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those skilled in the art will recognize that the foregoing description is merely illustrative and is not intended to limit the invention, which is further set forth in the appended claims.

Claims

1. 1. A composition for providing a hard surface with residual antimicrobial activity, comprising: a quaternary ammonium biocide; and a film-forming agent comprising polyethyleneimine; and providing about a 2 or greater log reduction against Staphylococcus aureus after being subjected to an abrasion resistance test according to EPA 01-1A.

2. 10. The composition of claim 1 having a pH of about 9 or greater, preferably about 9.5 or greater.

3. The composition of claim 1 or 2, further comprising a nonionic surfactant.

4. 3. The composition of claim 1 or 2, further comprising a strengthening agent different from the quaternary ammonium biocide, the strengthening agent comprising a C12 to C24 fatty alkyl quaternary ammonium compound or a silane quaternary ammonium, preferably the strengthening agent being a cetyltrimethylammonium compound, a lauryltrimethylammonium compound, a stearyldimethylbenzylammonium compound, a soyatrimethylammonium compound, a behentrimethylammonium compound, a dimethylditallow quaternary ammonium compound, or a combination thereof.

5. 3. The composition of claim 1 or 2, wherein the quaternary ammonium biocide is a dialkyldimethylammonium compound, an alkyldimethylbenzylammonium compound, an alkyltrimethylammonium compound, or a combination thereof, preferably the quaternary ammonium biocide is a C8 dialkyldimethylammonium compound, a C10 dialkyldimethylammonium compound, a C12 to C16 alkyldimethylbenzylammonium compound, a C8 to C18 alkyltrimethylammonium compound, or a combination thereof.

6. 3. The composition of claim 1 or 2, wherein the composition is a ready-to-use composition and the quaternary ammonium biocide is present in the composition in an amount of from about 0.01% to about 5% by weight, preferably from about 0.05% to about 4% by weight, more preferably from about 0.1 to about 3% by weight, and even more preferably from about 0.15% to about 2% by weight, based on the weight of the composition.

7. 3. The composition of claim 1 or 2, wherein the composition is a ready-to-use composition and the film-forming agent is present in the composition in an amount of from about 0.1 to about 10% by weight, preferably from about 0.5% to about 9.5% by weight, and even more preferably from about 1% to about 9% by weight.

8. 3. The composition of claim 1 or 2, wherein the composition is a concentrated composition and the quaternary ammonium biocide is present in the composition in an amount of from about 0.1% to about 50% by weight, preferably from about 0.5% to about 40% by weight, more preferably from about 1 to about 30% by weight, and even more preferably from about 1.5% to about 20% by weight, based on the weight of the composition.

9. 3. The composition of claim 1, wherein the composition is a concentrated composition and the film-forming agent is present in the composition in an amount of 0.1% to about 50% by weight, preferably about 0.5% to about 40% by weight, more preferably about 1 to about 35% by weight, and even more preferably about 1.5% to about 32.5% by weight, based on the weight of the composition.

10. 5. The composition of claim 4, wherein the quaternary ammonium biocide, the enhancer, or both, is a quaternary ammonium carbonate, a quaternary ammonium bicarbonate, a quaternary ammonium halide, a quaternary ammonium phosphate, a quaternary ammonium sulfate, or a combination thereof.

11. The composition of claim 1 or 2, further comprising a chelating agent.

12. 12. The composition of claim 11, wherein the chelating agent is a C1 to C10 carboxylic acid, preferably the C1 to C10 carboxylic acid is citric acid, sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, or a mixture thereof.

13. The composition of claim 1 or 2, which does not contain any film-forming agent other than the polyethyleneimine.

14. 3. The composition of claim 1 or 2, further comprising a second surfactant, a pH adjuster, a drying agent, an aqueous carrier, or a combination thereof.

15. 4. The composition of claim 3, wherein the nonionic surfactant comprises an alkyl polyglucoside, an alcohol polyglycol ether, an amine ethoxylate, a fatty alcohol alkoxylate, a polyethylene glycol, an alcohol PEG-ether, a fatty acid ethoxylate, a glycerol ester, or a combination thereof, preferably wherein the nonionic surfactant is an alkyl polyglucoside.

16. 15. The composition of claim 14, wherein the second surfactant is a zwitterionic surfactant, preferably the second surfactant is cocamidopropyl betaine, cocamidopropyl hydroxylsultaine, or a combination thereof.

17. 1. A method of providing residual sanitization to a hard surface, comprising: applying a composition to the hard surface, wherein the composition quaternary ammonium biocides, Film-forming agents containing polyethyleneimine and subjecting the hard surface to a rub cycle using a GardCo Washability and Wear Tester set between 2.25 and 2.5, wherein the composition provides about a 2 or greater log reduction against Staphylococcus aureus after being rubbed for at least 2 seconds; A method comprising:

18. 18. The method of claim 17, wherein the composition has a pH of about 9 or greater, preferably about 9.5 or greater.

19. 19. The method of claim 17 or 18, wherein the hard surface exhibits a log reduction after being subjected to 2 to 12 friction cycles of about 2 to about 5 seconds.

20. 19. The method of claim 17 or 18, wherein the composition further provides about a 2 or greater log reduction against Klebsiella aerogenes.

21. 19. The method of claim 17 or 18, wherein the hard surface is a non-porous or inanimate surface or a non-porous and inanimate surface.

22. 19. The method of claim 17 or 18, wherein the composition further comprises a non-ionic surfactant.

23. 19. The method of claim 17 or 18, wherein the composition further comprises a strengthening agent different from the quaternary ammonium biocide, the strengthening agent comprising a C12 to C24 fatty alkyl quaternary ammonium compound or a silane quaternary ammonium, preferably the strengthening agent is a cetyltrimethylammonium compound, a lauryltrimethylammonium compound, a stearyldimethylbenzylammonium compound, a soyatrimethylammonium compound, a behentrimethylammonium compound, a dimethylditallow quaternary ammonium compound, or a combination thereof.

24. 19. The method of claim 17 or 18, wherein the quaternary ammonium biocide is a dialkyldimethylammonium compound, an alkyldimethylbenzylammonium compound, an alkyltrimethylammonium compound, or a combination thereof, preferably the quaternary ammonium biocide is a C8 dialkyldimethylammonium compound, a C10 dialkyldimethylammonium compound, a C12 to C16 alkyldimethylbenzylammonium compound, a C8 to C16 alkyltrimethylammonium compound, a C8 to C18 alkyltrimethylammonium compound, or a combination thereof.