Long-lasting disinfectant cleaning compositions and methods of use thereof

Abstract

The present disclosure provides an antimicrobial composition comprising an antimicrobial component having at least one quaternary ammonium compound; a synthetic polymer comprising at least one cationic monomer Ab, optionally at least one anionic monomer Ba, and optionally at least one nonionic monomer Ca; an organic acid; and a surfactant selected from cationic surfactants, amphoteric surfactants, and combinations thereof; and at least one nonionic surfactant selected from the group consisting of low hydrophile-lipophile balance (HLB) nonionic surfactants with a delocalized electronic structure having moderate to poor water solubility. When applied to surfaces, the composition exhibits good cleaning ability and provides strong, long-lasting disinfection.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 62 / 804,923, filed February 13, 2019, the entire disclosure of which is incorporated herein by reference. [Background technology]

[0002] Antimicrobial compositions marketed as disinfectants or cleaners with germicidal activity typically achieve greater than 99.9% kill of bacteria or viruses only at the time of use. Recontamination of "clean" surfaces allows microorganisms to survive and spread by contact until they are treated again. The germicidal cleaner market currently does not address long-lasting disinfection in high-touch areas, including homes, public places, and healthcare environments. This creates a demand from today's health-conscious consumers who care about a clean home but lack the time to regularly clean and disinfect.

[0003] A significant technical challenge in developing long-lasting disinfectant cleaning compositions is that cleaning requires the presence of effective surfactants for soil removal, but the presence of such surfactants reduces the durability or long-lasting properties of the residual film. Degradation of the residual disinfectant film makes it very difficult to achieve 12-24 hours of continuous disinfection.

[0004] Re-soiling or contamination of surfaces requires further treatment with such compositions. Thus, there is a need for disinfectant cleaning formulations that provide high microbial kill without the need for repeated applications. However, designing compositions that meet the above requirements is a difficult task given the unpredictable and complex interactions between the components. [Brief explanation of the drawings]

[0005] [Figure 1]1 is a flowchart showing the RSS-12h analysis performed in the examples. [Figure 2] It provides a frame of reference for adjusting cleaning applications to desired performance. [Figure 3] This shows poor cleaning performance of a long-lasting disinfectant (Formula A pH 4.5). [Figure 4] 1 shows the effect of varying amounts of TSP-8EO on cleaning performance. [Figure 5] 1 shows the cleaning impact of a formulation containing a blend of TSP-4EO and TSP-8EO compared to Benchmark A. [Figure 6] 10 demonstrates an embodiment in which removal of lactic acid improves wetting of the substrate. [Figure 7] The effect of various nonionic surfactants on cleaning is shown. Summary of the Invention

[0006] The present disclosure provides an antimicrobial composition comprising an antimicrobial component comprising at least one quaternary ammonium compound, at least one cationic monomer A b , optionally at least one anionic monomer Ba, and optionally at least one nonionic monomer C a A hard surface treatment composition is provided, comprising a surfactant selected from a synthetic polymer comprising: an organic acid; a cationic surfactant; an amphoteric surfactant; and a combination thereof; and at least one nonionic surfactant selected from a low hydrophilic-lipophilic balance (HLB) nonionic surfactant with a delocalized electronic structure having moderate to poor water solubility. A method for providing residual antimicrobial activity to a surface is also provided, comprising applying a composition of the present disclosure to the surface. The present disclosure also provides a substrate having residual antimicrobial activity, including a substrate where at least a portion of the substrate is coated with a composition of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present disclosure relates to cleaning compositions that provide continuous surface disinfection benefits for 12 to 24 hours with a single application, eliminating the need for repeated decontamination. The cleaning effectiveness of these compositions is provided by including low hydrophile-lipophile balance (HLB) nonionic surfactants with a delocalized electronic structure that has moderate to poor water solubility. Such disinfectant cleaning compositions provide long-lasting disinfection while providing a residual film that is abrasion-resistant to wet and dry wiping.

[0008] The compositions achieve at least 95% or greater kill (e.g., 99.9% kill) of microorganisms (e.g., bacteria, viruses, or fungi) in 12 to 24 hours without the need for repeated treatment. To verify the 24-hour long-term disinfection claim by the U.S. Environmental Protection Agency (EPA), the compositions are evaluated using the Residual Self-Disinfection (RSS) method, EPA Protocol #01-1A (https: / / www.epa.gov / sites / production / files / 2015-09 / documents / cloroxpcol_final.pdf). To verify long-term disinfection, all existing test protocols typically emulate the maximum amount of recontamination and abrasion over a 24-hour period, with expected contact and wiping before reapplication. An intermediate protocol, involving approximately half the level of abrasion and redeposition to the surface, is presented herein as the "RSS-12h" test protocol.

[0009] In one embodiment, a film formed from the composition kills at least 99.9% (e.g., a log3 reduction) of microorganisms according to the Residual Self-Disinfecting (RSS) Activity Test (EPA Protocol #01-1A). In one embodiment, a film formed from the composition kills at least 99.9% (e.g., a log3 reduction) of gram-positive and gram-negative bacteria according to the Residual Self-Disinfecting (RSS) Activity Test (EPA Protocol #01-1A).

[0010] The long-lasting kill claim is demonstrated by the RSS test, which challenges the applied composition by subjecting it to recontamination (reinoculation with microorganisms) and abrasion (wear cycles). An intermediate test protocol ("RSS-12h") with approximately half the number of reinoculation and abrasion cycles is used to predict durable kill for up to 12 hours before reapplication of the test product. As outlined in Figure 1, this procedure requires preparation of test bacterial (microbial) cultures over the first week (see EPA Protocol #01-1A), followed by testing in the second week.

[0011] The test involves inoculating the surface with bacteria, followed by applying the product to the substrate and allowing it to dry. The substrate can be glass, polycarbonate, or steel. The substrate is then subjected to abrasion—a re-inoculation regimen of three "wear cycles." Abrasion is performed on a 1084 gwt rectangular steel block covered with fabric with a thin polyurethane foam layer underneath. Each wear cycle consists of a "dry" abrasion and a "wet" abrasion, the latter in which the fabric cover is wetted with a mist of water using Preval® spray. Each abrasion (dry / wet) is characterized by a back-and-forth movement of the block across the test substrate. Following each abrasion cycle, the surface is re-inoculated with bacterial cultures. The RSS-12h includes a three-wear cycle / three-inoculation test regimen, compared to the full RSS test, which outlines a six-wear cycle / six-inoculation test regimen. All other details of the test method are as outlined in EPA Protocol #01-1A.

[0012] The test substrate is allowed to dry overnight, then finally inoculated again for 5 minutes (disinfectant test), followed by total substrate neutralization. Surviving bacteria are then harvested from the surface, serially diluted and cultured on agar plates, and allowed to form colonies over 24-48 hours. The surviving bacteria are then counted as the number of colonies. The difference between the number of inoculated and surviving bacteria provides an efficacy rating on a logarithmic scale: kill (e.g., 99.9% kill) or log reduction (e.g., 3 log reduction). Other microorganisms, such as fungi or viruses, can be substituted for bacteria in this test. In one embodiment, the microorganism is 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.

[0013] The composition of the present disclosure is a liquid formulation.One preferred method of using the composition of the present disclosure is to apply a layer of the composition to a substrate and then dry the composition or allow the composition to dry.The action of applying a layer of the composition to a substrate and then drying it or allowing it to dry is known herein as "treating" the substrate.When the solvent evaporates, the composition is considered to form a film on the substrate.The dried layer of the composition is known herein as a "film".

[0014] In one embodiment, the composition comprises an antimicrobial component comprising at least one quaternary ammonium compound, at least one cationic monomer A b , optionally at least one anionic monomer B a and optionally at least one nonionic monomer C aThe composition comprises at least one nonionic surfactant selected from the group consisting of a synthetic polymer comprising the compound (I), an organic acid, a cationic surfactant, an amphoteric surfactant, and a combination thereof, and a low HLB nonionic surfactant with a delocalized electronic structure and moderate to poor water solubility. In one embodiment, the composition comprises two or more (e.g., three, four, five, etc.) nonionic surfactants selected from the group consisting of a low HLB nonionic surfactant with a delocalized electronic structure and moderate to poor water solubility.

[0015] In one embodiment, the nonionic surfactant is selected from the group consisting of nonionic surfactants with a delocalized electronic structure having an HLB value of less than 9. In one embodiment, the nonionic surfactant is selected from the group consisting of nonionic surfactants with a delocalized electronic structure having an HLB value of less than 8. In one embodiment, the nonionic surfactant is selected from the group consisting of nonionic surfactants with a delocalized electronic structure having an HLB value of less than 7. In one embodiment, the nonionic surfactants have a combination of different HLB values. In one embodiment, the low HLB nonionic surfactant with a delocalized electronic structure and moderate to poor water solubility is selected from the group consisting of tristyrylphenol ethoxylates, terpene alkoxylates, alkanolamides, and combinations thereof. In one embodiment, the low HLB nonionic surfactant with a delocalized electronic structure and moderate to poor water solubility is selected from the group consisting of amine surfactants. In one embodiment, the nonionic surfactant is a tristyrylphenol ethoxylate with a low degree of ethoxylation (e.g., less than 8 ethylene oxide (EO) moieties).

[0016] In one embodiment, the pH of the composition ranges from about 0 to about 5.5. In another embodiment, the pH of the composition is less than 5.5. In another embodiment, the pH of the composition ranges from 2 to 4.9. In yet another embodiment, the pH of the composition ranges from 3 to 4.8. In one embodiment, the pH of the composition ranges from 0.5 to 3.

[0017] The antimicrobial compositions of the present disclosure include at least one quaternary ammonium compound. In one embodiment, the quaternary ammonium compound is an antimicrobial "quat." The term "quaternary ammonium compound" or "quat" generally refers to a compound having the following formula: TIFF0007758569000001.tif41161, where R1-R4 are alkyl groups that can be similar or different, substituted or unsubstituted, saturated or unsaturated, branched or unbranched, and cyclic or acyclic, and can contain ether, ester, or amide linkages, which can be aromatic or substituted aromatic groups. In one embodiment, the groups R1, R2, R3, and R4 each have a chain length of less than C20. X - is an anionic counterion. The term "anionic counterion" includes any ion capable of forming a salt with a quaternary ammonium. Examples of suitable counterions include halides such as chloride, bromide, fluoride, and iodide, sulfonate, propionate, methosulfate, saccharinate, ethosulfate, hydroxide, acetate, phosphate, carbonate, bicarbonate, and nitrate. In one embodiment, the anionic counterion is chloride.

[0018] In some embodiments, quaternary ammonium compounds having carbon chains of less than 20 or C2-C20 are included in the compositions of the present disclosure. In other embodiments, quaternary ammonium compounds having carbon chains of C6-C18, C12-C18, C12-C16, and C6-C10 are included in the compositions of the present disclosure. Examples of quaternary ammonium compounds useful in the present disclosure include, but are not limited to, alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, and didecyl dimethyl ammonium chloride. A single quaternary ammonium compound or a combination of two or more quaternary ammonium compounds may be included in the compositions of the present disclosure. Further examples of quaternary ammonium compounds useful in the present disclosure include, but are not limited to, benzethonium chloride, ethylbenzylalkonium chloride, ethylbenzethonium chloride, myristyltrimethylammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium chloride (CTAB), carnitine, dophanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride, choline, denatonium, and mixtures thereof.

[0019] 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, bisquaternary ammonium salts, and polymeric quaternary ammonium salts, each of which is discussed herein.

[0020] Monoalkyltrimethylammonium salts contain one R group that is a long-chain alkyl group, and the remaining R groups are short-chain alkyl groups, such as methyl or ethyl groups. Some non-limiting examples of monoalkyltrimethylammonium salts include cetyltrimethylammonium bromide, available commercially under the trade names Rhodaquat® M242C / 29 and Dehyquart® A, alkyltrimethylammonium chloride, available commercially as Arquad® 16, alkylaryltrimethylammonium chloride, and cetyldimethylethylammonium bromide, available commercially as Ammonyx® DME.

[0021] Monoalkyldimethylbenzylammonium salts contain one R group that is a long-chain alkyl group, a second R group that is a benzyl radical, and the remaining two R groups are short-chain alkyl groups, such as methyl or ethyl groups. Some non-limiting examples of monoalkyldimethylbenzylammonium salts include alkyldimethylbenzylammonium chloride, available commercially as Barquat® from Lonza Inc., and benzethonium chloride, available commercially as Lonzagard® from Lonza Inc. Additionally, monoalkyldimethylbenzylammonium salts can be substituted; a non-limiting example of such salts is dodecyldimethyl-3,4-dichlorobenzylammonium chloride. Finally, there is the mixture of alkyldimethylbenzyl and alkyldimethyl-substituted benzyl(ethylbenzyl)ammonium chloride, available commercially as BTC® 2125M from Stepan Company and 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-dimethyl-N-benzyl-N-octadecylammonium chloride.

[0022] Dialkyldimethylammonium salts contain two R groups that are long-chain alkyl groups, and the remaining R groups are short-chain alkyl groups, such as methyl groups. Some non-limiting examples of dialkyldimethylammonium salts include didecyldimethylammonium halide, commercially available from Lonza Inc. as Bardac® 22, didecyldimethylammonium chloride, commercially available from Lonza Inc. as Bardac® 2250, dioctyldimethylammonium chloride, commercially available from Lonza Inc. as Bardac® LF and Bardac® LF-80, and octyldecyldimethylammonium chloride, sold as a mixture with didecyl and dioctyldimethylammonium chloride, commercially available from Lonza Inc. as Bardac® 2050 and 2080.

[0023] Heteroaromatic ammonium salts contain one R group that is a long-chain alkyl group, and the remaining R groups are provided by some aromatic system. Thus, 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 cetylpyridinium halide, available commercially as Sumquat® 6060 / CPC from Zeeland Chemical Inc., 1-[3-chloroalkyl]-3,5,7-triaza-1-azoniaadamantane, available commercially as Dowicil® 200 from The Dow Chemical Company, and alkyl-isoquinolinium bromide.

[0024] Polysubstituted quaternary ammonium salts are monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, or heteroaromatic ammonium salts, where the anionic portion of the molecule is a large, high molecular weight (MW) organic ion. Some non-limiting examples of polysubstituted quaternary ammonium salts include alkyldimethylbenzylammonium saccharinate and dimethylethylbenzylammonium cyclohexylsulfamate.

[0025] Bis-quaternary ammonium salts have the general formula: TIFF0007758569000002.tif26161 (wherein the R groups can be long- or short-chain alkyl, benzyl radicals, or can be provided by aromatic systems. Z is a carbon-hydrogen chain attached to each quaternary nitrogen.) Some non-limiting examples of bisquaternary ammonium salts include 1,10-bis(2-methyl-4-aminoquinolinium chloride)-decane and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride]hexane, or triclobismium chloride.

[0026] In one embodiment, the quaternary ammonium compounds are medium to long chain alkyl R groups, such as 8 carbons to about 20 carbons, 8 carbons to about 18 carbons, about 10 to about 18 carbons, and about 12 to about 16 carbons, which provide good solubility and antimicrobial properties.

[0027] In one embodiment, the quaternary ammonium compound is a short dialkyl chain quaternary ammonium compound having an R group of from 2 carbons to about 12 carbons, from 3 carbons to about 12 carbons, or from 6 carbons to about 12 carbons.

[0028] The composition can include from about 100 to about 20,000 ppm of one or more quaternary ammonium compounds. In various embodiments, the composition includes from about 500 to about 20,000 ppm, from about 500 to about 10,000 ppm, from about 100 to about 500 ppm, or from about 500 to about 5000 ppm of one or more quaternary ammonium compounds.

[0029] Polymers suitable for use in the compositions of the present disclosure include polymers containing at least one cationic monomer A b , optionally at least one anionic monomer B a and optionally at least one nonionic monomer C a In one embodiment, the synthetic polymer includes a homopolymer, copolymer, terpolymer, block copolymer, random polymer, linear polymer, comb polymer, or branched polymer thereof.

[0030] Any combination of these types of monomers can be used. For example, suitable polymers include: b and at least one monomer of type B a Polymers of type A comprising, consisting of, or consisting essentially of at least one monomer of b and at least one monomer of type C a and polymers comprising, consisting of, or consisting essentially of at least one of each of the three types of monomers.

[0031] In one embodiment, the cationic monomer A bcomprises an ammonium group of formula -NR3+, where R is the same or different and represents a hydrogen atom, an alkyl group containing 1 to 10 carbon atoms, or a benzyl group, optionally bearing a hydroxyl group, and comprises an anion (counterion). Examples of anionic counterions are halides such as chloride and bromide, sulfate, hydrosulfate, alkyl sulfates (e.g., containing 1 to 6 carbon atoms), sulfonate, phosphate, nitrate, citrate, carbonate, bicarbonate, formate, and acetate.

[0032] Cationic Monomer A b Examples include, but are not limited to: TIFF0007758569000003.tif17161

[0033] Diallyldimethylammonium halides, such as diallyldimethylammonium chloride (DADMAC) or the corresponding bromides. Alternatively, the counterion can be sulfate, nitrate, or phosphate. One or more CH3 groups can be C2- 12 Similar monomer units can be used, such as those in which one or more CH groups are replaced with, for example, a C alkyl group, or one or more CH groups are replaced with an alkyl group having 2 to 12 carbon atoms, for example, 2 to 6 carbon atoms. In other words, other similar commercially available monomers or polymers containing such monomers can be used. TIFF0007758569000004.tif15161

[0034] N,N,N-trimethyl-3-((2-methyl-1-oxo-2-propenyl)amino)-1-propanaminium halide, for example chloride (MAPTAC, also known as methacryl-amido(propyl)-trimethylammonium halide).

[0035] Cationic Monomer A b Further examples include, but are not limited to: 1. Aminoalkyl (meth)acrylate, aminoalkyl (meth)acrylamide, 2. Monomers containing at least one secondary, tertiary or quaternary amine functional group or a heterocyclic group containing a nitrogen atom, vinylamine or ethyleneimine, in particular (meth)acrylate and (meth)acrylamide derivatives. 3. Diallyldialkylammonium salts, 4. Mixtures thereof, salts thereof, and macromonomers derived therefrom; 5. Dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ditert-butylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, 6. Ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine, 7. Trimethylammonium ethyl (meth)acrylate chloride, trimethylammonium ethyl (meth)acrylate methyl sulfate, dimethylammonium ethyl (meth)acrylate benzyl chloride, 4-benzoylbenzyldimethylammonium ethyl acrylate chloride, trimethylammonium ethyl (meth)acrylamide (2-(acryloxy)ethyltrimethylammonium, also known as TMAEAMS) chloride, trimethylammonium ethyl (meth)acrylate (2-(acryloxy)ethyltrimethylammonium, also known as TMAEAMS) methyl sulfate, trimethylammonium propyl (meth)acrylamide chloride, vinylbenzyltrimethylammonium chloride, 8. Diallyldimethylammonium chloride, 9. The following formula A(II): TIFF0007758569000005.tif39161 (wherein R1 is a hydrogen atom or a methyl group or an ethyl group; R2, R3, R4, R5, and R6 are the same or different and are linear or branched C1 to C6, preferably C1 to C4, alkyl, hydroxyalkyl, or aminoalkyl groups; m is an integer of 0 to 10, for example 1; n is an integer of 1 to 6, preferably 2 to 4; Z represents a -C(O)O- or -C(O)NH- group or an oxygen atom; A is (CH2) p group, p is an integer of 1 to 6, preferably 2 to 4, and B is a linear or branched C2-C 12 , typically C3 to C6, optionally interrupted by one or more heteroatoms or heterogroups, in particular O or NH, and optionally substituted by one or more hydroxyl or amino groups, preferably hydroxyl groups, and X, identical or different, represents a counterion, and mixtures thereof, and macromonomers derived therefrom).

[0036] Other cationic monomers have the general formula A(I): TIFF0007758569000006.tif34161, wherein R1 and R4, independently of one another, represent a hydrogen atom or a linear or branched C1-C6 alkyl group; R2 and R3, independently of one another, represent an alkyl, hydroxyalkyl, or aminoalkyl group, where the alkyl group is a linear or branched C1-C6 chain, preferably a methyl group; n and m are integers from 1 to 3; and X represents a counterion, which may be the same or different, compatible with the water-soluble or water-dispersible properties of the polymer. In one embodiment, X is selected from the group consisting of a halide anion, sulfate anion, hydrogen sulfate anion, phosphate anion, nitrate anion, citrate anion, formate anion, or acetate anion.

[0037] The polymers used in the present invention may have a polymeric amphoteric structure, with charge and surface adsorption determined by pH. In one embodiment, the polymer is an acrylic acid amine-functional polymer. Examples of suitable hydrophilic polymers are described in U.S. Pat. Nos. 6,569,261, 6,593,288, 6,703,358, and 6,767,410, the disclosures of which are incorporated herein by reference. These documents describe water-soluble or water-dispersible copolymers comprising, in the form of polymerized units, (1) at least one amine-functional monomer, (2) at least one hydrophilic monomer having acidic properties, and (3) optionally at least one neutral hydrophilic monomer having ethylenic unsaturation. The copolymer comprises a quaternary ammonium acrylamido acid copolymer.

[0038] Anionic Monomer B a Examples of the acrylic acid include, but are not limited to, acrylic acid, methacrylic acid, α-ethacrylic acid, β,β-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylideneacetic acid, propylideneacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacryloylalanine, N-acryloylhydroxyglycine, sulfopropyl acrylate, sulfoethyl acrylate, sulfoethyl methacrylate, sulfoethyl methacrylate, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, phosphoethyl acrylate, phosphonoethyl acrylate, phosphopropyl acrylate, phosphonopropyl acrylate, phosphoethyl methacrylate, phosphonoethyl methacrylate, phosphopropyl methacrylate, and phosphonopropyl methacrylate, and the ammonium and alkali metal salts of these acids.

[0039] Examples of nonionic monomers Ca include alkyl acrylates, 2-(dimethylamino)ethyl methacrylate (DMAEMA), TIFF0007758569000007.tif45161N-vinylpyrrolidone (NVP), N-vinylimidazole, acrylamide, and TIFF0007758569000008.tif55161, methacrylamide.

[0040] Examples of polymers suitable for use in the compositions of the present disclosure are polymers comprising, consisting of, or consisting essentially of DMAEMA, MAPTAC, and methylacrylic acid.

[0041] Suitable polymers include those sold under the trade name Mirapol® as Mirapol® Surf-SHO, Mirapol® Surf-S110, Mirapol® HSC-310, Mirapol® CP-412, Mirapol® Surf-S200 or Mirapol® Surf-S500, available from Solvay, Novecare.

[0042] Other suitable polymers include polymers comprising, consisting of, or consisting essentially of DADMAC and acrylamide, such as those sold by Surfacare under the tradename Polyquat® 7 or PQ7, or by Lubrizol under the tradename Merquat® S. Other suitable polymers include polymers comprising, consisting of, or consisting essentially of DADMAC and methacrylamide and / or acrylic acid or methacrylic acid.

[0043] Polymers comprising, consisting of, or consisting essentially of MAPTAC and acrylamide or methacrylamide are also suitable for use in the compositions of the present disclosure. Polymers comprising, consisting of, or consisting essentially of MAPTAC and vinylpyrrolidone, such as Polyquat® 28, are also suitable. Suitable polymers include those sold under the trade names Polyquart® Pro (polyquat 28 and silicone) and BASF's Polyquart® Ampo 140.

[0044] Other suitable polymers include polymers comprising, consisting of, or consisting essentially of MAPTAC and acrylic acid or methacrylic acid, such as those sold under the trade name Polyquat® Ampho, e.g., Polyquat® Ampho 149.

[0045] Polymers comprising, consisting of, or consisting essentially of DMAEMA and vinylpyrrolidone are suitable for use in the compositions of the present disclosure. An example of such a polymer is sold by BRB International under the name PQ11.

[0046] Other suitable polymers include polymers comprising, consisting of, or consisting essentially of DMAEMA and acrylamide, such as those sold under the trade name Polyquat® 5.

[0047] In one embodiment, the molecular weight of the polymer ranges from about 130,000 g / mol to about 2 million g / mol.

[0048] In one embodiment, the amount of polymer in the composition ranges from about 200 ppm to about 4000 ppm.

[0049] The compositions of the present disclosure further comprise one or more organic acids. In one embodiment, 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 counterion acid can be a polymeric acid, such as poly(acrylic acid) or other polycarboxylic acids (e.g., maleic anhydride, methacrylic acid, etc.), or homopolymers or copolymers thereof (e.g., methyl methacrylate, butyl acrylate, etc.), such as those in the Rhodoline® series available from Solvay. The compositions can contain 500 to 7,000 ppm of one or more organic acids.

[0050] In the compositions of the present disclosure, the surfactant is selected from cationic surfactants, amphoteric surfactants, and combinations thereof. Cationic surfactants are surfactants that dissolve in water and provide a net cationic charge. In one embodiment, when present, the cationic surfactant is selected from cationic amine oxides, cationic betaines, propionates, amphoacetates, and combinations thereof. Amine oxides, propionates, amphoacetates, and betaines are cationic under the acidic pH conditions of the present disclosure. In one embodiment, the propionates are selected from cationic C8-C22 propionates and salts thereof. In another embodiment, the cationic C8-C22 propionates are selected from alkylampho(di)propionates, alkylaminopropionates, alkylamphopropionates, salts thereof, and combinations thereof. In one embodiment, the cationic amphoacetates are represented by the following formula: amphoacetate according to TIFF0007758569000009.tif16161, and the following formula: Diamphoacetates according to TIFF0007758569000010.tif27161, where R is an aliphatic group of 8 to 18 carbon atoms and M is a cation such as sodium, potassium, ammonium, or substituted ammonium. Sodium lauroamphoacetate, sodium cocoamphoacetate, disodium lauroamphoacetate, and disodium cocoamphodiacetate are preferred in some embodiments.

[0051] In one embodiment, the betaine is selected from cationic C8-C22 betaines and salts thereof. In a further embodiment, the cationic C8-C22 betaine is selected from alkyl dimethyl betaines, alkyl amidopropyl betaines, alkyl ampho(di)acetates, salts thereof, and combinations thereof. When referring to "salts thereof" of cationic surfactants herein, 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. The use of alternative salts, e.g., alkaline earth metal salts such as Ca and Mg, is also contemplated, although the solubility of the product may need to be considered when using such salts.

[0052] The amphoteric surfactant comprises both a basic and an acidic hydrophilic group and an organic hydrophobic group. In one embodiment, when present, the amphoteric surfactant is selected from sultaines, taurates, and combinations thereof. In one embodiment, the composition comprises a combination of one or more cationic and amphoteric surfactants.

[0053] In addition to the ingredients described herein, the compositions may also include polar carrier solvents (e.g., water), chelating agents, fragrances, preservatives, dyes, corrosion inhibitors, builders, cleaning solvents, and other ingredients known to be useful in antimicrobial compositions.

[0054] Compositions according to the present disclosure include both disinfectant cleaning compositions and concentrates that vary only in the relative ratio of water to other ingredients. The concentrates can be used undiluted (1:0 concentrate:water) to very dilute (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.

[0055] Also disclosed is a method of providing residual antimicrobial activity to a surface, comprising applying a composition of the present disclosure to the surface.

[0056] The composition may be applied to a surface by any method, including manual and mechanical methods and combinations thereof. For example, the composition may be applied by spraying (pump, aerosol, pressure, etc.), pouring, spreading, metering (e.g., with a pole or wand), wiping, wiping, brushing, dipping, mechanical application, other application methods, or combinations thereof.

[0057] In one embodiment, the compositions of the present disclosure are suitable for use in a "spray and wipe" application. In such applications, the user typically applies an effective amount of the cleansing composition using a pump and then wipes the treated area with a cloth, towel, or sponge, typically a disposable paper towel or sponge, within minutes.

[0058] The compositions of the present disclosure, whether as described herein or in the form of concentrates or super concentrates, can also be applied to hard surfaces using wet wipes. The wipes can be woven or nonwoven. 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 the art and are often referred to as wipes. Such substrates can be resin-bonded, hydroentangled, thermally bonded, meltblown, needle-punched, or any combination of the former.

[0059] The nonwoven fabric can be a combination of wood pulp fibers and woven-length synthetic fibers formed by well-known dry-foam or wet-lay processes. Synthetic fibers such as rayon, nylon, Orlon, and polyester, as well as blends thereof, can be used. The wood pulp fibers should comprise 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. The wood pulp fibers provide absorbency, abrasion, and dirt retention, while the synthetic fibers provide the strength and resilience of the substrate.

[0060] The composition of the present disclosure is absorbed into the wipe to form a saturated wipe.The wipes can then be individually sealed in a pouch and opened as needed, or multiple wipes can be placed in a container for use as needed.When the container is closed, it is sufficiently sealed to prevent any ingredients from evaporating from the composition.

[0061] Substrates having residual antimicrobial activity are also provided, including substrates in which at least a portion of the substrate is coated with a composition of the present disclosure. The formulations of the present disclosure can be used by applying them to any substrate. Some suitable substrates include, for example, countertops, mirrors, sinks, toilets, light switches, doorknobs, walls, floors, ceilings, partitions, handrails, computer screens, keyboards, equipment, etc. Suitable substrates can be found in a variety of environments, including, for example, food preparation areas, homes, industrial environments, architectural environments, medical environments, 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), Formica, metal, glass, ceramic tile, paper (such as, for example, wallpaper), fabrics, finished or unfinished wood, etc.

[0062] Use of the compositions of the present disclosure to substantially reduce or control the formation of microbial colonies on or at a surface is also provided. In one embodiment, a film formed from the composition kills at least 95% of microorganisms for at least three abrasion cycles by RSS-12h. In another embodiment, a film formed from the composition kills at least 95% of microorganisms according to Environmental Protection Agency (EPA) Protocol #01-1A Residual Self-Disinfecting Activity Test (e.g., six abrasion cycles for a 24-hour demand). In another embodiment, a film formed from the composition kills at least 99.9% of microorganisms for at least three abrasion cycles by RSS-12h. In yet another embodiment, a film formed from the composition kills at least 99.9% of microorganisms according to Environmental Protection Agency (EPA) Protocol #01-1A Residual Self-Disinfecting Activity Test (e.g., six abrasion cycles for a 24-hour demand).

[0063] In one embodiment, a film formed from the composition kills at least 95% of gram-positive and gram-negative bacteria, fungi, or enveloped and non-enveloped viruses for at least three abrasion cycles by RSS-12h. In another embodiment, a film formed from the composition kills at least 95% of gram-positive and gram-negative bacteria, fungi, or enveloped and non-enveloped viruses according to Environmental Protection Agency (EPA) Protocol #01-1A Residual Self-Disinfecting Activity Test (e.g., six abrasion cycles for a 24-hour requirement). In another embodiment, a film formed from the composition kills at least 99.9% of gram-positive and gram-negative bacteria, fungi, or enveloped and non-enveloped viruses for at least three abrasion cycles by RSS-12h. In yet another embodiment, a film formed from the composition kills at least 99.9% of gram-positive and gram-negative bacteria, fungi, or enveloped and non-enveloped viruses according to Environmental Protection Agency (EPA) Protocol #01-1A Residual Self-Disinfecting Activity Test (e.g., 6 abrasion cycles for a 24-hour requirement).

[0064] While specific embodiments are discussed, this specification is illustrative only and not limiting. Many variations of the present disclosure will become apparent to those skilled in the art upon review of this specification.

[0065] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0066] As used in the specification and claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0067] As used herein, unless otherwise indicated, the term "about" or "approximately" refers to an acceptable error for a particular value as determined by one of ordinary skill in the art, which depends in part on how the value is measured or determined. In certain embodiments, the term "about" or "approximately" means within 1, 2, 3, or 4 standard deviations. In certain embodiments, the term "about" or "approximately" means within 50%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, or 0.05% of the specified value or range.

[0068] It is also understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between and including the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value of 1 or more and a maximum value of 10 or less. The disclosed numerical ranges are continuous, and therefore include all values ​​between the minimum and maximum values. Unless otherwise specified, the various numerical ranges specified in this application are approximations.

[0069] The present disclosure is further described by reference to the following examples, which are illustrative only and are not intended to be limiting. [Example]

[0070] ASTM Procedures for Cleaning ASTM Cleaning Method D4488 is intended to test the performance of products used on resilient floors and washable walls. The method involves soil preparation, cleaning setup, and evaluation of performance under hard surface cleaning conditions. The surfaces are cleaned using a linear cleaning capacity device. The method is designed to mimic the way consumers soil and then clean surfaces. This test is used to test the cleaning effectiveness of all types of multipurpose household cleaners.

[0071] Substrate Preparation: This test protocol requires the preparation of masonite tiles with a double coating of latex paint using a paint roller. The paint must be interior acrylic flat white. The brand of paint is predetermined by the customer to be highly porous to allow for stain absorption. The ASTM method traditionally required the California Paints Brand, but this has since been discontinued. The tiles are then allowed to dry at 45°C for 24 hours before applying the stain. The next day, a pencil mark approximately 3.5 inches long is made in the center of the test area, and cheesecloth is used to delineate the boundaries of where the stain should be applied.

[0072] Cheesecloth Preparation: The stain is applied to the substrate using cheesecloth. The cheesecloth should be cut to dimensions of 18 inches by 36 inches and then folded in half several times to provide a final 2.5 inch by 2 inch piece that should be secured in a large 2 inch binder clip.

[0073] Sponge Preparation: Cellulose sponges are used to clean surface soils. The sponges are cut into four pieces to fit snugly into the sponge box of the abrasion tester, as described below. The sponges are then thoroughly washed, wrung out, and semi-dried before applying the product.

[0074] Stain preparation: A blend of 33% vegetable shortening is combined with 33% lard, 33% vegetable oil, and 1% carbon black. The mixture is warmed at 75°C for 30 minutes and applied 24 hours before testing to freshen the stain.

[0075] Application of Soil to Substrate: Once the oil and carbon black blend is heated and homogenized, it can be applied to the substrate using cheesecloth while maintaining constant heat and mixing. The cheesecloth is soaked in the heated mixture for several minutes to allow it to absorb into the cheesecloth, and then applied downward at a moderate speed in a total of six strokes. Application of the soil to the substrate is perpendicular to the cleaning direction of the scrubbing device. The cheesecloth is soaked in the heated mixture between each stroke.

[0076] Cleaning test: 15g of cleaning agent is pipetted evenly across the surface of a cellulose sponge. It is then placed in a sponge box (total weight approximately 350g) and placed on a board fixed to a linear cleaning device. A predetermined number of cycles and speeds are established to ensure the sponge is passed over the surface in a consistent manner, usually a total of 5 cycles.

[0077] Soil Blend Ratio: When the wallboard cleaning method was initially implemented, the ratio of lard, oil, shortening, and carbon black soils was different from that of the ASTM method. A modified ratio (30% vegetable shortening, 30% lard, 30% vegetable oil, and 10% carbon black) was initially implemented for the test protocol with a higher amount of carbon black. Additional carbon black was used to visualize the differences between the various products tested. This may be due to several factors, such as the particle size of the carbon black and its aggregation behavior with the polymer in the formulation.

[0078] Base Paint: Per ASTM method, the paint type was specified by California Paints (Item 53300) to be an acrylic flat white interior paint. An alternative flat white paint was used because the supplier no longer produces the exact version outlined in the test method due to its lack of scrub resistance. It was decided that Behr Pro Dead FlatPaint would be used for future testing.

[0079] Carbon Black Supplier: ASTM methods require the use of Acros Carbonlamp, but this exact grade has been discontinued, so we tried various types of carbon black. We identified a grade of carbon black (Panther 405) that gave good cleaning consistency across various cleaners.

[0080] Soil Application: During the development phase of the cleaning protocol, a 50 mil (1 mil = 1 / 1000 inch) drawdown bar was used. The soil was pipetted parallel to the top board and then flow coated with one stroke from the drawdown bar. This form of application was subsequently phased out to better comply with ASTM protocols.

[0081] Comparative Example 1 - Evaluation of Current Sanitizer Cleaning Benchmarks Benchmarks of readily available, ready-to-use trigger sprays for germicidal cleaners were tested for cleaning performance in the ASTM D4488 wallboard cleaning test. All of these products claim to kill >99.9% of bacteria and viruses, making them efficient germicides. However, Benchmark A (quat-based all-purpose cleaner - APC) is significantly more effective at removing carbonaceous and greasy soils than Benchmark B (bleach-based APC), Benchmark C (citric acid-based bathroom cleaner - BC), and HarshFree Benchmark D (peroxide-based APC). None of these cleaner-sanitizers provide the long-lasting cleaning sanitization required to pass the RSS-12h or RSS-24h protocols. The germicidal cleaners provide a frame of reference for adjusting cleaning applications to desired performance (Figure 2).

[0082] Comparative Example 2 - Long-lasting disinfectant cleaning effect The composition of long-lasting disinfectant Formulation A is shown in Table 1. Films prepared from Formulation A were evaluated using the RSS-12h protocol with E. aerogenes, a modified version of the Residual Self-Disinfection (RSS) method, EPA Protocol #01-1A, described above. All films were prepared by pipetting 150 microliters of the formulation onto a (1 x 1) inch steel substrate and allowed to air dry. Formulation A provides a potent formulation that passes the RSS-12h test with a 4.82 LR (greater than log reduction -3), making it a long-lasting disinfectant. Formulation A has a pH of 4.5 with additional lactic acid for pH control, as detailed below, where the added amine oxide is cationic, providing a clear, stable solution. Formulation A does not contain a nonionic surfactant.

[0083] TIFF0007758569000011.tif124170

[0084] Formulation A was further evaluated for cleaning performance per ASTM D4488 as described above and compared to the best performing cleaner, Benchmark A. As can be seen in Figure 3, Formulation A underperforms compared to the cleaning effectiveness of Benchmark A. Benchmark A removed approximately 70% of the soil, while Formulation A removed approximately 30%.

[0085] Example 3 - Addition of low HLB tristyrylphenol ethoxylate (TSP-xEO) The addition of tristyrylphenol ethoxylate surfactant in Formulation A showed an immediate improvement in the dispersion of carbon black. The effect on cleaning performance of adding different concentrations of TSP-8EO to Formulation A (Table 2) was investigated while maintaining the composition at a pH of 4.5.

[0086] TIFF0007758569000012.tif94170

[0087] The cleaning performance at various concentrations of added TSP-8EO is shown in Figure 4. The addition of TSP-8EO significantly improves cleaning at concentrations above 0.5%.

[0088] Example 4 - Effect of various quat concentrations on RSS-12h Formulation B (Table 3) was prepared using Mirapol® HSC-310, adjusted the concentration of citric acid, and reduced TSP-8EO. Formulation B demonstrated very similar cleaning to Benchmark A (Figure 5), one of the most effective germicidal cleaners on the market.

[0089] TIFF0007758569000013.tif140170

[0090] The effect of minimizing acid on abrasion and RSS-12h was investigated. Formulation B was further adapted to remove lactic acid from the composition while maintaining additional polyvalent citric acid and GLDA (Formulation C - Table 3). Removing lactic acid from the formulation resulted in an interesting wetting pattern on the steel tiles used in RSS-12h. In contrast to what was seen with Formulations A and B, no corner wetting of the product was observed. In the absence of lactic acid, the product was more wet on the surface (Figure 6). This improved wetting effect is desirable when testing for abrasion resistance and RSS-12h.

[0091] Samples of the above formulations were prepared for RSS-12h. These samples included Formulations B and C, with and without lactic acid. Formulation C (without lactic acid) demonstrated a 4.55 log reduction and passed RSS-12h. Achieving a log reduction of greater than 3 meets the 12-hour requirement for a germicidal cleaner at 99.9% residual kill after three wet abrasions and three dry abrasions. Removal of lactic acid (Formulation C) did not impact cleaning efficacy, and even at pH 4.0, it performed equivalently to the market-leading Benchmark A while providing long-lasting disinfection.

[0092] In another embodiment, a reduction in the quat content was explored. It is desirable to have the minimum amount of quats feasible to obtain an acceptable residual feel while achieving long-lasting disinfection. Formulation D is a clear, stable composition at half (5000 ppm) of the quats, as shown in Table 4.

[0093] TIFF0007758569000014.tif136170

[0094] Formulation D demonstrated a 3.99 log reduction in the RSS-12h test. Achieving a log reduction of greater than 3 requires a cleaning disinfectant to achieve a 12-hour claim of 99.9% residual kill after three wet abrasions and three dry abrasions. Due to the reduction in quats, cleaning efficacy was slightly reduced. However, even at pH 4.0, Formulation D's performance was comparable to most benchmarks (except Benchmark A) while providing long-lasting kill.

[0095] Example 5 - RSS-24h for disinfectant cleaners with various quat concentrations The performance of RSS-24h was investigated using formulations E and F (Table 5).

[0096] TIFF0007758569000015.tif142170

[0097] Formula E nearly passes the RSS-24h test at 2.76 LR. Formula F successfully passes the RSS-24h test at 3.76 LR. The HLB of the mixed nonionic surfactants (TSP-4EO + TSP-8EO) in Formula F is lower than that in Formula E. The formulas also provide excellent cleaning performance.

[0098] As shown in Table 5.1, further performance improvements of RSS-24h can be achieved by using a low HLB nonionic surfactant such as tristyrylphenol ethoxylate-6.5EO instead of the 8EO mixture, even when blended with 4EO. Both Formulation G and Formulation H pass RSS-24h against E. aerogenes on stainless steel with LR of 3.95 and 4.18, respectively. Both formulations are at pH 4.5.

[0099] TIFF0007758569000016.tif151170

[0100] To further evaluate the formulation's effectiveness in terms of antimicrobial performance [ready-to-use (RTU) applications], Formulation H liquid was tested for virucidal efficacy against human coronavirus (ATCC VR-740, strain 229E). For viral efficacy testing, the EPA recommends the AOAC Use-Dilution Test (modified for viruses) or ASTM E1053. The formulation was tested with an organic soil challenge of 5% fetal bovine serum for a 10-minute exposure time. Recovery was tested in the WI-38 (human lung) cell line. Complete inactivation of the test virus was demonstrated. A log reduction of 3.00 or greater in virus titer was demonstrated per well and per volume inoculated per carrier (PASSED). Results of all test controls met the acceptance criteria for a valid test.

[0101] The potent use of low HLB nonionic tristyrylphenol ethoxylates was further explored by lowering the "quat" concentration below 3000 ppm while improving cleaning performance (Table 5.2). Reducing the "quat" concentration is desirable to improve the formulation's hazard profile. Further improved cleaning performance is achieved by increasing the overall surfactant concentration while increasing the polymer concentration. Formulations I, J, and K outlined in Table 5.2 all pass RSS-24h and provide excellent cleaning performance.

[0102] TIFF0007758569000017.tif135170

[0103] The performance of various polymers was also examined in terms of RSS-24h performance. The polymer mentioned above, Mirapol® HSC-310, is an acrylic acid / DADMAC copolymer (anion-cation). Table 5.3 outlines the use of three other polymers: HSC-500 (polysulfobetaine), HSC-500VPA (polysulfobetaine vinylphosphonic acid copolymer), and HSC-2 (ethyl ester of acrylic acid / DADMAC copolymer). HSC-500 (sulfobetaine) contains both cationic and anionic moieties, HSC-500VPA contains an additional phosphonate anion, and HSC-2 contains a more hydrophobic nonionic / cationic moiety. Another commercially available form of HSC-500 with added citric acid is outlined herein as Mirapol® Surf S500. When RSS-24h was performed with Enterobacter aerogenes on stainless steel at the use concentrations outlined in Table 5.3, Formula L demonstrated 1.81 LR (98.45% kill), which improved to 3.15 LR (99.93% kill) with Formula M, and 4.66 LR (99.998% kill) with Formula N. Formulas L, M, and N have pHs of 5.5, 5.5, and 4.2, respectively. The "quat" (ADBAC+DDAC) concentration was further reduced from Formula N (5000 ppm) to Formula O (2900 ppm) to Formula P (1000 ppm). All Formulas N, O, and P are at pH 4.2. Even at a 1000 ppm "quat" (ADBAC+DDAC) concentration, Formulation P showed "total kill" with an RSS-24h of over 4.66 LR or 99.99% kill.

[0104] TIFF0007758569000018.tif170170

[0105] Example 6 - Long-lasting dilutable concentrate Formulations Q and R (Table 6) were diluted and tested for cleaning performance and RSS-12h with E. aerogenes on steel.

[0106] Cleaning performance was comparable to other dilutable concentrate benchmarks at similar dilution factors. Table 6 shows 30-fold dilutions of Q and R (Q-30X and R-30X, respectively) and a further 60-fold dilution of R (R-60X). 100 microliters of the diluted compositions were applied to steel substrates in RSS-12h. While Formulation Q has higher total activity compared to Formulation R (16% w / w), the RSS-12h results show that even the 30-fold and 60-fold dilutions of Formulation R are greater than 3 LR.

[0107] TIFF0007758569000019.tif140170

[0108] Example 7 - Improved Environmental Profile In another embodiment, to further improve the environmental profile of the concentrate, the formulation was adapted to reduce the hazardous components. These compositions are shown in Table 7 as Formulations S and T. DDAC was removed (a more chronic environmental hazard), and ADBAC was used at a reduced amount (15,900 ppm vs. 18,000 ppm). These compositions were then further diluted 30-fold (S-30X and T-30X), applied (100 microliters) to steel substrates, and tested using the RSS-12h protocol with E. aerogenes. These environmentally improved compositions pass the RSS-12h with greater than 3 LR.

[0109] TIFF0007758569000020.tif147170

[0110] Example 8 - Nonionic Surfactants Three nonionic surfactants were added to Formulation A at 0.5% actives to vary cleaning performance. The addition of alcohol ethoxylates (Rhodasurf® BC-630 and Rhodasurf® 91-6) to Formulation A did not improve cleaning performance. In contrast, tristyrylphenol ethoxylate 8-EO showed a dramatic improvement in cleaning performance at the same use concentration (Figure 7).

[0111] The disclosed subject matter has been described with reference to detailed descriptions of specific embodiments thereof. It is not intended that such details be deemed limitations on the scope of the disclosed subject matter, except to the extent that they are included in the appended claims.

[0112] Thus, the exemplary embodiments described herein are well adapted to achieve the objects and advantages set forth above, as well as those inherent therein. The specific embodiments disclosed above are merely illustrative, as the exemplary embodiments described herein may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Moreover, no limitations to the details of construction or design shown herein are intended, except as set forth in the claims below. It is therefore evident that the specific exemplary embodiments disclosed above may be altered, combined, or modified, and all such variations are deemed to be within the scope and spirit of the exemplary embodiments described herein. The exemplary embodiments illustratively disclosed herein and described herein can be practiced in the absence of elements not specifically disclosed herein and / or optional elements disclosed herein. Compositions and methods are described in terms "comprising," "containing," or "including" various components or steps, but compositions and methods can also "consist essentially of" or "consist of" various components, materials, and steps. As used herein, the term "consisting essentially of" shall be interpreted to mean including the recited components, materials, or steps and such additional components, materials, or steps that do not materially affect the basic and novel characteristics of the composition or method. In some embodiments, a composition according to an embodiment of the present disclosure "consisting essentially of" the recited components or materials does not contain additional components or materials that alter the basic and novel characteristics of the composition. In the event of a discrepancy in the usage of a word or term in this specification and one or more patents or other documents that may be incorporated herein by reference, the definition consistent with this specification shall be governed.

Claims

1. a. an antimicrobial component comprising at least one quaternary ammonium compound; b. i. at least one cationic monomer A ｂ and, ii. Optionally, at least one anionic monomer B ａ and, iii. Optionally, at least one nonionic monomer C ａ and, a synthetic polymer comprising c. an organic acid; d. a surfactant selected from the group consisting of cationic surfactants, amphoteric surfactants, and combinations thereof; e. at least one tristyrylphenol ethoxylate nonionic surfactant with a delocalized electronic structure having a hydrophilic-lipophilic balance (HLB) value of less than 9; 1. A hard surface treatment composition comprising:

2. 10. The composition of claim 1, wherein a film formed from the composition kills at least 95% of microorganisms upon at least three abrasion cycles by RSS-12h.

3. 10. The composition of claim 1, wherein the antimicrobial component is selected from the group consisting of monoalkyldimethylbenzyl ammonium salts, dialkyldimethyl ammonium salts, and combinations thereof.

4. Monomer A ｂ The composition of claim 1 , wherein is selected from the group consisting of diallyldimethylammonium halides.

5. The polymer comprises a monomer B selected from the group consisting of acrylic acid, methacrylic acid, and combinations thereof. ａ The composition of claim 1 comprising:

6. The polymer comprises a monomer C selected from the group consisting of 2-(dimethylamino)ethyl methacrylate (DMAEMA), N-vinylpyrrolidone (NVP), N-vinylimidazole, acrylamide, methacrylamide, alkyl acrylate, and combinations thereof. ａ The composition of claim 1 comprising:

7. 10. The composition of claim 1, wherein the organic acid is selected from the group consisting of citric acid, malic acid, maleic acid, lactic acid, succinic acid, glutaric acid, adipic acid, and combinations thereof.

8. 10. The composition of claim 1, wherein the surfactant comprises a cationic surfactant selected from the group consisting of cationic amine oxides.

9. 10. The composition of claim 1, wherein the surfactant comprises an amphoteric surfactant selected from the group consisting of sultaines, taurates, and combinations thereof.

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

11. 10. A method of providing residual antimicrobial activity to a surface, comprising applying the composition of claim 1 to said surface.

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

13. 10. Use of the composition of claim 1 to substantially reduce or control the formation of microbial colonies on or at a surface.

14. 14. The use of claim 13, wherein a film formed from the composition kills at least 95% of gram-positive and gram-negative bacteria or enveloped and non-enveloped viruses according to a modified version of Environmental Protection Agency (EPA) Protocol #01-1A Residual Self-Disinfecting Activity Test.

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