Compositions and methods for persistent disinfection

Abstract

The present invention relates to compositions and methods for long-lasting disinfection. In particular, an antimicrobial composition is disclosed comprising: an antimicrobial component having at least one quaternary ammonium compound; a cationic polysaccharide; an organic acid; and a surfactant selected from the group consisting of cationic surfactants, amphoteric surfactants, nonionic surfactants, and combinations thereof. This composition provides robust long-lasting disinfection when applied to a surface.

Description

[0001] This application is a divisional application of the following application: Application date: April 9, 2019; Application number: 2019800310189; Invention title: "Composition and method for persistent disinfection".

[0002] Cross-reference to related applications This application claims the benefit of priority to U.S. Provisional Application Serial No. 62 / 654,652, filed April 9, 2018, pursuant to 35 USC §119(e), and the entire disclosure of that application is incorporated herein by reference. Background Technology

[0003] It is often desirable to provide a biocidal surface on which microorganisms, many of which are potentially harmful, cannot survive, at least for a given period of time. Most material surfaces are not typically resistant to microbial contamination. A useful way to improve the microbial tolerance of a surface is to treat it with a formulation that provides biocidal action and also prevents future growth until the next application.

[0004] A common method for treating surfaces is to apply a layer of liquid formulation to the surface and then dry or allow the layer to dry. It is desirable that such liquid formulations be clear and stable during storage. It is also desirable that such liquid formulations spread evenly when applied to a hard, flat surface. It is desirable that such films, upon drying, possess one or more of the following desirable properties: transparency, non-stickiness; durability against repeated touch or wiping; no long-term buildup; and the ability to maintain biocidal efficacy over a long period of normal use after application to the surface.

[0005] Commercially available antimicrobial compositions, as disinfectants or cleaning agents with disinfecting activity, typically achieve microbial kill rates of 99.9% or higher. However, recontamination or re-polluting of surfaces requires additional treatment with such compositions. Therefore, there is a need for antimicrobial formulations that provide high microbial kill rates without the need for repeated application. However, designing compositions that meet these requirements is a challenging task due to the unpredictable and complex interactions between the components. Summary of the Invention

[0006] This disclosure provides hard surface treatment compositions comprising: an antimicrobial component including at least one quaternary ammonium compound; a cationic polysaccharide derived from a natural source; an organic acid; and a surfactant selected from cationic surfactants, amphoteric surfactants, nonionic surfactants, and combinations thereof. Methods for providing a surface with residual antimicrobial activity are also provided, including the step of applying the composition of this disclosure to the surface. This disclosure also provides a substrate with residual antimicrobial activity, the substrate comprising a substrate in which at least a portion thereof is coated with the composition of this disclosure. Attached Figure Description

[0007] Figure 1 This is a flowchart describing the RSS-12 h analysis performed in the example. Detailed Implementation

[0008] This disclosure relates to compositions that provide more durable disinfection to treated surfaces and include cationic polysaccharides derived from natural sources. The compositions of the present invention achieve a microbial (e.g., bacteria, viruses, or fungi) kill rate (e.g., 99.9%) within 12 to 24 hours, avoiding the need for repeated treatments. Suitable techniques for evaluating the effectiveness of the compositions disclosed herein include standard U.S. and European methods.

[0009] To verify the United States Environmental Protection Agency's (EPA) 24-hour long-term disinfection requirement, the Residual Self-Disinfecting (RSS) method was used, EPA Protocol #01-1A ( https: / / www.epa.gov / sites / production / files / 2015-09 / documents / cloroxpcol_final.pdf The composition was evaluated. To validate long-term disinfection, all existing test protocols simulated maximum recontamination and abrasion by pre-touching and wiping before reapplication, typically over a 24-hour period. An intermediate protocol (with approximately half the level of abrasion and recontamination challenge on the surface) is presented here as the “RSS-12 h” test protocol.

[0010] To meet the need for a standard European testing method that can measure and assess residual antimicrobial activity, the British Standards Institute (BSI) recently published BSI-PAS-2424, entitled: “Quantitative surface test for the evaluation of residual antimicrobial (bactericidal and / or yeasticidal) efficacy of liquid chemical disinfectants on hard non-porous surfaces - Test method.” Most methods involving antimicrobial efficacy testing involve applying the product to the surface and allowing it to stand for a period of time before microbial attack. A limitation of such methods is that the surface remains undisturbed after application. In fact, the Lancaster University report, “Cleaning Behaviours in the Home,” based on consumer research, shows that in home or workplace environments, once a product is applied to a surface, that surface is continuously exposed to abrasion such as touching and wiping. This results in surface recontamination before the product is applied again (typically every 24 hours). Test method BSI PAS 2424 is designed to reflect the actual conditions under which the product is intended to be used.

[0011] The EPA-RSS, RSS-12 h, and BSI-PAS 2424 methods all attempt to simulate the efficacy of persistent disinfectants by combining wet and dry abrasion cycles in the test protocol. Besides the obvious similarities between the test methods, there are some significant differences between the RSS and PAS2424 methods.

[0012] 1. Microorganisms: The number and types of microorganisms tested by the two methods differ and are listed below. The EPA-RSS list is much shorter (e.g., Gram+ve and Gram-ve bacteria), while PAS-2424 includes four bacterial strains and one yeast strain.

[0013] 2. In addition to the applied geometry, the weights used for abrasion testing are also very different between the two methods. The normal force (including boat weight) applied in the EPA-RSS test method is 1084 g ± 0.2 g, which is 5 times that of the normal force (210 g ± 2 g) applied in the BSI PAS 2424 method.

[0014] 3. Wear Cycles: Compared to the 3 wear cycles of BSI-PAS 2424 (as in the RSS-12 h test protocol), the EPA-RSS method uses 6 wear cycles.

[0015] In the embodiments, according to the Residual Self-Disinfecting (RSS) activity test (EPA Protocol #01-1A), the film formed by the composition kills at least 99.9% (e.g., log 3 reduction) of microorganisms. In the embodiments, according to the Residual Self-Disinfecting (RSS) activity test (EPA Protocol #01-1A), the film formed by the composition kills at least 99.9% (e.g., log 3 reduction) of Gram-positive and Gram-negative bacteria.

[0016] The requirement for durable sterilization was confirmed by an RSS test, which attacks the applied composition by subjecting it to recontamination (re-inoculation with microorganisms) and abrasion (wear cycles). An intermediate test protocol (with approximately half the number of re-inoculation and wear cycles) (“RSS-12 h”) was used to predict sterilization durability for up to 12 hours before reapplication of the test product. Figure 1 As outlined in the document, this procedure requires the preparation of test bacterial (microbial) cultures within the first week (see EPA Protocol #01-1A), followed by testing within the second week.

[0017] The test involved inoculating a surface with bacteria, followed by applying the product to a substrate and allowing it to dry. The substrate could be glass, polycarbonate, or steel. This substrate was then subjected to an abrasion-re-inoculation protocol with three "wear cycles." Abrasion was performed using a rectangular steel block weighing 1084 g covered with a fabric having a thin polyurethane foam underlayer. Each abrasion cycle consisted of a "dry" abrasion and a "wet" abrasion, the latter using Prevalence with the fabric cover. ® The sprayer is used to wet the substrate with a water mist. Each abrasion (dry / wet) is characterized by the back-and-forth movement of the block across the entire test substrate. After each abrasion cycle, the surface is inoculated with a bacterial culture. The RSS-12 h test involves 3 abrasion cycles / 3 inoculation tests, compared to the full RSS test which outlines a 6-abrasion-cycle / 6-inoculation test protocol. All other details of the test method are outlined in EPA protocol #01-1A.

[0018] Allow the test substrate to dry overnight, and then inoculate it again (disinfectant test) for 5 minutes, followed by neutralization of the entire substrate. Viable bacteria are then collected from the surface and incubated on agar plates using a serial dilution method to allow colonies to form within 24–48 hours. The viable bacteria are then counted by colony count. The difference between the inoculated bacterial count and the viable bacterial count yields a efficacy assessment expressed as a percentage kill rate (e.g., 99.9% kill rate) or a logarithmic reduction on a logarithmic scale (e.g., 3-log reduction). The bacteria in this test can be substituted for other microorganisms, such as fungi or viruses. In this example, the microorganisms are selected from Gram-positive bacteria (e.g., Staphylococcus aureus), Gram-negative bacteria (e.g., Enterobacter aerogenes), fungi, enveloped viruses, non-enveloped viruses, and combinations thereof.

[0019] The compositions disclosed herein are liquid formulations. A preferred method of utilizing the compositions disclosed herein is to apply a layer of the composition onto a substrate and then dry the composition or allow it to dry. The act of applying a layer of the composition onto a substrate and then drying it or allowing it to dry is referred to herein as “treating” the substrate. It is anticipated that as the solvent evaporates, the composition will form a film on the substrate. The dried layer of the composition is referred to herein as a “film”.

[0020] In the embodiments, the composition comprises: an antimicrobial component comprising at least one quaternary ammonium compound; a cationic polysaccharide derived from a natural source; an organic acid; and a surfactant selected from cationic surfactants, amphoteric surfactants, nonionic surfactants, and combinations thereof.

[0021] In one embodiment, the pH of the composition is in the range of about 2 to about 12. In another embodiment, the pH of the composition is in the range of 3 to 10. In yet another embodiment, the pH of the composition is in the range of 3 to 5. In still another embodiment, the pH of the composition is in the range of 4 to 9.

[0022] The antimicrobial compositions disclosed herein comprise at least one quaternary ammonium compound. In the embodiments, the quaternary ammonium compound is an antimicrobial "quaternary ammonium compound". The term "quaternary ammonium compound (quat)" generally refers to any composition having the following formula: Wherein R1-R4 can be the same or different, substituted or unsubstituted, saturated or unsaturated, branched or unbranched, and cyclic or acyclic alkyl groups, and may contain ether, ester or amide bonds; they can be aromatic groups or substituted aromatic groups. In the examples, groups R1, R2, R3, and R4 each have a chain length less than C20. -The term "anionic balance ion" includes any ion that can form a salt with quaternary ammonium. Examples of suitable balance ions include halide ions (such as chloride, bromide, fluoride, and iodide ions), sulfonate, propionate, methylsulfate, saccharinate, ethylsulfate, hydroxide, acetate, phosphate, carbonate, bicarbonate, and nitrate. In this example, the anionic balance ion is chloride.

[0023] In some embodiments, quaternary ammonium compounds having carbon chains of less than 20 or C2-C20 are included in the compositions disclosed herein. In other embodiments, quaternary ammonium compounds having carbon chains of C6-C18, C12-C18, C12-C16, and C6-C10 are included in the compositions disclosed herein. Examples of quaternary ammonium compounds that can be used in the quaternary ammonium compounds disclosed herein include, but are not limited to, alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, octyldecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, and disecyl dimethyl ammonium chloride. A single quaternary ammonium compound or a combination of more than one quaternary ammonium compound may be included in the compositions disclosed herein. Other examples of quaternary ammonium compounds that may be used in this disclosure include, but are not limited to, benzyl chloride, ethylbenzylalkonium chloride, ethylbenzyl chloride, myristyltrimethylammonium chloride, methylbenzyl chloride, cetalkonium chloride, cetrimonium bromide (CTAB), carnitine, dofanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide, benzozoline, choline, denatonium, and mixtures thereof.

[0024] In some embodiments, depending on the nature of the R group, the anion, and the number of quaternary nitrogen atoms present, antimicrobial quaternary ammonium compounds can be classified into one of the following categories: monoalkyltrimethylammonium salts; monoalkyldimethylbenzylammonium salts; dialkyldimethylammonium salts; heteroaromatic ammonium salts; polysubstituted quaternary ammonium salts; bis-quaternary ammonium salts; and polymeric quaternary ammonium salts. Each category will be discussed herein.

[0025] Monoalkyltrimethylammonium salts contain one R group, which is a long-chain alkyl group, and the remaining R groups are short-chain alkyl groups, such as methyl or ethyl. Some non-limiting examples of monoalkyltrimethylammonium salts include hexadecyltrimethylammonium bromide, commercially available under the trade names Rhodaquat® M242C / 29 and Dehyquart® A; alkyltrimethylammonium chloride, commercially available as Arquad® 16; alkylaryltrimethylammonium chloride; and hexadecyldimethylethylammonium bromide, commercially available as Ammonyx® DME.

[0026] Monoalkyl dimethyl benzyl ammonium salts contain one long-chain alkyl R group, a second benzyl R group, and the remaining two R groups are short-chain alkyl groups, such as methyl or ethyl. Some non-limiting examples of monoalkyl dimethyl benzyl ammonium salts include alkyl dimethyl benzyl ammonium chloride, commercially available as Barquat® from Lonza Inc.; and benzyl ammonium chloride, commercially available as Lonzagard® from Lonza Inc. Additionally, monoalkyl dimethyl benzyl ammonium salts can be substituted. Non-limiting examples of such salts include dodecyl dimethyl-3,4-dichlorobenzyl ammonium chloride. Finally, mixtures of alkyl dimethyl benzyl and alkyl dimethyl-substituted benzyl (ethyl benzyl) ammonium chloride are available as BTC® 2125M from Stepan Company and as Barquat® 4250 from Lonza Inc. Other examples include N,N-benzyldimethyloctylammonium chloride, N,N-benzyldimethyldecylammonium chloride, N-dodecyl-N-benzyl-N,N-dimethylammonium chloride, N-tetradecyl-N-benzyl-N,N-dimethylammonium chloride, N-hexadecyl-N,N-dimethyl-N-benzylammonium chloride, and N,N-dimethylN-benzylN-octadecylammonium chloride.

[0027] Dialkyl dimethyl ammonium salts contain two long-chain alkyl R groups, and the remaining R group is a short-chain alkyl group, such as methyl. Some non-limiting examples of dialkyl dimethyl ammonium salts include dialcyl dimethyl ammonium halide, commercially available from the Lonza Group as Bardac® 22; dialcyl dimethyl ammonium chloride, commercially available from the Lonza Group as Bardac® 2250; dioctyl dimethyl ammonium chloride, commercially available from the Lonza Group as Bardac® LF and Bardac® LF-80; and octyldecyl dimethyl ammonium chloride, sold as a mixture with dialcyl and dioctyl dimethyl ammonium chloride (commercially available from the Lonza Group as Bardac® 2050 and 2080).

[0028] Heteroaromatic ammonium salts contain an R group, which is a long-chain alkyl group, and the remaining R groups are provided by some aromatic system. Therefore, the quaternary nitrogen to which the R group is attached is part of an aromatic system such as pyridine, quinoline, or isoquinoline. Some non-limiting examples of heteroaromatic ammonium salts include hexadecylpyridinium halide, commercially available as Sumquat® 6060 / CPC from Zeeland Chemical Company; 1-[3-chloroalkyl]-3,5,7-triaza-1-azainium adamantane, commercially available as Dowicil® 200 from The Dow Chemical Company; and alkyl-isoquinolineium bromides.

[0029] Polysubstituted quaternary ammonium salts are monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, or heteroaromatic ammonium salts, wherein the anionic moiety of the molecule is a large, high molecular weight (MW) organic ion. Some non-limiting examples of polysubstituted quaternary ammonium salts include alkyldimethylbenzylsaccharin ammonium and dimethylethylbenzylcyclohexylaminosulfonate ammonium.

[0030] Biquaternary ammonium salts contain two symmetrical quaternary ammonium moieties with the following general formula: The R group can be a long-chain or short-chain alkyl group, a benzyl group, or provided by an aromatic system. Z is a carbon-hydrogen chain attached to each quaternary nitrogen. Some non-limiting examples of bis-quaternary ammonium salts include 1,10-bis(2-methyl-4-aminoquinolineonium chloride)-decane; and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride]hexane or triclobisonium chloride.

[0031] In the examples, the quaternary ammonium compound is a medium to long chain alkyl R group, such as from 8 carbons to about 20 carbons, from 8 carbons to about 18 carbons, from about 10 carbons to about 18 carbons, and from about 12 carbons to about 16 carbons, and provides a soluble and good antimicrobial agent.

[0032] In the examples, the quaternary ammonium compound is a short dialkyl chain quaternary ammonium compound having an R group, such as from 2 carbons to about 12 carbons, from 3 carbons to about 12 carbons, or from 6 carbons to about 12 carbons.

[0033] The composition may contain one or more quaternary ammonium compounds ranging from about 100 to about 20,000 ppm. In various embodiments, the composition contains one or more quaternary ammonium compounds ranging from about 500 to about 20,000 ppm, from about 500 to about 10,000 ppm, or from about 500 to about 5,000 ppm.

[0034] The cationic polysaccharides used in this disclosure are selected from polymers having a polysaccharide backbone containing cationic groups and are derived from natural sources. In the examples, the cationic polysaccharides derived from natural sources are selected from: cationic guar gum, cationic cellulose, and cationic starch. "Cationic" means permanently positively charged or non-permanently charged regardless of pH; for example, a derivative that can be cationic below a given pH and amphoteric or neutral above that pH. These cationic polysaccharides can be obtained by chemically modifying natural polysaccharides. This chemical modification (also referred to as "derivation") makes it possible to introduce side groups into the polysaccharide backbone. In the examples, the cationic groups carried by the cationic polysaccharides according to this disclosure are quaternary ammonium groups.

[0035] Guar gum is a polysaccharide composed of galactose and mannose. The main chain is a straight chain of mannose residues linked by β1,4-, and every other mannose residue is linked by 1,6- to the straight chain of mannose residues, forming short side branches.

[0036] In the context of this disclosure, these cationic guar gums are cationic derivatives of guar gum.

[0037] In the case of these cationic polysaccharides, such as cationic guar gum, the cationic group can be a quaternary ammonium group with three groups, which can be the same or different, preferably selected from hydrogen, alkyl, hydroxyalkyl, epoxyalkyl, alkenyl, or aryl, and preferably containing 1 to 22 carbon atoms, more specifically 1 to 14, and advantageously 1 to 3 carbon atoms. The counterion is typically a halogen. An example of such a halogen is chlorine.

[0038] Examples of these quaternary ammonium salts include: 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTMAC), 2,3-epoxypropyltrimethylammonium chloride (EPTAC), diallyl dimethylammonium chloride (DMDAAC), vinylbenzene trimethylammonium chloride, trimethylammonium ethyl methacrylate chloride, methacrylamidopropyltrimethylammonium chloride (MAPTAC), and tetraalkylammonium chloride.

[0039] One example of a cationic functional group in these cationic polysaccharides is the trimethylamino(2-hydroxy)propyl group, which has a counterion. Various counterions can be used, including but not limited to halide ions such as chloride, fluoride, bromide, and iodide ions, sulfate, methyl sulfate, and mixtures thereof.

[0040] In the embodiments, the cationic guar gum disclosed herein is selected from: cationic hydroxyalkyl guar gum, such as cationic hydroxyethyl guar gum (HE guar gum), cationic hydroxypropyl guar gum (HP guar gum), and cationic hydroxybutyl guar gum (HB guar gum); and cationic carboxylalkyl guar gum, including cationic carboxymethyl guar gum (CM guar gum), cationic carboxypropyl guar gum (CP guar gum), cationic carboxybutyl guar gum (CB guar gum), and carboxymethyl hydroxypropyl guar gum (CMHP guar gum).

[0041] In the embodiments, the cationic guar gum disclosed herein is guar gum hydroxypropyltrimethylammonium chloride or hydroxypropyl guar gum hydroxypropyltrimethylammonium chloride.

[0042] In the embodiments, the cationic polysaccharide is a blend of cationic guar gum and one or more film-forming water-soluble polymers. In the embodiments, the film-forming polymer is selected from polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), copolymers containing PVP, chitosan, ionic polymers (e.g., anionic polymers containing carboxylic acid or sulfonic acid groups and their salts wherein protons are replaced by lithium, sodium, potassium, etc.), and polyacrylamide.

[0043] In another embodiment, the cationic polysaccharide is depolymerized guar gum. In this embodiment, cationic guar gum can be prepared by depolymerizing cationically modified guar gum with a high molecular weight to “split” the guar gum polymer into the desired size. It should be understood that the cationic guar gum disclosed herein can also be prepared by depolymerizing natural guar gum followed by a cationization reaction to provide a polymer with cationic functionality. Various depolymerization methods are well known in the art and can be used, such as treatment and irradiation with a peroxide compound (e.g., hydrogen peroxide). Examples of such methods are disclosed in U.S. Patent Nos. 4,547,571, 6,383,344, and 7,259,192. Using methods generally known in the art, those skilled in the art can readily perform cationization of guar gum. Alternatively, low molecular weight guar gum can be obtained by harvesting guar beans still in the early stages of development, resulting in harvested guar beans containing low molecular weight natural guar gum. These guar gums can then be subjected to cationization to provide them with cationic functionality.

[0044] Among cationic guar gum derivatives, those that can be mentioned are guar hydroxypropyltrimethylammonium chloride (INCI name), such as Jaguar® C13S, C14S, or C17, Jaguar® Excel, and Jaguar® C 2000 sold by Solvay, or hydroxypropyl guar hydroxypropyltrimethylammonium chloride (INCI name), such as Jaguar® C162 sold by Solvay.

[0045] In one embodiment, the cationic polysaccharide is cationic cellulose. In another embodiment, the cationic cellulose is a cellulose ether (e.g., hydroxyethyl cellulose and hydroxymethyl cellulose). Examples of cellulose ethers are provided in U.S. Patent No. 6,833,347.

[0046] The cationic cellulose that can be used in the compositions disclosed herein is cellulose modified with a quaternary ammonium cationic group. In embodiments, the quaternary ammonium group has three groups, which may be the same or different and are selected from hydrogen, alkyl groups with 1 to 10 carbon atoms (e.g., 1 to 6 carbon atoms; 1 to 3 carbon atoms), and aryl groups, which may be the same or different. In embodiments, the quaternary ammonium group is selected from trialkylammonium groups (e.g., trimethylammonium, triethylammonium, tributylammonium, aryldialkylammonium, benzyldimethylammonium) that are each combined with a counterion and an ammonium group (e.g., pyridinium and imidazoline) wherein the nitrogen atom is a member of a cyclic structure. In embodiments, the counterion of the quaternary ammonium group is a halogen (e.g., chloride, bromide, or iodide ion).

[0047] The cationic substituents on cationic starch are the same as those described above for cationic guar gum and cationic cellulose.

[0048] In the examples, the cationic polysaccharides are derived from amphoteric polysaccharides that are cationic at lower pH values. Suitable amphoteric polysaccharides in the examples include polysaccharide derivatives containing both cationic and anionic substituents. These amphoteric polysaccharides are derived or modified to contain cationic groups or substituents. Substituted polysaccharides are formed by derivatization of the hydroxyl functionality of the polysaccharide. The cationic group can be amino, ammonium, imino, thionium, or phosphonium. Such cationic derivatives include those containing nitrogen-containing groups comprising primary, secondary, tertiary, and quaternary amines, and thionium and phosphonium groups attached via either ether or ester bonds. In the examples, the cationic derivatives contain tertiary amino and quaternary ammonium ether groups.

[0049] The degree of substitution (DS) of a cationic polysaccharide is the average number of hydroxyl groups substituted per sugar unit. DS can be notably determined by titration.

[0050] According to one aspect of this disclosure, the DS of the cationic polysaccharide is in the range of 0.1 to 1, preferably from 0.13 to 1, more preferably from 0.15 to 1, and even more preferably from 0.16 to 0.3.

[0051] The charge density (CD) of cationic polysaccharides refers to the ratio of the number of positive charges on the monomer units that make up the polymer to the molecular weight of the monomer units.

[0052] According to one aspect of this disclosure, the charge density of these cationic polysaccharides is in the range of 0.5 to 3 (meq / gm), preferably 0.8 to 2 (meq / gm), more preferably 0.8 to 1.6 (meq / gm), and particularly 0.9 to 1.4 (meq / gm).

[0053] These cationic polysaccharides may have an average molecular weight (Mw) between about 100,000 Daltons and 3,500,000 Daltons, preferably between about 500,000 Daltons and 3,500,000 Daltons, and more preferably between 1,500,000 Daltons and 3,500,000 Daltons.

[0054] In the examples, the amount of cationic polysaccharide in the composition ranges from about 200 ppm to about 5,000 ppm.

[0055] The compositions disclosed herein further comprise one or more organic acids. In embodiments, the organic acid is selected from citric acid, malic acid, maleic acid, oxalic acid, glutaric acid, succinic acid, lactic acid, glycolic acid, fumaric acid, acetic acid, benzoic acid, propionic acid, sorbic acid, tartaric acid, formic acid, and mixtures of one or more such organic acids. In another embodiment, the ionic acid may be a polymeric acid, such as poly(acrylic acid) or other polycarboxylic acids (e.g., maleic anhydride, methacrylic acid, etc.) or their homopolymers or copolymers (e.g., methyl methacrylate, butyl acrylate, etc.), such as Rhodoline available from Solvay. ® Those in the series. The composition may contain one or more organic acids ranging from 500 to 7,000 ppm.

[0056] In the compositions disclosed herein, the surfactant is selected from cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0057] Cationic surfactants are surfactants that dissolve in water to produce a net cationic charge. In embodiments, when present, the cationic surfactant is selected from cationic amine oxides, cationic betaine, propionates, amphoteric acetates, and combinations thereof. Under the acidic pH conditions disclosed herein, amine oxides, propionates, amphoteric acetates, and betaine are cationic. In embodiments, propionates are selected from cationic C8-C22 propionates and their salts. In another embodiment, cationic C8-C22 propionates are selected from alkyl amphoteric (di)propionates, alkylaminopropionates, alkyl amphoteric propionates, their salts, and combinations thereof. In embodiments, cationic amphoteric acetates are selected from amphoteric acetates according to the following formula: And amphoteric acetates according to the following formula: Wherein R is an aliphatic group having 8 to 18 carbon atoms, and M is a cation, such as sodium, potassium, ammonium, or substituted ammonium. In some embodiments, sodium lauroamphoacetate, sodium cocoamphoacetate, disodium lauroamphoacetate, and disodium cocoamphodiaacetate are preferred.

[0058] In the examples, the betaine is selected from cationic C8-C22 betaines and their salts. In another example, the cationic C8-C22 betaine is selected from alkyl dimethyl betaine, alkylamidopropyl betaine, alkyl amphoteric (di)acetate, their salts, and combinations thereof. When referred to herein as “its salt” of a cationic surfactant, these can be any suitable salt. In one embodiment, the salt is based on a monovalent cation (such as Na, K, or NH4). In one embodiment, the salt is based on an alkali metal (such as Na or K). Alternative salts, such as alkaline earth metal salts like Ca and Mg, may also be considered; however, the solubility of the product must be taken into account when using such salts.

[0059] Amphoteric surfactants contain both basic and acidic hydrophilic groups as well as organic hydrophobic groups. In the examples, when present, the amphoteric surfactants are selected from sulfobetaine, taurine esters, and combinations thereof.

[0060] Descriptions of nonionic surfactants are given in U.S. Patent Nos. 4,287,080 and 4,470,923. Particularly noteworthy are condensates of alkylene oxides, particularly ethylene oxide (linear or branched) and optionally propylene oxide with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides, and fatty amines; amine oxides; sugar derivatives, such as alkyl polyglycosides or fatty acid esters with sugars, particularly sucrose monopalmitate; long-chain tertiary phosphine oxides (having 8 to 28 carbon atoms); dialkyl sulfoxides; block copolymers of polyethylene oxide and propylene oxide; polyalkoxylated esters of sorbitol; fatty acid esters of sorbitol; and poly(ethylene oxide) and fatty acid amides modified thereon to impart hydrophobic properties (e.g., fatty acid mono- and diethanolamides containing 10 to 18 carbon atoms).

[0061] For example, a typical nonionic surfactant is: - Polyoxyalkylated C8-C containing 2 to 50 olefin oxide (ethylene oxide and / or propylene oxide) units 18 Aliphatic carboxylic acids, especially those with 12 (average) or 18 (average) carbon atoms, - Polyoxyalkylated C6-C containing 2 to 50 olefin oxide (ethylene oxide and / or propylene oxide) units 24Aliphatic alcohols, especially those having 12 (average) or 18 (average) carbon atoms; examples include Antarox® B12DF, Antarox® FM33, Antarox® FM63 and Antarox® V74 from Solvay, Plurafac® LF 400 and Plurafac® LF 220 from BASF, Rhodasurf® ID 060, Rhodasurf® ID 070 and Rhodasurf® LA 42, Rhodasurf® LA 9, Rhodasurf® BC-630 from Solvay, and Synperonic® A5, A7 and A9 from Imperial Chemical Industries (ICI). - Amine oxides, such as dodecyl di(2-hydroxyethyl)amine oxide, - Phosphine oxides, such as tetradecyl dimethyl phosphine oxide.

[0062] In one embodiment, the nonionic surfactant has a hydrophilic-lipophilic balance (HLB) value of less than 13. In another embodiment, the nonionic surfactant has an HLB value of less than 12. Nonionic surfactants with different HLB values ​​can be used.

[0063] In the embodiments, the composition comprises a combination of one or more cationic, amphoteric, and nonionic surfactants.

[0064] In the embodiments, the compositions disclosed herein are substantially free of anionic surfactants. With respect to the term "substantially free," we mean that the described compositions, formulations, or components contain less than 3% by weight, preferably less than 1%, more preferably 0.1% by weight, or less of anionic surfactants.

[0065] In addition to the components described herein, the composition may also contain polar carrier solvents (e.g., water), fragrances, preservatives, dyes, corrosion inhibitors, detergent builders, cleaning solvents, and other components known to be used in antimicrobial compositions.

[0066] The compositions disclosed herein include both disinfectant cleaning compositions and concentrates, differing only in the relative proportions of water and other components. In the embodiments, the concentrated formulation comprises at least one quaternary ammonium compound in an amount ranging from about 800 ppm to about 40,000 ppm; or from about 4,000 ppm to about 30,000 ppm; or from about 10,000 ppm to about 25,000 ppm; a cationic polysaccharide derived from a natural source in an amount ranging from about 800 ppm to about 30,000 ppm; or from about 2,000 ppm to about 25,000 ppm; or from about 4,000 ppm to about 20,000 ppm; an organic acid in an amount ranging from about 1,000 ppm to about 35,000 ppm; or from about 5,000 ppm to about 25,000 ppm; or from about 15,000 ppm to about 25,000 ppm; and a surfactant selected from cationic surfactants, amphoteric surfactants, and combinations thereof in an amount ranging from about 2,000 ppm to about 90,000 ppm; or from about 10,000 ppm to about 3 ... From ppm to about 75,000 ppm; or from about 20,000 ppm to about 70,000 ppm.

[0067] The concentrate can be used undiluted (concentrate:water = 1:0) to extremely dilute solutions (e.g., 1:10,000). In one embodiment, the dilution range is from about 1:1 to about 1:1,000. In another embodiment, the dilution range is from about 1:1 to about 1:500. In yet another embodiment, the dilution range is from about 1:10 to about 1:128.

[0068] A method for providing a surface with residual antimicrobial activity is also disclosed, the method comprising the step of applying the composition disclosed herein to the surface.

[0069] The composition can be applied to a surface by any method, including manual methods and machine methods, and combinations thereof. For example, the composition can be applied by spraying (pump, aerosol, pressure, etc.), pouring, spreading, metering (e.g., with a rod or strip), mopping, wiping, brushing, dipping, mechanical application, other application methods, or combinations thereof.

[0070] In the embodiments, the compositions disclosed herein are suitable for “spray and wipe” application. In this type of application, the user typically applies an effective amount of the cleaning composition using a pump, and then wipes the treated area clean with a cloth, towel, or sponge (typically disposable paper towels or sponges) within a few minutes.

[0071] The compositions disclosed herein, whether described herein or in concentrated or super-concentrated form, can also be applied to hard surfaces using a wet wipe. The wipe can be woven or nonwoven in nature. The fabric substrate can include nonwoven or woven pouches, sponges, in the form of abrasive or non-abrasive cleaning pads. Such fabrics are commercially known in this field and are commonly referred to as wipes. Such substrates can be resin-bonded, spunlace, thermally bonded, meltblown, needle-punched, or any combination of the former.

[0072] Nonwoven fabrics can be a combination of wood pulp fibers and synthetic fibers of textile length formed by well-known dry or wet lay-up methods. Synthetic fibers such as rayon, nylon, orylon, and polyester, as well as blends thereof, can be used. Wood pulp fibers should constitute about 30% to about 60% by weight of the nonwoven fabric, preferably about 55% to about 60% by weight, with the remainder being synthetic fibers. Wood pulp fibers provide absorbency, abrasion resistance, and dirt retention, while synthetic fibers provide base strength and resilience.

[0073] The disclosed composition is absorbed onto a wiping cloth to form a saturated wiping cloth. The wiping cloths can then be individually sealed in a pouch and opened as needed, or multiple wiping cloths can be placed in a container for use on a need-to-use basis. The container is fully sealed when closed to prevent any component from evaporating from the composition.

[0074] Also provided are substrates with residual antimicrobial activity, comprising a substrate wherein at least a portion of the substrate is coated with the composition disclosed herein. The formulations disclosed herein can be used by applying to any substrate. Some suitable substrates include, for example, countertops, mirrors, sinks, toilets, light switches, door handles, walls, floors, ceilings, partitions, railings, computer screens, keyboards, instruments, etc. Suitable substrates can be found in a variety of settings, such as food preparation areas, homes, industrial settings, architectural settings, medical settings, sinks, toilets, etc. The substrate can be made of any material; some suitable substrate compositions include, for example, plastics (including, for example, laminates and wall coverings), fire-retardant laminates, metals, glass, tiles, paper (e.g., wallpaper), fabrics, finished or unfinished wood, etc.

[0075] The use of the compositions disclosed herein for substantially reducing or controlling the formation of microbial colonies on or around a surface is also provided. In one embodiment, a film formed by the composition kills at least 95% of microorganisms within at least three abrasion cycles, according to RSS-12 h. In another embodiment, a film formed by the composition kills at least 95% of microorganisms according to the Environmental Protection Agency (EPA) Protocol #01-1A residual self-disinfecting activity test (e.g., 6 abrasion cycles for a 24-hour requirement). In one embodiment, a film formed by the composition kills at least 95% of microorganisms according to BSI-PAS 2424. In another embodiment, a film formed by the composition kills at least 99.9% of microorganisms within at least three abrasion cycles, according to RSS-12 h. In yet another embodiment, a film formed by the composition kills at least 99.9% of microorganisms according to the Environmental Protection Agency (EPA) Protocol #01-1A residual self-disinfecting activity test (e.g., 6 abrasion cycles for a 24-hour requirement). In another embodiment, according to BSI-PAS 2424, the membrane formed by the composition kills at least 99.9% of microorganisms.

[0076] In one embodiment, according to RSS-12 h, the film formed by the composition kills at least 95% of Gram-positive and Gram-negative bacteria, fungi, and / or enveloped and non-enveloped viruses within at least 3 abrasion cycles. In another embodiment, according to the Environmental Protection Agency (EPA) Protocol #01-1A residual self-disinfecting activity test (e.g., 6 abrasion cycles for a 24-hour requirement), the film formed by the composition kills at least 95% of Gram-positive and Gram-negative bacteria, fungi, or enveloped and non-enveloped viruses. In yet another embodiment, according to RSS-12 h, the film formed by the composition kills at least 99.9% of Gram-positive and Gram-negative bacteria, fungi, or enveloped and non-enveloped viruses within at least 3 abrasion cycles. In yet another embodiment, according to the Environmental Protection Agency (EPA) protocol #01-1A residual self-disinfecting activity test (e.g., for a 24-hour requirement, 6 abrasion cycles), the film formed by the composition kills at least 99.9% of Gram-positive and Gram-negative bacteria, fungi, or enveloped and non-enveloped viruses.

[0077] Although specific embodiments have been discussed, this specification is illustrative only and not restrictive. Many variations of this disclosure will become apparent to those skilled in the art upon review of this specification.

[0078] 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 specification pertains.

[0079] As used in this specification and claims, the singular forms “a / an” and “the” include plural indicators unless the context clearly indicates otherwise.

[0080] As used herein, and unless otherwise specified, the terms “about” or “approximately” mean an acceptable error as determined by one of ordinary skill in the art for a particular value, depending in part on how the value is measured or determined. In some embodiments, the terms “about” or “approximately” mean within 1, 2, 3, or 4 standard deviations. In some embodiments, the terms “about” or “approximately” mean within 50%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.05% of a given value or range.

[0081] Furthermore, it should be understood that any numerical ranges listed herein are intended to include all subranges contained therein. For example, the range “1 to 10” is intended to include and encompass all subranges between the listed minimum value of 1 and the listed maximum value of 10; that is, a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because these disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless otherwise clearly indicated, the various numerical ranges specified in this application are approximate values.

[0082] This disclosure will be further described with reference to the following examples. These examples are illustrative only and are not intended to be limiting.

[0083] Example 1. Evaluation of biocidal activity of membrane residues: BSI-PAS 2424 protocol. Membranes prepared from formulations A and B (Table 1) were evaluated using the BSI-PAS 2424 protocol as described above.

[0084] Table 1. Example 2. The effect of nonionic surfactants on film spreading was studied on polycarbonate surfaces.

[0085] Compositions with improved wettability (Formulation C) are shown in Table 2 below.

[0086] Table 2. Preparation C 100 μL equal portions of formulations A and C were evenly spread on a polycarbonate (1 inch × 1 inch) substrate and imaged at 10-second intervals. Liquid formulation A immediately began to dewet and receded into the pool, while the liquid film of formulation C remained essentially static and covered the entire substrate, dewetting slightly from the corners.

[0087] Preparation A (wetted at 5 minutes) <50% of surface area.

[0088] Preparation C (wetted at 5 minutes) > 90% of surface area.

[0089] The liquid film is dried to form a uniformly spread film with greater coverage on the surface, and then used to test biocidal activity through a more stringent RSS-12 h test.

[0090] Example 3. Assessment of biocidal activity of membrane residues: EPA protocol.

[0091] The membrane prepared from formulation C was evaluated using the RSS-12 h protocol (a modified version of the Residual Self-Disinfecting (RSS) method, EPA Protocol #01-1A) as described above. Protocol #01-1A is an EPA-approved method for measuring long-term disinfection requirements (i.e., "kill later" durability requirements). Protocol #01-1A (the entire contents of which are incorporated herein by reference) measures the residual self-disinfecting activity of a dried chemical residue (membrane) against the following bacteria on a non-living, rigid, non-porous surface: Golden yellow staphylococcus , Klebsiella pneumoniae ,and / Or Enterobacter aerogenes Specifically, the surface was seeded, treated with the test product, dried, and then abraded under alternating wet and dry conditions, interspersed with several re-seedings. Figure 1 ).

[0092] The tests shown in Table 3 were performed on a steel substrate (1 inch × 1 inch) with *Enterobacter aerogenes* (a generally more resistant Gram-negative bacterium). The tests were performed in triplicate with formulation C (1-3) using surfactant Triton X-100 (1-3) as a control. Initial, intermediate (24 h), and final inoculation intensities are shown using the surviving microbial population as indicated by plate counts (cfu / ml, colony-forming units / mL) at the end of the final inoculation. All films were prepared by aspirating 150 μL of formulation C and allowing them to air dry. Formulation C provided an average reduction of >3 log bacterial population or >99.9% kill rate when applied to the steel surface. The passing threshold, as outlined in typical surface disinfection tests and as outlined in the RSS-12 h above, is a reduction of 3 log.

[0093] Table 3. Preparation C on stainless steel contaminated with Enterobacter aerogenes.

[0094] Example 4. The effect of RSS-12 and reduced "quaternary ammonium compound" content.

[0095] Disinfectant formulation C appears quite robust when providing >3 LR, even with reduced treatment volumes. This further applies to reducing the total biocide "quaternary ammonium compound" concentration while keeping all other components constant. Total "quaternary ammonium compound" is the sum of the typical "quaternary ammonium compounds" in ppm, allowing for significant reductions in the amount in formulation C from 0.7% w / w (7000 ppm) to 200 ppm, 500 ppm, and 1000 ppm. All membranes were prepared by aspirating 150 μL of the formulation onto a (1 × 1) inch steel substrate and allowing it to air dry. These modified compositions were tested on the steel substrate with Enterobacter aerogenes, as shown in Table 4, and via the RSS-12 protocol as needed at >3 LR.

[0096] Table 4. Modified formulation C with different amounts of "quaternary ammonium compound" (150 μL) on stainless steel containing Enterobacter aerogenes.

[0097] Example 5. Testing RSS-24 Formulation C was then further evaluated using the (EPA) protocol #01-1A residual self-disinfecting activity test, which requires six alternating abrasion cycles (wet and dry) over 24 hours. This test (specified RSS-24) is more aggressive than RSS-12, which has twice the number of wet and dry abrasion cycles and also involves five re-inoculations instead of the three required for RSS-12. It must be noted that the % relative humidity (%RH) is within the (45–55)% test range. When evaluated with 150 μL of formulation C on a (1 × 1) steel substrate containing *Enterobacter aerogenes*, a pass rate of >3LR (Table 5) indicates that RSS-24 has been passed.

[0098] Table 5. RSS-24 of formulation C (150 μL) on stainless steel contaminated with Enterobacter aerogenes.

[0099] The disclosed subject matter has been described in detail with reference to its specific embodiments. Such details are not intended to be considered as a limitation on the scope of the disclosed subject matter unless they are included in the appended claims and to that extent.

[0100] Therefore, the exemplary embodiments described herein are well adapted to achieve the mentioned purposes and advantages, as well as those inherent therein. The specific embodiments disclosed above are merely illustrative, as the exemplary embodiments described herein can be modified and practiced in ways that are obvious to those skilled in the art, but are equivalent, and that benefit from the teachings herein. Furthermore, no limitation is intended to be made on the details of the structures or designs shown herein, except as described in the following claims. It is therefore apparent that the specific illustrative embodiments disclosed above can be changed, combined, or modified, and all such changes are considered to be within the scope and spirit of the exemplary embodiments described herein. The exemplary embodiments described herein, which are illustratively disclosed herein, can be appropriately practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein. While compositions and methods are described as “comprising,” “containing,” or “including” various components or steps, these compositions and methods can also be “substantially composed of” or “comprise” these various components, substances, and steps. As used herein, the term "consistently comprising" should be understood to mean including the listed components, substances, or steps, as well as any additional components, substances, or steps that do not substantially affect the fundamental and novel characteristics of the composition or method. In some embodiments, a composition according to an embodiment of this disclosure is "consistently comprising" the listed components or substances, excluding any additional components or substances that alter the fundamental and novel characteristics of the composition. In the event of any conflict in the use of words or terms in this specification or in one or more patents or other documents incorporated herein by reference, the definitions consistent with this specification shall prevail.

Claims

1. A hard surface treatment composition comprising: a. An antimicrobial component containing at least one quaternary ammonium compound; b. Cationic polysaccharides derived from natural sources; c. Organic acids; and d. Surfactants selected from the group consisting of: Cationic surfactants, amphoteric surfactants, nonionic surfactants, and combinations thereof.

2. The composition of claim 1, wherein, According to RSS-12 h, the film formed by this composition kills at least 95% of microorganisms within at least 3 abrasion cycles.

3. The composition of claim 1, wherein, The antimicrobial component is selected from the group consisting of monoalkyl dimethyl benzyl ammonium salts, dialkyl dimethyl ammonium salts, and combinations thereof.

4. The composition of claim 1, wherein, The cationic polysaccharide is selected from the following group, which consists of cationic guar gum, cationic cellulose, cationic starch, and combinations thereof.

5. The composition according to claim 4, wherein, This cationic polysaccharide is cationic guar gum.

6. The composition according to claim 5, wherein, The cationic guar gum is selected from the group consisting of: guar gum hydroxypropyltrimethylammonium chloride, hydroxypropyl guar gum hydroxypropyltrimethylammonium chloride, and combinations thereof.

7. The composition of claim 1, wherein, The organic acid is selected from the following group, which consists of the following: Citric acid, malic acid, maleic acid, lactic acid, succinic acid, glutaric acid, adipic acid, and combinations thereof.

8. The composition of claim 1, wherein, The surfactant includes cationic surfactants selected from the group consisting of cationic amine oxides, cationic betaines, propionates, amphoteric acetates, and combinations thereof.

9. The composition of claim 1, wherein, The surfactant includes amphoteric surfactants selected from the group consisting of sulfobetaine, taurine esters, and combinations thereof.

10. The composition of claim 1, further comprising a polar solvent.

11. The composition of claim 1, wherein, According to the Environmental Protection Agency (EPA) Programme #01-1A residual self-disinfecting activity test, the film formed by the composition kills at least 95% of Gram-positive and Gram-negative bacteria, or enveloped and non-enveloped viruses.

12. A hard surface treatment concentrate composition comprising: a. An antimicrobial component comprising at least one quaternary ammonium compound in an amount ranging from 800 ppm to about 40,000 ppm; b. Cationic polysaccharides derived from natural sources, in amounts ranging from about 800 ppm to about 30,000 ppm; c. Organic acids, in amounts ranging from about 1,000 ppm to about 35,000 ppm; and d. Surfactants selected from the group consisting of: Cationic surfactants, amphoteric surfactants, nonionic surfactants, and combinations thereof, in amounts ranging from about 2,000 ppm to about 90,000 ppm.

13. A method for providing a surface with residual antimicrobial activity, the method comprising the step of applying the composition of claim 1 to the surface.

14. A substrate having residual antimicrobial activity, comprising a substrate wherein at least a portion thereof is coated with the composition of claim 1.

15. Use of the composition of claim 1 for substantially reducing or controlling the formation of microbial colonies on or at a surface.

16. The use as described in claim 15, wherein, According to a modified version of the Environmental Protection Agency (EPA) Programme #01-1A residual self-disinfecting activity test, the film formed by the composition kills at least 95% of Gram-positive and Gram-negative bacteria, or enveloped and non-enveloped viruses.

17. The use as described in claim 15, wherein, According to the Environmental Protection Agency (EPA) Programme #01-1A residual self-disinfecting activity test, the film formed by the composition kills at least 95% of Gram-positive and Gram-negative bacteria, or enveloped and non-enveloped viruses.

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