Reduced inhalation hazard sanitizers and disinfectants via high molecular weight polymers

Abstract

To provide antimicrobial compositions having reduced inhalation risks.SOLUTION: The invention provides antimicrobial compositions having reduced inhalation risks by combining ammonium compounds and polymers in combination with optional acid components, surfactants and / or additional functional ingredients. The antimicrobial compositions have a reduced risk of inhalation. Methods of making and employing the compositions are disclosed.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. § 119 to U.S. Provisional Patent Application No. 62 / 465,483, filed March 1, 2017, which is incorporated by reference herein in its entirety.

[0002] The present invention relates to the field of aqueous compositions for cleaning, disinfecting, and sterilizing. In some embodiments, an antimicrobial quaternary ammonium compound is provided in combination with a polymer component to provide a composition with disinfecting, sterilizing, and / or antimicrobial properties combined with a reduced inhalation risk. In other aspects, the antimicrobial quaternary ammonium compound is provided in combination with a surfactant component, a polymer component, and an additional functional component. In particular, the combination provides enhanced antimicrobial activity and a reduced inhalation risk compared to either the surfactant or the quaternary ammonium compound alone. Advantageously, the present invention provides cleaning compositions tailored to specific uses. [Background technology]

[0003] Antimicrobials are chemical compositions used to prevent microbiological contamination and deterioration of products, materials, and media (such as water process streams) and systems. Antimicrobial agents and compositions are used, for example, as disinfectants and sanitizers in hard surface cleaning, food preparation, animal feed, cooling water, hospitality services, hospital and medical applications, pulp and paper manufacturing, textile cleaning, and water treatment. Among the diverse categories of antimicrobial agents and compositions, quaternary ammonium compounds represent one of the largest classes of agents used. At low concentrations, quaternary ammonium-type antimicrobials are bacteriostatic, fungistatic, algicidal, sporostatic, and tuberculostatic. At moderate concentrations, they are bactericidal, fungicidal, algicidal, and virucidal against lipophilic viruses. However, at high concentrations, generally above about 2-3% by weight, they exhibit acute toxicity. According to the U.S. Environmental Protection Agency, contact with quaternary ammonium compounds can cause contact dermatitis and nasal irritation. Additionally, certain quaternary ammonium compounds are respiratory sensitizers and have been linked to asthma and other respiratory conditions. To limit inhalation doses, handling and use of quaternary ammonium compounds requires personal protection and adequate ventilation. Regarding the U.S. Environmental Protection Agency's Health Effects Testing Guideline, OPPTS 870.1300 for Acute Inhalation Toxicity, particle size analysis should be conducted during the development of a production system for such compositions to establish the stability of aerosol concentrations. The aerodynamic mass median diameter should be between 1 and 4 micrometers. The particle size of hygroscopic materials must be sufficiently small when dry to ensure that the swollen particle size remains within the 1 to 4 micrometer range.

[0004] Additionally, the spray device creates a spray pattern of the composition that contacts the target hard surface. While the majority of the composition becomes present on the target surface, a minor portion of the sprayable composition may become an airborne aerosol or mist (e.g., an airborne mist or finely divided aerosol) consisting of small particles of the cleaning composition that may remain suspended or dispersed in the atmosphere around the site of dispersion for a period of time, such as from about 5 seconds to about 10 minutes. Such airborne mist or finely divided aerosol generated during the spraying process may present substantial problems.

[0005] Such aqueous compositions with strong basic cleaning ingredients in the form of finely divided aerosols or mist can cause respiratory distress to users. To alleviate respiratory distress, some sprayable aqueous compositions have been formulated with reduced amounts of alkaline cleaning ingredients. Strong caustics have been replaced with bases of reduced alkalinity, such as bicarbonates, or with solvent materials. However, reducing the concentration or replacing these materials can often reduce the cleaning activity and effectiveness of the material during use. This necessitates the use of organic surfactants or glycol, alkyl ether, or dimethyl sulfoxide solvent materials to improve the detergent properties of the reduced alkaline material. Despite the improvements seen in sprayable aqueous compositions, there remains a need for improved compositions that provide effective cleaning, disinfecting, and sterilization while having reduced misting and therefore reduced inhalation.

[0006] Developments and improvements in polymers for various uses include EP 202,780, which discloses a particulate crosslinked copolymer of acrylamide and at least 5 mole percent of a dialkylaminoalkyl acrylate; U.S. Pat. No. 4,950,725, which discloses the addition of a crosslinking agent both at the beginning and during the polymerization process under conditions such that its availability to the reaction remains substantially constant throughout the process; EP 374,458, which discloses a water-soluble branched high molecular weight cationic polymer; and EP 102,459, which discloses a chain transfer agent at the end of the polymerization of DADMAC / acrylamide copolymers. 363,024, U.S. Pat. No. 4,913,775, which discloses the use of substantially linear cationic polymers such as acrylamide / dimethylaminoethyl acrylate methyl chloride quaternary salt copolymers, U.S. Pat. No. 5,393,381, which discloses branched cationic polyacrylamide powders such as acrylamide / dimethylaminoethyl acrylate quaternary salt copolymers, and WO2002002662, which discloses water-soluble cationic, anionic, and nonionic polymers synthesized using water-in-oil emulsion, dispersion, or gel polymerization and having fast solubilization rates, higher reductions in specific viscosity. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, the objective of the present invention is to reduce the inhalation risk of such compositions at high, medium, and low concentrations. Reduced inhalation risk can also be measured indirectly by reduced aerosol mass collection from high-volume air sampling. Reduced mass levels directly correlate with reduced inhalation. This reduction differs from reduced misting, determined from the droplet size of the applied solution, where increased droplet size indicates reduced misting and atomization. Indeed, an advantage of the liquid compositions of the present invention is that the risk of inhalation by users of the compositions is significantly reduced or eliminated. Thus, the compositions herein avoid potential health problems, such as nasal and / or throat irritation and / or coughing or even lung damage, that would otherwise result from inhaling quaternary ammonium compounds. A further advantage of the present invention is that eye irritation and / or damage is also prevented when using the cleaning compositions of the present invention.

[0008] Accordingly, one object of the claimed invention is to develop improved antimicrobial quaternary ammonium compound-based compositions.

[0009] A further object of the present invention is a reduced inhalation product suitable for formulations using the polymer in neutral, acidic, and / or alkaline formulations, including oxidizing formulations.

[0010] It is a further object of the present invention to provide effective antimicrobial quaternary ammonium compound-based compositions that have reduced risks of inhalation and exposure when in contact with biological materials.

[0011] It is a further object of the present invention to provide a synergistic composition of a quaternary ammonium compound and an additional functional ingredient to provide such improvement to acute toxicity levels.

[0012] One object of the present invention is to provide an activated composition with reduced acute toxicity and inhalation risk, having applications for use including, for example, hard surface disinfectants, facility disinfectants, water treatment, disinfecting and / or disinfecting surfaces including high level disinfectants for medical instruments, antimicrobial lubricants, laundry cleaning and disinfecting, antimicrobial agents with improved mildness and reduced irritation, improved combination products, third sink applications, etc., where antimicrobial quaternary ammonium compounds are used.

[0013] Other objects, advantages and features of the present invention will become apparent from the following specification taken in conjunction with the accompanying drawings. [Means for solving the problem]

[0014] Compositions according to the present invention offer the ability to maintain the same or improved antimicrobial efficacy of quaternary ammonium compounds while simultaneously reducing the risk of inhalation as a result of the incorporation of high molecular weight emulsion and dispersion polymers in the compositions.

[0015] In one aspect, a concentrated cleaning composition according to the present disclosure includes a cleaning component comprising a sanitizer, disinfectant, antimicrobial compound, or a combination thereof, and a polymer component that is a high molecular weight cationic, nonionic, or anionic polymer. According to the present disclosure, the cleaning component is a quaternary ammonium compound, an acid disinfectant, an oxidizing agent, an amine, or a combination thereof, while the polymer component is an inverse emulsion polymer, a dispersion polymer, a powder polymer, xanthan gum, or a combination thereof.

[0016] In one embodiment, a cleaning composition according to the present disclosure includes a cleaning component that is a quaternary ammonium compound and a polymer component that is a high molecular weight cationic or anionic inverse emulsion polymer, a high molecular weight cationic or anionic dispersion polymer, or a high molecular weight cationic or anionic powder polymer.

[0017] In a further aspect, a cleaning composition according to the present disclosure includes an acid disinfectant cleaning component and a polymer component that is a high molecular weight cationic, anionic, or nonionic inverse emulsion polymer, a high molecular weight cationic, anionic, or nonionic dispersion polymer, a high molecular weight cationic, anionic, or nonionic powder polymer, or xanthan gum.

[0018] In yet a further aspect, a cleaning composition according to the present disclosure includes an oxidizing agent cleaning component and a polymer component that is a high molecular weight cationic, anionic, or nonionic inverse emulsion polymer, a high molecular weight cationic, anionic, or nonionic dispersion polymer, a high molecular weight cationic, anionic, or nonionic powder polymer, or xanthan gum.

[0019] In yet a further aspect, a cleaning composition according to the present disclosure includes an amine cleaning component and a polymer component that is a high molecular weight cationic, anionic, or nonionic inverse emulsion polymer, a high molecular weight cationic, anionic, or nonionic dispersion polymer, a high molecular weight cationic, anionic, or nonionic powder polymer, or xanthan gum.

[0020] The cleaning composition according to the present disclosure may include a polymer component having a molecular weight of 1 million Da to 25 million Da, a particle size in the range of 0.1 to 10 microns, and a viscosity of 50 to 5,000 cPs. Furthermore, the cleaning composition may further include an acid component, the acid component being present in an amount of about 0.1% to about 30% by weight, the acid component providing pH control such that the cleaning composition has a pH of 0 to 6. Furthermore, the cleaning composition may further include at least one anionic surfactant, nonionic surfactant, amphoteric surfactant, or a combination thereof, the at least one surfactant being present in an amount of about 0.1% to about 30% by weight.

[0021] The cleaning compositions according to the present disclosure may further comprise at least one additional functional ingredient selected from the group consisting of additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, wetting agents, metal protecting agents, stabilizing agents, corrosion inhibitors, sequestering and / or chelating agents, solidifying agents, coating agents, pH adjusting components, fragrances and / or dyes, hydrotropes or couplers, buffering agents, and combinations thereof.

[0022] In one aspect of the present disclosure, the cleaning composition provides at least a 4 log kill on treated surfaces while providing a reduced inhalation risk. Further, the cleaning composition provides a reduced inhalation risk, and the median particle size of the composition is about 11 microns or greater.

[0023] In a further aspect of the disclosure, the cleaning composition comprises a compound of the formula: [ka] wherein the R1, R2, R3, and R4 groups each have a chain length of less than C20 and X- is an anionic counterion; and a polymeric component which is a high molecular weight cationic or nonionic polymer, wherein the composition is either a ready-to-use solution or a water-soluble concentrate and has a pH of about 0 to about 6.

[0024] According to one embodiment of the present disclosure, the quaternary ammonium compound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, polysubstituted quaternary ammonium salts, bisquaternary ammonium salts, polymeric quaternary ammonium salts, and combinations thereof. In a further embodiment of the present disclosure, the quaternary ammonium compound is present in an amount of about 1% to about 50% by weight.

[0025] In one embodiment of the present disclosure, the polymer component has a molecular weight of 1 million Da to 25 million Da, a particle size in the range of 0.1 to 10 microns, and a viscosity of 50 to 5000 cPs. Furthermore, the polymer component is acrylamide, methacrylamide, acrylic acid or a salt thereof, Nt-butylacrylamidosulfonic acid (ATBS) or a salt thereof, acrylamido-tert-butylsulfonic acid or a salt thereof, 2-(acryloyloxy)-N,N,N-trimethylethaneammonium (DMAEA.MCQ), diallyldimethylammonium chloride, dimethylaminoethyl acrylate methyl chloride quaternary salt, acrylamidopropyltrimethylammonium chloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, or a combination thereof.

[0026] In one embodiment of the present disclosure, the cleaning composition further comprises an acid component, the acid component being present in an amount of about 0.1% to about 30% by weight, to provide pH control such that the cleaning composition has a pH of 0 to 6.

[0027] In a further aspect of the present disclosure, the cleaning composition further comprises at least one anionic surfactant, nonionic surfactant, amphoteric surfactant, or combination thereof, wherein the at least one surfactant is present in an amount of from about 0.1% to about 30% by weight.

[0028] In yet a further aspect of the present disclosure, the cleaning composition further comprises at least one additional functional ingredient selected from the group consisting of additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, wetting agents, metal protecting agents, stabilizing agents, corrosion inhibitors, sequestering and / or chelating agents, solidifying agents, coating agents, pH adjusting components, fragrances and / or dyes, hydrotropes or couplers, buffering agents, and combinations thereof.

[0029] The cleaning compositions according to the present disclosure provide at least 4 log kill on treated surfaces while providing a reduced inhalation risk. Additionally, the cleaning compositions according to the present disclosure provide a reduced inhalation risk, and the median particle size of the compositions is about 11 microns or greater.

[0030] Methods of using the compositions are also included in embodiments of the present disclosure. In one aspect of the present disclosure, a method of killing microorganisms comprises applying a cleaning composition according to the present disclosure to a substrate, wherein the composition provides at least a 4 log kill on the treated surface while providing a reduced inhalation risk.

[0031] While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive. DETAILED DESCRIPTION OF THE INVENTION

[0032] The embodiments of the present invention are not limited to specific compositions, methods of making and / or using the same for hard surface disinfection and sanitization, including antimicrobial and / or disinfecting applications of the cleaning composition, along with alternative cleaning and uses of the cleaning composition, which may vary and are understood by those skilled in the art. To facilitate understanding of the present invention, certain terms are first defined. It should be further understood that all terminology used herein is solely for the purpose of describing specific embodiments and is not intended to be limiting in any manner or scope. For example, when used in this specification and the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the context clearly dictates otherwise. Furthermore, all units, prefixes, and symbols may be expressed in their SI-recognized form.

[0033] Numerical ranges described herein are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of the invention are presented in range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to specifically disclose all possible subranges, fractions, and individual numbers within that range. For example, the description of a range such as 1 to 6 should be considered to specifically disclose subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual numbers within that range, e.g., 1, 2, 3, 4, 5, and 6, and decimals and fractions, e.g., 1.2, 3.8, 1½, and 4¾. This applies regardless of the broadness of the range.

[0034] In order to make the present invention easier to understand, certain terms are first defined. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. Many methods and materials similar to, modified, or equivalent to those described herein can be used to practice the present invention without undue experimentation, and preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology is used in accordance with the definitions set forth below.

[0035] As used herein, the term "about" refers to variations in numerical quantities that may occur, for example, through typical measuring and liquid handling procedures used to actually make a concentrate or use solution, through inadvertent errors in these procedures, through differences in manufacture, source, purity of ingredients used to make the composition or carry out the method, etc. The term "about" also encompasses amounts that vary due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether modified by the term "about," the claims include the equivalent of the amount.

[0036] The term or abbreviation "AcAm" refers to acrylamide.

[0037] "Actives" or "percent actives" or "percent actives by weight" or "actives concentration" are used interchangeably herein and refer to the concentration of ingredients involved in cleaning expressed as a percentage minus inactive ingredients such as water or salt.

[0038] As used herein, the terms "active chlorine," "chlorine," and "hypochlorite" are all used interchangeably and are intended to mean the measurable chlorine available in a use solution as assessed by standard titration techniques known to those skilled in the art. In preferred embodiments, the inverse emulsion polymer compositions provide chlorine-free cleaning compositions.

[0039] As used herein, the terms "aerosol" and "mist" refer to an airborne dispersion of small particles comprising a cleaning composition that may remain suspended or dispersed in the atmosphere surrounding the cleaning site for at least 5 seconds, and more commonly 15 seconds to 10 minutes.

[0040] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, and includes straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).

[0041] Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl." As used herein, the term "substituted alkyl" refers to an alkyl group having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, methyl ... The substituents may include nitro, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0042] As used herein, the term "cleaning" refers to methods used to promote or aid in stain removal, bleaching, microbial population reduction, and any combination thereof. As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, and some algae. As used herein, the term "microbe" is synonymous with microorganism. For purposes of this patent application, successful microbial reduction is achieved when the microbial population is reduced by at least about 50%, or significantly more than that, by washing with water. Greater reduction in microbial population provides a greater level of protection.

[0043] The term or abbreviation "DADMAC" refers to diallyldimethylammonium chloride.

[0044] The term or abbreviation "DMAEA" refers to dimethylaminoethyl acrylate.

[0045] The term or abbreviation "DMAEM" refers to dimethylaminoethyl methacrylate.

[0046] The term or abbreviation "DMAEA BCQ" refers to dimethylaminoethyl acrylate, benzyl chloride quaternary salt.

[0047] The term or abbreviation "DMAEA'MCQ" refers to dimethylaminoethyl acrylate, methyl chloride quaternary salt.

[0048] As used herein, the term "sanitizer" refers to an agent that kills all vegetative cells, including most recognized pathogenic microorganisms, using the procedures set forth in the AOAC Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2). According to this reference, a sanitizer should provide a 99.999% reduction (5-log order reduction) of several test organisms within 30 seconds at room temperature, 25±2°C. According to embodiments of the present invention, a sanitizer composition provides a 99.999% reduction (5-log order reduction) of desired organisms (including bacterial contamination) at use temperatures. Furthermore, a sanitizer should provide a 99.99% reduction (4-log order reduction) of several test organisms within 30 seconds at room temperature, 25±2°C. According to embodiments of the present invention, a sanitizer composition provides a 99.99% reduction (4-log order reduction) of desired organisms (including bacterial contamination) at use temperatures. Additionally, the disinfectant should provide a 99.9% reduction (3-log order reduction) of several test organisms within 30 seconds at room temperature, 25±2°C. According to embodiments of the present invention, the disinfectant composition provides a 99.9% reduction (3-log order reduction) of desired organisms (including bacterial contamination) at the temperature of use. As used herein, the term "high-level disinfection" or "high-level disinfectant" refers to a compound or composition that kills substantially all organisms except high levels of bacterial spores and is effective with chemical disinfectants approved for marketing as sterilants by the Food and Drug Administration. As used herein, the term "intermediate-level disinfection" or "intermediate-level disinfectant" refers to a compound or composition that kills mycobacteria, most viruses, and bacteria with chemical disinfectants registered by the Environmental Protection Agency (EPA) as tuberculocides.As used herein, the terms "low-level disinfection" or "low-level disinfectant" refer to a compound or composition that is a chemical disinfectant registered by the EPA as a hospital disinfectant and kills some viruses and bacteria. The term or abbreviation "EDTA 4Na+" refers to ethylenediaminetetraacetic acid, tetrasodium salt.

[0049] As used herein, the phrase "food processing surface" refers to the surfaces of utensils, machines, equipment, structures, buildings, etc. used as part of food processing, cooking, or storage activities. Examples of food processing surfaces include surfaces of food processing or cooking equipment (e.g., slicing, canning, or conveying equipment including flumes), surfaces of food processing ware (e.g., cookware, dishware, washware, and bar glasses), and surfaces of floors, walls, or fixtures of structures where food processing occurs. Food processing surfaces are found and used in food spoilage prevention air circulation systems, aseptic packaging sanitizers, food refrigeration and cooler cleaners and sanitizers, ware washing sanitizers, blancher washing and sanitizing, food packaging materials, cutting board additives, third sink sanitizers, beverage chillers and warmers, meat cooling or boiling water, automatic dish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial garment sprays, and non-aqueous to low-aqueous food preparation lubricants, oils, and rinse additives.

[0050] As used herein, "food product" includes any food substance that may require treatment with an antimicrobial agent or composition and is suitable for consumption with or without further cooking. Food products include meat (e.g., red meat and pork), seafood, poultry, produce (e.g., fruits and vegetables), eggs, live eggs, cooked foods, wheat, seeds, roots, tubers, leaves, stems, grains, flowers, sprouts, seasonings, or combinations thereof. The term "produce" refers to food products such as fruits and vegetables and plants or plant-derived materials that are typically sold uncooked, often unpackaged, and sometimes eaten raw.

[0051] The term "hard surface" refers to solid, substantially inflexible surfaces such as countertops, tiles, floors, walls, paneling, windows, plumbing fixtures, kitchen and bathroom fixtures, appliances, engines, circuit boards, and dishes. Hard surfaces can include, for example, healthcare surfaces and food processing surfaces.

[0052] As used herein, the phrase "healthcare surfaces" refers to surfaces of instruments, devices, carts, cages, furniture, structures, buildings, and the like, used as part of healthcare activities. Examples of healthcare surfaces include surfaces of medical or dental instruments, surfaces of medical or dental equipment, surfaces of electronic devices used to monitor patient health, and surfaces of floors, walls, or furniture of structures where healthcare is performed. Healthcare surfaces are found in hospitals, surgical, infirmary, birthing, mortuary, and clinical diagnostic rooms. These surfaces can be typified as "hard surfaces" (e.g., walls, floors, toilets, etc.), or textile surfaces, such as knitted, woven, and nonwoven surfaces (e.g., surgical gowns, curtains, bed linens, bandages, etc.), or patient care equipment (e.g., ventilators, diagnostic equipment, shunts, body scopes, wheelchairs, beds, etc.), or surgical and diagnostic equipment. Healthcare surfaces include items and surfaces used in animal healthcare.

[0053] As used herein, the term "instrument" refers to a variety of medical or dental instruments or devices that can benefit from cleaning with a composition according to the present invention.

[0054] As used herein, the phrases "medical instruments," "dental instruments," "medical devices," "dental equipment," "medical equipment," or "dental equipment" refer to instruments, devices, implements, appliances, instruments, and equipment used in medicine or dentistry. Such instruments, devices, and equipment may be cold sterilized, soaked, or cleaned, followed by heat sterilization, or may otherwise benefit from cleaning in the compositions of the present invention. These various instruments, devices, and equipment include, but are not limited to, diagnostic instruments, trays, pans, holders, racks, tweezers, scissors, shears, saws (e.g., bone saws and their blades), hemostats, knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, retractors, straighteners, punches, extractors, scoops, keratomes, spatulas, expressors, trocars, dilators, cages, glassware, tubes, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthroscopes), and related equipment, and the like, or combinations thereof.

[0055] As used herein, the term "microbe" is synonymous with microorganism. For purposes of this patent application, successful microbial reduction is achieved when the microbial population is reduced by at least about 50%, or significantly more than that, by washing with water. Greater reduction in microbial population provides a greater level of protection. The distinction between antimicrobial "cidal" or "static" activity, definitions describing the degree of effectiveness, and official laboratory protocols for measuring this effectiveness are important considerations for understanding the relevance of antimicrobial agents and compositions. Cleaning compositions can affect two types of microbial cell damage. The first is a lethal, irreversible effect that results in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, so that organisms can repopulate once the agent is removed. The former is referred to as microbiocidal, and the latter as microbistatic. Disinfectants and disinfectants are, by definition, agents that provide antimicrobial or microbicidal activity. In contrast, antiseptics are generally described as inhibitors or microbistatic compositions.

[0056] As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, and some algae.

[0057] As used herein, the term "disinfectant" refers to an agent that reduces the number of bacterial contaminants to a safe level as determined by public health requirements. In one embodiment, disinfectants for use in the present invention will provide at least a 99.999% reduction (a 5-log reduction). These reductions can be evaluated using the procedures set forth in paragraph 960.09 and applicable sections of "Germicidal and Detergent Sanitizing Action of Disinfectants," Official Methods of Analysis of the Association of Official Analytical Chemists, 15th Edition, 1990 (EPA Guideline 91-2). According to this reference, disinfectants should provide a 99.999% reduction (a 5-log reduction) of several test organisms within 30 seconds at room temperature, 25±2°C. According to embodiments of the present invention, disinfecting compositions provide a 99.999% reduction (a 5-log reduction) of desired organisms (including bacterial contamination) at use temperatures. Additionally, disinfectants should provide a 99.99% reduction (4-log order reduction) of several test organisms within 30 seconds at room temperature, 25±2°C. According to embodiments of the present invention, disinfectant compositions provide a 99.99% reduction (4-log order reduction) of desired organisms (including bacterial contamination) at use temperatures. Additionally, disinfectants should provide a 99.9% reduction (3-log order reduction) of several test organisms within 30 seconds at room temperature, 25±2°C. According to embodiments of the present invention, disinfectant compositions provide a 99.9% reduction (3-log order reduction) of desired organisms (including bacterial contamination) at use temperatures. The distinction between antimicrobial "cidal" and "static" activity, definitions describing the degree of effectiveness, and official laboratory protocols for measuring this effectiveness are important considerations for understanding the relevance of antimicrobial agents and compositions. Cleaning compositions can affect two types of microbial cell damage. The first is a lethal, irreversible effect that results in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, so that the organism can reproduce again once it is free of the drug.The former are called microbiocidal, the latter microbistatic. Disinfectants and disinfectants, by definition, are agents that provide antimicrobial or microbiocidal activity. In contrast, preservatives are generally described as inhibitors or microbistatic compositions.

[0058] The distinction between antimicrobial "cidal" or "static" activity, definitions describing the degree of effectiveness, and formal laboratory protocols for measuring this effectiveness are important considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of microbial cell damage. The first is a lethal, irreversible action that results in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, so that organisms can regenerate once the agent is removed. The former is called microbiocidal, and the latter is called microbistatic. Disinfectants and disinfectants are, by definition, agents that provide antimicrobial or microbicidal activity. In contrast, antiseptics are generally described as inhibitors or microbistatic compositions.

[0059] As used herein, the term "surfactant" is a compound containing a lipophilic segment and a hydrophilic segment that, when added to water or a solvent, reduces the surface tension of the system.

[0060] The term "viscosity" is used herein to describe the properties of the sprayable aqueous compositions for cleaning, disinfecting, and sterilizing according to the present invention. As one skilled in the art will understand, both dynamic (shear) viscosity and bulk viscosity can be used to describe the characteristics of a composition. The shear viscosity of a liquid describes its resistance to shear flow. The bulk viscosity of a liquid describes its ability to exhibit a form of internal friction that resists its flow without shear. Viscosity measurements described herein use the physical units of poise (P) or centipoise (cPs).

[0061] As used herein, the term "ware" refers to eating and cooking utensils, tableware, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors. As used herein, the term "warewashing" refers to the washing, cleaning, or rinsing of ware. Ware also refers to items made of plastic. Types of plastics that can be cleaned with the compositions according to the present invention include, but are not limited to, those containing polycarbonate polymers (PC), acrylonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers (PS). Another exemplary plastic that can be cleaned using the compounds and compositions of the present invention includes polyethylene terephthalate (PET).

[0062] As used herein, "weight percent," "wt-%," "percent by weight," "% by weight," and variations thereof refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition multiplied by 100. As used herein, it is understood that "percent," "%," and the like are intended to be synonymous with "weight percent," "wt%," and the like.

[0063] As used herein, the term "water soluble" refers to a composition or ingredient that is at least 90% water soluble, at least 95% water soluble, at least 98% water soluble, at least 99% water soluble, or at least 99.9% water soluble.

[0064] The methods and compositions of the invention may comprise, consist essentially of, or consist of the components and ingredients of the invention, as well as other components described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or ingredients, but only if the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.

[0065] Cleaning Composition According to the present invention, a cleaning composition comprises at least one disinfectant, sanitizer, and / or antimicrobial compound and at least one polymer compound, providing cleaning activity with reduced acute toxicity as a result of the composition's reduced inhalation risk. The present invention relates to a reduced-misting and reduced-inhalation aqueous cleaning composition comprising, consisting of, or consisting essentially of at least one disinfectant, sanitizer, and / or antimicrobial compound and at least one polymer compound. In some embodiments, the composition can be dispensed with a trigger sprayer, such as a non-low-speed or low-speed trigger sprayer. The composition can also be dispensed in alternative ways. The cleaning composition offers ease of manufacturing as a result of the rapid dispersion of the polymer into a homogeneous solution. In addition to ease of manufacturing, the cleaning composition offers additional benefits, including ease of application when using a spray application due to a reduced viscosity profile that allows for ease of use with a spray trigger. Still further, the cleaning composition provides little or no misting of the formulation, providing increased cleaning speed compared to compositions containing conventional thickeners. Further aspects of reduced misting compositions are discussed in U.S. Patent Application No. 15 / 602,532, filed May 23, 2017, now U.S. Patent Application Publication No. 2017 / 0335254, and U.S. Patent Application No. 15 / 603,039, filed May 23, 2017, now U.S. Patent Application Publication No. 2017 / 0335253, each of which is incorporated by reference in its entirety.

[0066] The cleaning composition may be referred to as a non-Newtonian fluid. Newtonian fluids have a short relaxation time and a direct correlation between shear viscosity and extensional viscosity (the extensional viscosity of a liquid is equal to three times the shear viscosity). Shear viscosity is a measure of a fluid's ability to resist movement of layers relative to one another. Elongational viscosity, also known as extensional viscosity, is a measure of a fluid's ability to stretch elastically under elongational stress. Non-Newtonian fluids do not have a direct correlation between shear viscosity and extensional viscosity, and can store elastic energy when under strain, resulting in an extensional viscosity that is exponentially greater than the shear viscosity, resulting in the effect of thickening under strain (i.e., shear thickening). These properties of non-Newtonian fluids result in cleaning compositions that have a low viscosity when not under shear, but thicken when under stress from a trigger sprayer that forms larger droplets.

[0067] In some embodiments, the cleaning composition has a relatively low shear viscosity when not under strain. In one embodiment, the shear viscosity of a cleaning composition containing an inverse emulsion polymer(s) corresponds to that of water and may be referred to as a "low-viscosity liquid." A suitable shear viscosity for a cleaning composition containing a polymer(s) is about 1 to 1000 cPs, preferably 1 to 100 cPs. In one example, the antimist component does not increase the shear viscosity of the cleaning composition when not under strain; the increased shear viscosity is provided by other components, such as surfactants. The present invention provides unexpected benefits in the viscosity of antimist compositions as a result of the flexible viscoelastic composition provided by the inverse emulsion polymer.

[0068] In some embodiments, the median particle size of the dispensed solution of the reduced-mist cleaning composition is sufficiently large to reduce misting and thereby reduce the inhalation risk associated with high-mist compositions. As those skilled in the art will appreciate, particles having a droplet size of less than about 10 microns can be easily inhaled. Also, particles having a droplet size of less than about 0.1 microns can be easily inhaled into the lungs. Therefore, in many aspects of the present invention, testing and evaluation of cleaning compositions according to the present invention focuses on reducing misting, particularly reducing or eliminating the particle size to about 10 microns or less. In one aspect of the present invention, suitable median particle sizes are about 11 microns or more, 50 microns or more, 70 microns or more, about 10 microns or more, about 150 microns or more, or about 200 microns or more. The suitable median particle size may depend on the composition of the ready-to-use (RTU) composition. For example, a suitable median particle size for a strongly alkaline or acidic use solution may be about 100 microns or more, more specifically about 150 microns or more, and even more specifically about 200 microns or more. Suitable median particle size for moderately alkaline or acidic RTU may be about 11 microns or greater, preferably about 50 microns or greater, and more preferably about 150 microns or greater.

[0069] Cleaning compositions according to the present invention beneficially provide compositions that are stable with respect to polymer retention, solution stability, and microbial effectiveness, with the polymer remaining stable for at least about one year at ambient temperatures of about 60° F. to about 80° F., or at least about two years at ambient temperatures of about 60° F. to about 80° F. Stability is measured by the maintained anti-misting properties of the cleaning composition.

[0070] In one aspect, a cleaning composition according to the present invention comprises, consists of, and / or consists essentially of ingredients as set forth in Table 1, wherein the active disinfectant, sanitizing, and / or antimicrobial compounds used influence the choice of polymer morphology and charge to provide the unexpected and beneficial effect of having reduced inhalation risk coupled with disinfecting, sanitizing, and / or antimicrobial properties. [Table 1]

[0071] Cleansing ingredients The cleaning compositions according to the present invention contain a cleaning compound comprising at least one disinfectant, sanitizer, or antimicrobial compound. In one embodiment of the present invention, the cleaning component is a quaternary ammonium compound, an acid disinfectant, an oxidizer, an amine, or a combination thereof.

[0072] Quaternary ammonium compounds According to one embodiment of the present invention, a cleaning composition comprises at least one quaternary ammonium compound and at least one polymeric compound. Without wishing to be limited to a particular theory of the present invention, the cleaning composition of the present invention, when used at an acidic pH, affects the interaction between the quaternary ammonium compound and proteins. In particular, the use of the quaternary ammonium compound at an acidic pH reduces the electrostatic interaction between the positively charged quaternary ammonium compound and negatively or partially negatively charged biological materials, reducing the toxicity and inhalation risks associated with the quaternary ammonium compound. Furthermore, the addition of the polymeric component makes the composition resistant to the formation of a certain amount of mist or aerosol during storage and application, which can cause respiratory distress.

[0073] The cleaning composition according to the present invention overcomes concerns about the acute toxicity of quaternary ammonium compounds while providing effective antimicrobial and / or disinfecting capabilities. The composition of a quaternary ammonium compound and an acid component reduces acute toxicity. Without wishing to be bound by any particular theory, controlling the pH of a concentrated composition containing a quaternary ammonium compound reduces electrostatic interactions between the quaternary ammonium compound and biological materials, particularly during inhalation. The theoretical surface charge of casein protein as a function of pH is summarized in Table 2, which illustrates the pH-electrostatic charge relationship of proteins, i.e., biological materials. As shown in Table 2 and understood by those skilled in the art, as the pH approaches the isoelectric point, proteins exhibit a net zero charge. [Table 2]

[0074] At the physiological pH of the lung, approximately 7.25-7.45, most biological materials have an anionic charge. Therefore, if the biological material is less anionic, i.e., near / at / below its respective isoelectric point or pKa, then the quaternary ammonium compound and the biological material would have reduced electrostatic interactions, according to the theoretical fit shown in Table 2.

[0075] In one aspect of the invention where a surfactant is included in the cleaning composition, cationic surfactants are not preferred due to increased electrostatic interactions and therefore increased toxicity of the composition.

[0076] As such, anionic, nonionic and amphoteric surfactants, and their combinations, are preferred to reduce the interaction between biological material and quaternary ammonium compounds.Similarly, acid components are selected to help control pH and reduce electrostatic interaction.Further discussion of quaternary ammonium compounds and their suitability for use in reduced inhalation cleaning compositions can be found in U.S. Patent Application No. 15 / 445,146, filed February 28, 2017 [Attorney Docket No. PT10767USU1], the entire contents of which are incorporated herein by reference.

[0077] A cleaning composition according to one embodiment of the present invention includes at least one quaternary ammonium compound. Certain quaternary ammonium compounds are known to have antimicrobial activity. Therefore, a variety of quaternary ammonium compounds with antimicrobial activity can be used in the compositions of the present invention. In one aspect, the quaternary ammonium compound is an antimicrobial "quat." The term "quaternary ammonium compound" or "quat" generally refers to any composition having the formula: [ka] wherein R1-R4 are alkyl groups that may be the same or different, substituted or unsubstituted, saturated or unsaturated, branched or unbranched, and cyclic or acyclic, and may contain ether, ester, or amide bonds; they may be aromatic or substituted aromatic groups. In one embodiment, the R1, R2, R3, and R4 groups each have a chain length of less than C20. X- is an anionic counterion. The term "anionic counterion" includes any ion that can form a salt with a quaternary ammonium salt. Examples of suitable counterions include halides such as chloride and bromide, propionate, methosulfate, saccharinates, ethosulfate, hydroxide, acetate, phosphate, carbonate (e.g., commercially available from Lonza as Carboquat H), and nitrate. Preferably, the anionic counterion is chloride.

[0078] In some embodiments, the quaternary ammonium having a carbon chain of less than 20 is included in the composition of the present invention.Examples of quaternary ammonium compounds useful in the present invention 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, to name a few.A single quaternary ammonium or a combination of two or more quaternary ammonium compounds can be included in the composition of the present invention. Further examples of quaternary ammonium compounds useful in the present invention include, but are not limited to, benzethonium chloride, ethylbenzethonium chloride, myristyltrimethylammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium bromide (CTAB), carnitine, dophanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride, choline, cocamidopropyl betaine (CAPB), and denatonium.

[0079] In some embodiments, quaternary ammonium compounds having carbon chains of less than 20 or C2-C20 are included in the compositions of the present invention. In some 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 invention. Examples of quaternary ammonium compounds useful in the present invention 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, to name a few. A single quaternary ammonium compound or a combination of two or more quaternary ammonium compounds may be included in the compositions of the present invention. Other examples of quaternary ammonium compounds that are useful in the present invention include, but are not limited to, benzethonium chloride, ethylbenzylalkonium chloride, myristyltrimethylammonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetrimonium bromide (CTAB), carnitine, dophanium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzododecinium bromide, benzoxonium chloride, choline, cocamidopropyl betaine (CAPB), denatonium, and mixtures thereof.In one embodiment, the combination of quaternary ammonium compounds is particularly preferred for the present composition, for example, commercially available product Bardac 205 / 208M.

[0080] In some embodiments, depending on the R group, the nature of 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.

[0081] 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, commercially available under the trade names Rhodaquat M242C / 29 and Dehyquart A; alkyltrimethylammonium chloride, commercially available as Arquad 16; alkylaryltrimethylammonium chloride; and cetyldimethylethylammonium bromide, commercially available as Ammonyx DME.

[0082] Monoalkyldimethylbenzyl ammonium salts contain one R group that is a long-chain alkyl group, a second R group that is a benzyl radical, and the two remaining R groups are short-chain alkyl groups such as methyl or ethyl groups. Monoalkyldimethylbenzyl ammonium salts are generally compatible with nonionic surfactants, detergent builders, fragrances, and other ingredients. Some non-limiting examples of monoalkyldimethylbenzyl ammonium salts include alkyldimethylbenzyl ammonium chloride, commercially available from Lonza Inc. as Barquat, and benzethonium chloride, commercially available from Lonza Inc. as Lonzagard. In addition, monoalkyldimethylbenzyl ammonium salts may be substituted. Non-limiting examples of such salts include dodecyldimethyl-3,4-dichlorobenzyl ammonium chloride. Finally, there are mixtures of alkyldimethylbenzyl and alkyldimethyl-substituted benzyl (ethylbenzyl) ammonium chlorides, commercially available from Stepan Company as BTC 2125M and from Lonza Inc. as Barquat 4250.

[0083] 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.

[0084] Heteroaromatic ammonium salts contain one R group that is a long-chain alkyl group, and the remaining R groups are provided by several aromatic systems. 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, commercially available as Sumquat 6060 / CPC from Zeeland Chemical Inc., 1-[3-chloroalkyl]-3,5,7-triaza-1-azoniaadamantane, commercially available as Dowicil 200 from The Dow Chemical Company, and alkyl-isoquinolinium bromide.

[0085] Polysubstituted quaternary ammonium salts are monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, or heteroaromatic ammonium salts in which 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.

[0086] Bis-quaternary ammonium salts have the general formula: [ka] where the R groups may be long- or short-chain alkyl, benzyl radicals, or may be provided by aromatic systems. 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-aminoquinolinium chloride)-decane, and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride]hexane or triclobissonium chloride.

[0087] 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 soluble and good antimicrobial agents.

[0088] In one embodiment, the quaternary ammonium compound is a short dialkyl chain quaternary ammonium compound having an R group of 2 carbons to about 12 carbons, 3 carbons to about 12 carbons, or 6 carbons to about 12 carbons.

[0089] In a preferred embodiment, the quaternary ammonium compound is alkylbenzyl ammonium chloride, dialkylbenzyl ammonium chloride, a blend of alkylbenzyl ammonium chloride and dialkylbenzyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, a blend of didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloride, or a mixture thereof. In a preferred embodiment, the quaternary ammonium compound used in the cleaning compositions of the present invention consists of a mixture of dialkyl quaternary ammonium and alkylbenzyl quaternary ammonium.

[0090] According to embodiments of the present invention providing cleaning compositions, an effective amount of a quaternary ammonium compound is provided in combination with a polymer to provide antimicrobial efficacy against a broad spectrum of microorganisms, including Gram-negative microorganisms such as E. coli. Suitable concentrations of the quaternary ammonium compound in such use solutions include at least about 10 ppm, at least about 50 ppm, or at least about 100 ppm, or at least about 150 ppm, or at least about 200 ppm, or at least about 250 ppm, or at least about 300 ppm, or about 100-500 ppm, or about 100-300 ppm, or any range therein. In some embodiments, activated microbial compositions according to the present invention provide efficacy against Gram-negative conventional requirements of greater than 150 ppm of quaternary ammonium compound for any antimicrobial efficacy at concentrations less than about 150 ppm, or less than about 100 ppm, due to the synergistic effect of the quaternary ammonium compound in combination with anionic surfactants and / or acids. While not intended to be limiting, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0091] Additional suitable concentrations of the quaternary ammonium compound in a use solution of the cleaning composition include about 1 ppm to about 10,000 ppm, 1 ppm to about 1,000 ppm, 5 ppm to about 400 ppm, 10 ppm to about 400 ppm, 20 ppm to about 400 ppm, 25 ppm to about 400 ppm, 50 ppm to about 400 ppm, 75 ppm to about 400 ppm, or 100 ppm to about 400 ppm. Additional suitable concentrations of the quaternary ammonium compound in a use solution of the cleaning composition include about 0.0001% to about 10% by weight, about 0.001% to about 10% by weight, about 0.01% to about 10% by weight, and about 1.0% to about 10% by weight. While not intended to be limiting by the present invention, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0092] Acid disinfectant Various acid disinfectants can be used in accordance with the present invention. In embodiments of the present invention, the acid disinfectant can be a carboxylic acid, a peracid, a mineral acid, an organic acid, an amino acid, a fatty acid, or a linear alkyl benzene. It should be understood that derivatives and combinations of each of the acid disinfectants can be used in accordance with the present invention.

[0093] In one aspect of the present invention, the acid disinfectant is a carboxylic acid. Generally, carboxylic acids have the formula R-COOH, where R can represent any number of different groups, including aliphatic, alicyclic, aromatic, and heterocyclic groups, all of which can be saturated or unsaturated, and substituted or unsubstituted. Carboxylic acids with one, two, three, or more carboxyl groups also occur. Carboxylic acids tend to acidify aqueous compositions in which they are present because the hydrogen atom of the carboxyl group is active and can appear as an anion. When combined with aqueous hydrogen peroxide, the carboxylic acid component within the present composition generally functions as an antimicrobial agent as a result of the presence of the active hydrogen atom. The carboxylic acid component within the present invention also maintains the composition at an acidic pH. Examples of such carboxylic acids include, but are not limited to, acetic acid, citric acid, succinic acid, adipic acid, hydroxyacetic acid, and lactic acid. Those skilled in the art will understand that other carboxylic acids can be used for the purposes of the present invention.

[0094] Various C6-C18 peroxyacids, such as peroxyfatty acids, monoperoxy- or diperoxydicarboxylic acids, and peroxyaromatic acids, can be used in the compositions of the present invention. The C6-C18 peroxyacids used in the present invention can be structurally represented as follows: R1--CO3H, where R1 is a hydrocarbon moiety having approximately 5 to 17 carbon atoms (C18 peroxyacids are generally structurally represented as C7--CO3H). R1 ​​can have substituents in the chain, such as --OH, CO2H, or heteroatoms (e.g., --O--, as in alkyl ether carboxylic acids), so long as the antimicrobial properties of the overall composition are not significantly affected. It should be recognized that the "R1" substituent or heteroatom can alter the overall acidity (i.e., pKa) of the carboxylic acids described herein. Such modifications are within the contemplation of the present invention, so long as advantageous antimicrobial performance is maintained. Furthermore, R1 can be linear, branched, cyclic, or aromatic. Preferred hydrocarbon moieties (ie, preferred R1 moieties) include straight chain saturated hydrocarbon aliphatic moieties having 7 to 11 carbon atoms (or 8 to 12 carbon atoms per molecule).

[0095] Specific examples of suitable C6-C18 carboxylic acids that can be reacted with hydrogen peroxide to form peroxy fatty acids include saturated fatty acids such as hexanoic acid (C6), enanthic acid (heptanoic acid) (C7), caprylic acid (octanoic acid) (C8), pelargonic acid (nonanoic acid) (C9), capric acid (decanoic acid) (C10), undecylic acid (undecanoic acid) (C11), lauric acid (dodecanoic acid) (C12), tridecylic acid (tridecanoic acid) (C13), myristic acid (tetradecanoic acid) (C14), palmitic acid (hexadecanoic acid) (C16), and stearic acid (octadecanoic acid) (C18). These acids can be derived from both natural and synthetic sources. Natural sources include animal and vegetable fats or oils, which must be fully hydrogenated. Synthetic acids can be produced by the oxidation of petroleum waxes. Particularly preferred peroxy fatty acids for use in the compositions of the present invention are straight chain monoperoxy aliphatic fatty acids such as peroxyoctanoic acid, peroxydecanoic acid, or mixtures thereof.

[0096] Other suitable C6-C18 peroxyacids are derived from the oxidation of dicarboxylic and aromatic acids. Suitable dicarboxylic acids include adipic acid (C6) and sebacic acid (C10). One example of a suitable aromatic acid is benzoic acid. These acids can be reacted with hydrogen peroxide to form peracid forms suitable for use in the compositions of the present invention. Preferred peracids in this group include monoperoxy- or diperoxyadipic acid, monoperoxy- or diperoxysebacic acid, and peroxybenzoic acid.

[0097] The peroxyacids provide antimicrobial activity against a wide variety of microorganisms, such as gram-positive (e.g., Staphylococcus aureus) and gram-negative (e.g., Escherichia coli) microorganisms, yeast, mold, bacterial spores, and the like. When the C6-C18 peroxyacids are combined with C1-C4 peroxycarboxylic acids, they exhibit significantly improved activity compared to C1-C4 peroxycarboxylic acids or C6-C18 peroxycarboxylic acids alone. The C1-C4 peroxycarboxylic acid component can be derived from a C1-C4 carboxylic or dicarboxylic acid by reacting the acid with hydrogen peroxide. Examples of suitable C1-C4 carboxylic acids include acetic acid, propionic acid, glycolic acid, and succinic acid. Preferred C1-C4 peroxycarboxylic acids for use in the compositions of the present invention include peroxyacetic acid, peroxypropionic acid, peroxyglycolic acid, peroxysuccinic acid, or mixtures thereof.

[0098] The peracid component used in the compositions of the present invention can be prepared in a simple manner by mixing a hydrogen peroxide (H2O2) solution with the desired amount of acid. For higher molecular weight fatty acids, a hydrotropic coupler may be required to help solubilize the fatty acid. To produce the peracid compositions of the present invention, the H2O2 solution can also be added to pre-made peracids, such as peracetic acid or various peracid fatty acids. Concentrates can contain about 1-50% by weight, preferably about 5-25% by weight, of hydrogen peroxide. U.S. Patent No. 5,200,189, filed July 31, 1991, further discloses the use of peracids in cleaning compositions and is incorporated herein by reference in its entirety.

[0099] In one aspect of the present invention, the acid disinfectant is a mineral acid, i.e., an inorganic acid. Examples of such mineral acids include, but are not limited to, phosphoric acid, sulfamic acid, sulfuric acid, nitric acid, and hydrochloric acid. Generally, all mineral acids form hydrogen ions and conjugate base ions when dissolved in water. For example, sulfuric acid forms hydrogen sulfate in aqueous solution by complete ionization, forming hydronium ions and hydrogen sulfate. Such conjugate bases are also useful acid components for the purposes of the present invention.

[0100] In one aspect of the present invention, the acid disinfectant is an organic acid. Suitable organic acids include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzenesulfonic acid, formic acid, acetic acid, mono-, di-, or trihalocarboxylic acids, picolinic acid, dipicolinic acid, and mixtures thereof.

[0101] In one aspect of the present invention, the acid disinfectant is an amino acid and / or an amino acid derivative. Generally, amino acids contain an amine functional group and a carboxylic acid functional group, usually with a side chain group for each amino acid. Suitable amino acids and / or amino acid derivatives include, but are not limited to, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, selenocysteine, pyrrolidin, and derivatives thereof.

[0102] In one aspect of the present invention, the acid disinfectant is a fatty acid and / or a fatty acid surfactant. Antimicrobially active acids are used in disinfection procedures. For example, U.S. Patent No. 404,040 describes disinfectant compositions containing aliphatic, short-chain fatty acids, a fatty acid hydrotrope or solubilizer, and a hydrotrope-compatible acid. U.S. Patent No. 5,330,769 describes fatty acid disinfectant concentrates and diluted final solutions containing individual amounts of germicidal fatty acids, a hydrotrope, a strong acid group consisting of phosphoric acid and sulfuric acid or mixtures thereof sufficient to lower the pH of the final solution to about 1-5, and a stabilizing weak acid component selected from the group consisting of propionic acid, butyric acid, and valeric acid, and mixtures thereof. As used herein, the term "fatty acid" includes any of a group of carboxylic acids containing an alkyl chain. In some embodiments, the alkyl group can be linear or branched, and saturated or unsaturated. The alkyl group chain can contain any carbon atom length. In some embodiments, the alkyl group chain contains 4-12 carbon atoms, 5-11 carbon atoms, or 8-10 carbon atoms. Exemplary fatty acids can be selected from hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, caproic acid, caprylic acid, capric acid, and mixtures thereof. Exemplary longer alkyl chain fatty acids can be selected from, for example, myristic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, decosahexaenoic acid, gadoleic acid, erucic acid, margaric acid, behenic acid, ricinoleic acid, lignoceric acid, licanic acid, eleostearic acid, and mixtures thereof.

[0103] In one aspect of the present invention, the acid disinfectant is a linear alkylbenzene. Suitable linear alkylbenzenes include linear alkylbenzene sulfonates (LAS) and linear alkylbenzene sulfonic acids (LABSA). Others that can be used include alkylbenzene sulfonates, alkyl sulfonates, alkyl ether sulfates, alpha olefin sulfonates, alkyl sarcosinates, and mixtures thereof.

[0104] oxidizing agent According to one embodiment of the present invention, the cleaning composition comprises at least one oxidizing agent and at least one polymeric compound. The oxidizing agent can be any oxidizing agent compatible with cationic, nonionic, and / or anionic polymers. Examples of such oxidizing agents include non-organic oxidizing agents such as hydrogen peroxide, sodium percarbonate, sodium periodate, sodium persulfate, ammonium persulfate, sodium perborate, sodium peroxide, calcium peroxide, silver(II) oxide, ozone, and chlorine dioxide. Oxidizing agents also include organic oxidizing agents, such as diacyl peroxides such as benzoyl peroxide, ketone peroxides such as 2,4-pertanedione peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate, peroxyesters such as t-butyl peroxymaleic acid, dialkyl peroxides such as dicumyl peroxide, hydroperoxides such as t-butyl hydroperoxide, and peroxyketals such as 2,2-di(t-butylperoxy)butane. Additional oxidizing agents are disclosed in US Pat. No. 5,616,616, filed Jun. 1, 1994, which is incorporated herein by reference in its entirety.

[0105] amine The cleaning component can also be an antimicrobial amine. The amine can be a primary, secondary, or tertiary amine. Alternatively, the composition can include a quaternary ammonium compound. The amine concentration in the system can range from about 0.5 to about 8.5% by weight, about 1.0 to about 3.0% by weight, or about 1.25 to about 2.0% by weight. The amine is preferably a tertiary amine. However, other exemplary antimicrobial amines include fatty amines; fatty amine salts, such as fatty ammonium salts; and amines sold by Tomah, such as PA-19, PA-1618, PA-1816, DA-18, DA-19, DA-1618, and DA-1816. or ether amines having the formula R1-O-R2-NH2, R1-O-R2-NH-R3-NH2, or mixtures thereof, where (independently) R1 = linear saturated or unsaturated C6-C18 alkyl, R2 = linear or branched C1-C8 alkyl, and R3 = linear or branched C1-C8 alkyl, or R1 = linear C12-C16 alkyl, R2 = C2-C6 linear or branched alkyl, and R3 = C2-C6 linear or branched alkyl, or R1 = linear C12-C16 alkyl, or a mixture of linear C10-C12 and C14-C16 alkyl, R2 = C3, and R3 = C3; ether amine salts, such as ether ammonium salts; N-coco-1,3-propylene diamine (Duomeen® - AkzoChemie America, Armak diamines such as N-oleyl-1,3-propylenediamine (Duomeen®-AkzoChemie America, Armak Chemicals, etc.), N-tallow-1,3-propylenediamine (Duomeen®-AkzoChemie America, Armak Chemicals, etc.); diamine salts such as diamine acetate (or other counterions), or R1 = C10-C18 aliphatic groups, or R 10 = C10 to C18 aliphatic group and R 11 = C1-C5 alkyl group of formula R 10 OR 11and R2=C1-C5 alkylene group, or R1=C10-C18 aliphatic group derived from a fatty acid, and R2=propylene, + (CH3COO) - or [(R1)NH2(R2)NH3 + ] + Diamine salts having the formula (CHCOO)- Additional suitable amines are disclosed in U.S. Patent No. 7,964,548, filed April 5, 2010, which is incorporated herein by reference in its entirety.

[0106] Polymer Component The cleaning compositions according to the present invention comprise a polymer component. As shown in Table 1, the selection of cleaning components influences the desired charge of the polymer to achieve the desired reduced inhalation risk while beneficially providing cleaning, disinfecting, sanitizing, and / or antimicrobial efficacy. In one aspect of the invention, the polymer can have a cationic, nonionic, or anionic charge and can be in the form of an inverse emulsion polymer, a dispersion polymer, a powder polymer, and / or xanthan gum.

[0107] Inverse Emulsion Polymer A cleaning composition according to one embodiment of the present invention comprises an inverse emulsion polymer. In one aspect, the inverse emulsion polymer is a water-soluble modified polymer. In one aspect, the inverse emulsion polymer can be cationic, anionic, nonionic, amphoteric, and / or associative. The terms emulsion polymer and latex polymer can be used interchangeably herein and refer to water-in-oil (W / O) emulsion polymers, including cationic, anionic, nonionic, and / or zwitterionic polymers.

[0108] In one embodiment, the inverse emulsion polymer has a high molecular weight of about 3,000 Da to about 50 million Da, about 500,000 Da to about 30 million Da, about 1 million Da to about 25 million Da, preferably about 3 million Da to about 20 million Da.

[0109] In one embodiment, the inverse emulsion polymer has an intrinsic viscosity greater than about 1, more preferably greater than about 6, and even more preferably from about 15 to about 30 dL / g. The reduced specific viscosity of the inverse emulsion polymer is generally greater than 3, preferably greater than about 8, and often greater than about 24 dL / g.

[0110] In one embodiment, the inverse emulsion polymers according to the present invention have a particle size ranging from about 0.1 to about 10 microns, preferably from about 0.25 to about 3 microns.

[0111] In one embodiment, the inverse emulsion polymers according to the present invention have a bulk viscosity ranging from about 50 to 5000 cPs, preferably from about 100 to 2000 cPs.

[0112] Inverse emulsion polymers according to the present invention are stabilized dispersions of flexible polymer chains containing aqueous droplets in an inert hydrophobic phase. In one embodiment, inverse emulsion polymers are composed of three components, including (1) a hydrophobic or hydrocarbon-continuous oil phase, (2) an aqueous phase, and (3) a water-in-oil emulsifier (i.e., a surfactant system). In one embodiment, the inverse emulsion polymer is hydrocarbon-continuous with a water-soluble polymer dispersed within the hydrocarbon matrix. The inverse emulsion polymer is then "inverted" or activated for use by shearing, dilution, and typically using another surfactant to release the polymer from the particles. See U.S. Pat. No. 3,734,873, which is incorporated herein by reference. Representative preparations of high molecular weight inverse emulsion polymers are described in U.S. Pat. Nos. 2,982,749, 3,284,393, and 3,734,873, each of which is incorporated herein by reference.

[0113] In another embodiment, the inverse emulsion polymer is formed by polymerization of an aqueous solution of monomers under free radical polymerization conditions to form a polymer solution, as disclosed in U.S. Patent Nos. 6,605,674 and 6,753,388, each of which is incorporated herein by reference. In a preferred embodiment, the inverse emulsion polymer is obtained by polymerizing an aqueous solution of ethylenically unsaturated water-soluble or water-dispersible monomers and / or comonomers emulsified in a hydrophobic continuous phase by using an oil-soluble and / or water-soluble initiator via radical polymerization.

[0114] As used herein, the term "monomer" of an inverse emulsion polymer refers to a polymerizable allylic, vinyl, or acrylic compound. The monomer can be anionic, cationic, nonionic, and / or zwitterionic. In some embodiments, vinyl monomers are preferred, while in other embodiments, acrylic acid and / or acrylamide monomers, such as acrylic acid or its salts, Nt-butylacrylamidosulfonic acid (ATBS) or its salts, acrylamido-tertiary butylsulfonic acid or its salts, and 2-(acryloyloxy)-N,N,N-trimethylethaneammonium (DMAEA.MCQ), are more preferred.

[0115] In one embodiment, the nonionic monomers are particularly suitable for use in neutral, acidic, alkaline, and / or oxidizing cleaning compositions. Representative nonionic water-soluble monomers include acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-tert-butylacrylamide, N-methylolacrylamide, and the like.

[0116] In one embodiment, the anionic monomer is particularly suitable for use in alkaline, neutral, and / or oxidizing cleaning compositions. Representative anionic monomers include acrylic acid and its salts, including but not limited to, sodium acrylate and ammonium acrylate, methacrylic acid and its salts, including but not limited to, sodium methacrylate and ammonium methacrylate, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), the sodium salt of ATBS, acrylamido-tertiary butylsulfonic acid or its salts, sodium vinylsulfonate, styrene sulfonate, maleic acid and its salts, including but not limited to, the sodium and ammonium salts, sulfonates, itaconates, sulfopropyl acrylate or methacrylate, or other water-soluble forms of these or other polymerizable carboxylic or sulfonic acids. Sulfomethylated acrylamide, allyl sulfonate, sodium vinyl sulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid, sulfomethylated acrylamide, phosphonomethylated acrylamide, etc.

[0117] In one embodiment, the cationic monomer is particularly suitable for use in acidic and / or oxidizing cleaning compositions. Representative cationic monomers include dialkylaminoalkyl acrylates and methacrylates, as well as dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dialkylaminoalkyl acrylamides or methacrylamides and their quaternary or acid salts, such as acrylamidopropyltrimethylammonium chloride, dimethylaminoethyl acrylate methyl chloride quaternary salt ...acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride and dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate.

[0118] In one embodiment, the zwitterionic monomers are particularly suitable for use in neutral, acidic, alkaline, and / or oxidizing cleaning compositions. Exemplary zwitterionic monomers include N,N-dimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, 2-(methylthio)ethylmethacryloyl-S-(sulfopropyl)-sulfonium betaine, 2-[(2-acryloylethyl)dimethylammonio]ethyl 2-methylphosphate, 2-(acryloyloxyethyl)-2'-(trimethylammonium phosphate), ... ammonium)ethyl phosphate, [(2-acryloylethyl)dimethylammonio]methylphosphonic acid, 2-methacryloyloxyethyl phosphorylcholine (MPC), 2-[(3-acrylamidopropyl)dimethylammonio]ethyl 2'-isopropyl phosphate (AAPI), 1-vinyl-3-(3-sulfopropyl)imidazolium hydroxide, (2-acryloxyethyl)carboxymethyl methylsulfonium chloride, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, N-(4-sulfobutyl)-N-methyl-N,N-diallylamine ammonium betaine (MDABS), N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine, and the like.

[0119] In one aspect, the aqueous phase is prepared by mixing together in water one or more water-soluble monomers and polymerization additives such as inorganic or hydrophobic salts, chelating agents, pH buffers, processing aids, etc. In one embodiment, the monomers are ethylenically unsaturated water-soluble or water-dispersible monomers and / or comonomers. In a further embodiment, the monomers are emulsified in the hydrophobic or hydrocarbon-continuous oil phase by radical polymerization using an oil-soluble and / or water-soluble initiator, and the polymers can be nonionic, anionic, cationic, and / or zwitterionic. In a preferred embodiment, the monomer is selected from acrylamides or methacrylamides, such as acrylic acid or its salts, Nt-butylacrylamidosulfonic acid (ATBS) or its salts, acrylamido-tertiary butylsulfonic acid or its salts, or 2-(acryloyloxy)-N,N,N-trimethylethaneammonium (DMAEA.MCQ). In a further preferred embodiment, the monomer is further selected from the group consisting of diallyldimethylammonium chloride, dimethylaminoethyl acrylate methyl chloride quaternary salt, acrylamidopropyltrimethylammonium chloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, methacrylamidopropyltrimethylammonium chloride, acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, and ammonium methacrylate.

[0120] In a preferred embodiment, the monomers are acrylamide and diallyldimethylammonium chloride. In a more preferred embodiment, the monomers are acrylamide and dimethylaminoethyl acrylate methyl chloride quaternary salt. In a more preferred embodiment, the monomers are acrylamide, dimethylaminoethyl acrylate, benzyl chloride quaternary salt, and dimethylaminoethyl acrylate methyl chloride quaternary salt. Representative copolymers of acrylic acid and acrylamide useful as microparticles include Nalco® 8677 PLUS, available from Nalco Chemical Company, Naperville, IL, USA. Other copolymers of acrylic acid and acrylamide are described in U.S. Patent No. 5,098,520, which is incorporated herein by reference.

[0121] The degree of polymerization of the monomer in the aqueous phase is determined by the change in reaction density in a water-in-oil emulsion polymerization, by measuring the heat of reaction calorimetrically, by quantitative infrared spectroscopy, or by measuring the level of unreacted monomer by chromatography.

[0122] In one embodiment, the water phase is added (under high shear mixing or vigorous agitation) to the oil phase to form an emulsion.

[0123] The hydrophobic / hydrocarbon (or oil) phase is prepared by mixing together an inert hydrocarbon liquid and one or more oil-soluble surfactants. The hydrophobic liquid is selected from the group consisting of benzene, xylene, toluene, mineral oil, kerosene, naphtha, petroleum, and combinations thereof. In a preferred embodiment, the hydrophobic liquid is an isoparaffinic hydrocarbon. The surfactant mixture should have a low HLB to ensure the formation of an oil-continuous emulsion. Commercially available surfactants suitable for water-in-oil emulsion polymerization are summarized in the North American Edition of McCutcheon's Emulsifiers & Detergents, which is incorporated by reference in its entirety.

[0124] In one embodiment, the inverse emulsion polymer is a free-flowing liquid. In the simplest methodology, an aqueous solution of the inverse emulsion polymer can be produced by adding the desired amount of emulsion polymer to water with vigorous mixing in the presence of a high HLB surfactant, as described in U.S. Pat. No. 3,734,873, the entire contents of which are incorporated herein by reference.

[0125] An effective amount of inverse emulsion polymer is provided in the cleaning composition to provide a ready-to-use, reduced inhalation risk composition having a lower concentration than conventional viscosity-modifying polymers. Beneficially, the inverse emulsion polymer is highly concentrated for dilution systems and maintains viscoelasticity even in such highly concentrated formulations. Suitable concentrations of inverse emulsion polymer in concentrated formulations include about 0.0001% to about 1% by weight, about 0.0005% to about 0.5% by weight, about 0.01% to about 0.2% by weight, and more preferably about 5 ppm to 200 ppm of active inverse emulsion polymer. While not intended to be limiting by the present invention, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0126] Dispersion Polymer In one embodiment of the present invention, the polymer component is a dispersed polymer. Dispersed polymer refers to a dispersion of fine particles of polymer in an aqueous salt solution, which is prepared by polymerizing monomers with stirring in an aqueous salt solution in which the resulting polymer is insoluble. See U.S. Patent Nos. 8,992,688, 5,708,071, 4,929,655, 5,006,590, 5,597,859, and 5,597,858, as well as European Patent Nos. 657,478 and 630,909. A typical procedure for preparing solution and gel polymers involves preparing an aqueous solution containing one or more water-soluble monomers and any additional polymerization additives, such as chelating agents, pH buffers, etc. This mixture is placed in a reactor equipped with a mixer, thermocouple, nitrogen purge, and water condenser. The solution is vigorously mixed and heated to the desired temperature, after which one or more polymerization initiators are added. The solution is purged with nitrogen while maintaining the temperature and mixing for several hours. The viscosity of the solution typically increases during this period. After polymerization is complete, the reactor contents are cooled to room temperature and then transferred to storage. Solution and gel polymer viscosities vary widely and depend on the concentration and molecular weight of the active polymer component.

[0127] In one aspect of the invention, the dispersion polymer is a cationic, anionic, or nonionic high molecular weight dispersion polymer.

[0128] Suitable concentrations of dispersion polymer in concentrated formulations include from about 0.0001% to about 1% by weight, from about 0.0005% to about 0.5% by weight, from about 0.01% to about 0.2% by weight, and more preferably from about 5 ppm to 200 ppm of active dispersion polymer. Although not intended to be limited by the present invention, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0129] Powdered Polymer In one embodiment of the present invention, the polymer component is formulated as a dry or powdered polymer. In one example, the polymer component comprises a mixture of polyethylene oxide (PEO), polyacrylamide, and polyacrylate. In a further example, the polymer component comprises a mixture of PEO and polyacrylamide. PEO is a high molecular weight polymer. Suitable PEOs can have a molecular weight of about 3,000,000 to about 7,000,000. One commercially available PEO is Polyox WSR 301, which has a molecular weight of about 4,000,000 and is available from Dow. A suitable concentration range for PEO is about 0.01% to 0.3% by weight of the concentrated cleaning solution. A particularly suitable concentration range for PEO is about 0.01% to 0.2% by weight of the concentrated cleaning solution.

[0130] The polymer component may alternatively or additionally comprise polyacrylamide. Suitable polyacrylamides may have a molecular weight of about 8 to 16 million, more preferably about 11 to 13 million. One commercially available polyacrylamide is SuperFloc® N-300, available from Kemira Water Solutions, Inc. A suitable concentration range for polyacrylamide is about 0.01 to 0.3% by weight of the concentrated cleaning solution. A particularly suitable concentration range for polyacrylamide is about 0.01 to 0.2% by weight of the concentrated cleaning solution.

[0131] Polyacrylates are high molecular weight polymers. Suitable polyacrylate polymers can have a molecular weight of about 500,000 to about 3 million. More suitable polyacrylate polymers can have a molecular weight of at least about 1 million. One commercially available polyacrylate is Aquatreat® AR-7H, available from Akzo Nobel. A suitable polyacrylate concentration in a concentrated composition is about 0.5% to about 20% by weight. A particularly suitable polyacrylate concentration in a concentrated composition is about 1% to about 10% by weight.

[0132] In further embodiments of the present invention, other known suitable polymers may be formulated as dry polymers or powders for inclusion in cleaning compositions according to the present invention. Examples of such suitable polymers can be found in U.S. Patent Nos. 9,127,241 and 9,206,281, which are incorporated by reference in their entireties.

[0133] xanthan gum In one aspect of the present invention, the polymer component is xanthan gum. Xanthan is an exopolysaccharide of Xanthomonas campestras. It is produced by fermentation of corn sugar or other corn sweetener by-products. Xanthan contains a polybeta-(1→4)-D-glucopyranosyl backbone similar to that found in cellulose. Aqueous dispersions of xanthan gum and its derivatives exhibit novel and remarkable rheological properties. Low concentrations of the gum have relatively high viscosities, allowing for economical use and applications. Xanthan gum solutions exhibit high pseudoplasticity, i.e., rapid shear thinning, generally understood to be instantly reversible, occurs over a wide range of concentrations. Shear-free materials have viscosities that are considered pH-independent and temperature-independent over a wide range. Preferred xanthan materials include crosslinked xanthan materials. Xanthan polymers can be crosslinked with various known covalent crosslinkers reactive with the hydroxyl functional groups of large polysaccharide molecules, and can also be crosslinked using divalent, trivalent, or polyvalent metal ions. Such cross-linked xanthan gels are disclosed in U.S. Pat. No. 4,782,901, which is incorporated herein by reference. Suitable cross-linking agents for xanthan materials include metal cations such as Al+3, Fe+3, Sb+3, Zr+4, and other transition metals. Known organic cross-linking agents can also be used. A preferred cross-linked xanthan agent of the present invention is KELZAN AR, a product of Kelco, a division of Merck Incorporated. KELZAN AR is a cross-linked xanthan that provides a thixotropic cleaning agent capable of generating a large particle size mist or aerosol when sprayed.

[0134] Suitable concentrations of xanthan gum in the concentrated solution include about 0.0001% to about 1% by weight, about 0.0005% to about 0.5% by weight, about 0.01% to about 0.2% by weight, and more preferably about 5 ppm to 200 ppm by weight. Although not intended to be limiting by the present invention, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0135] Acid component The cleaning composition according to the present invention optionally includes at least one acid component. In other embodiments, the cleaning composition includes at least two acid components. The cleaning composition according to the present invention optionally includes at least one acid component when the cleaning component is a quaternary ammonium compound. Without wishing to be limited to a particular theory of the present invention, it is believed that the inclusion of an acid component maintains the pH of the cleaning composition at an acidic pH, thus allowing the quaternary ammonium compound to come into contact with biological material, such as lung tissue, reducing the risk of inhalation, i.e., toxicity. Under mildly acidic conditions, biological material may be at or near their respective isoelectric points. Therefore, reducing the electrostatic interaction between positively charged cleaning compounds or quaternary ammonium compounds and negatively or partially negatively charged biological material reduces the risk of toxicity and inhalation associated with cleaning compounds or quaternary ammonium compounds. Furthermore, cleaning compounds or quaternary ammonium compounds typically maintain a neutral or alkaline pH, where they function best, so the inclusion of an acid component in a cleaning composition based on a cleaning compound or quaternary ammonium compound is unexpected. In one embodiment of the present invention, the acid component is any compound that can act as a proton donor. In a further aspect of the invention, the acid component is a mineral acid, an organic acid, a carboxylic acid, an amino acid, an acidic chelating agent, and / or a compound capable of acting as a proton donor.

[0136] In a further aspect of the invention, at least two acid components are used in the composition according to the invention. Suitable acid components include carboxylic acids, mineral acids, organic acids, amino acids, acidic chelating agents, fatty acids, fatty acid surfactants, and / or compounds capable of acting as proton donors, and the components can be at least two of the same components of any suitable acid component class, at least two components of any suitable acid component class, or at least one component of any suitable acid class and at least one component of any different but still suitable acid class.

[0137] In one embodiment, the concentrated composition comprises about 0.1% to 30% by weight of the acid component, preferably about 0.1% to 25% by weight of the acid component, and more preferably about 1.0% to 20% by weight of the acid component. Additionally, although not intended to be limited by the present invention, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0138] Carboxylic Acid In one aspect of the present invention, the acid component is a carboxylic acid. Generally, carboxylic acids have the formula R-COOH, where R can represent any number of different groups, including aliphatic, alicyclic, aromatic, and heterocyclic groups, all of which can be saturated or unsaturated, and substituted or unsubstituted. Carboxylic acids with one, two, three, or more carboxyl groups also occur. Carboxylic acids tend to acidify aqueous compositions in which they are present because the hydrogen atom of the carboxyl group is active and can appear as an anion. When combined with aqueous hydrogen peroxide, the carboxylic acid component within the present composition generally functions as an antimicrobial agent as a result of the presence of the active hydrogen atom. The carboxylic acid component within the present invention also maintains the composition at an acidic pH. Examples of such carboxylic acids include, but are not limited to, acetic acid, citric acid, succinic acid, adipic acid, hydroxyacetic acid, and lactic acid. Those skilled in the art will understand that other carboxylic acids may be used for the purposes of the present invention.

[0139] mineral acids In one embodiment of the present invention, the acid component is a mineral acid, i.e., an inorganic acid. Examples of such mineral acids include, but are not limited to, phosphoric acid, sulfamic acid, sulfuric acid, nitric acid, and hydrochloric acid. Generally, all mineral acids form hydrogen ions and conjugate base ions when dissolved in water. For example, sulfuric acid forms hydrogen sulfate in aqueous solution by complete ionization, forming hydronium ions and hydrogen sulfate. Such conjugate bases are also useful acid components for the purposes of the present invention.

[0140] organic acid In one aspect of the present invention, the acid component is an organic acid. Suitable organic acids include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzenesulfonic acid, formic acid, acetic acid, mono-, di-, or trihalocarboxylic acids, picolinic acid, dipicolinic acid, and mixtures thereof.

[0141] amino acid In one aspect of the present invention, the acid component is an amino acid and / or an amino acid derivative. Generally, amino acids contain an amine functional group and a carboxylic acid functional group, usually with a side chain group for each amino acid. Suitable amino acids and / or amino acid derivatives include, but are not limited to, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, selenocysteine, pyrrolysine, and derivatives thereof.

[0142] Acidic chelating agents In one embodiment of the present invention, the acid component is an acidic chelating agent. As used herein, chelation refers to the binding or complexation of a bidentate or polydentate ligand. These ligands are often organic compounds and are referred to as chelants, chelators, chelating agents, and / or sequestering agents. A chelating agent forms multiple bonds with a single metal ion. A chelating agent is a chemical that forms a soluble complex molecule with certain metal ions, inactivating those ions so that they cannot normally react with other elements or ions to form precipitates or scale. The ligand forms a chelate complex with the substrate. The term refers to a complex in which a metal ion is bound to two or more atoms of the chelating agent. The chelating agent used in the present invention is one that has the ability to act as a proton donor.

[0143] Suitable chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Preferred chelating agents for use herein are amino acid-based chelating agents, preferably citrate, citrate, tartrate, and glutamic acid-N,N-diacetic acid and derivatives, and / or phosphonate-based chelating agents, preferably diethylenetriaminepentamethylphosphonic acid.

[0144] Aminocarboxylates include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetraproprionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof. Also included are MGDA (methylglycinediacetic acid), salts and derivatives thereof, and GLDA (glutamic acid-N,N-diacetic acid), salts and derivatives thereof. GLDA (salts and derivatives thereof) are particularly preferred according to the present invention, with the tetrasodium salt being particularly preferred.

[0145] Other suitable chelating agents include amino acid compounds or succinate compounds. The terms "succinate compounds" and "succinic acid compounds" are used interchangeably herein. Other suitable chelating agents are described in U.S. Patent No. 6,426,229. Specific suitable chelating agents include, for example, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDS), iminodiacetic acid (IDA), N-(2-sulfomethyl)aspartic acid (SMAS), N-(2-sulfoethyl)aspartic acid (SEAS), N-(2-sulfomethyl)glutamic acid (SMGL), N-(2-sulfoethyl)glutamic acid (SEGL), N-(2-sulfomethyl)glutamic acid (SEGL), N-(2-sulfoethyl)glutamic acid (SEGL), N-(2-sulfomethyl)aspartic acid (SMAS ... Suitable diacetic acids include N,N-methyliminodiacetic acid (MIDA), alanine-N,N-diacetic acid (ALDA), serine-N,N-diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid (ANDA), sulfanilic acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA), and sulfomethyl-N,N-diacetic acid (SMDA), as well as their alkali metal or ammonium salts. Ethylenediamine disuccinate ("EDDS"), particularly the [S,S] isomer, is preferred, as described in U.S. Patent No. 4,704,233. Hydroxyethyleneiminodiacetic acid, hydroxyiminodisuccinic acid, and hydroxyethylenediaminetriacetic acid are also preferred. Alanine is particularly preferred. N,N-bis(carboxymethyl)-, trisodium salt.

[0146] Other chelating agents include homopolymers and copolymers of polycarboxylic acids and their partially or fully neutralized salts, as well as monomeric polycarboxylic and hydroxycarboxylic acids and their salts. Preferred salts of the above compounds are ammonium and / or alkali metal salts, i.e., lithium, sodium, and potassium salts, with sodium salts being particularly preferred.

[0147] Suitable polycarboxylic acids are acyclic, alicyclic, polycyclic, and aromatic carboxylic acids, each of which preferably contains at least two carboxyl groups separated from each other by no more than two carbon atoms. Polycarboxylates containing two carboxyl groups include, for example, water-soluble salts of malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, and fumaric acid. Polycarboxylates containing three carboxyl groups include, for example, water-soluble citrate salts. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid. Another suitable polycarboxylic acid is a homopolymer of acrylic acid. Polycarboxylates end-capped with sulfonates are preferred.

[0148] Aminophosphonates are also suitable for use as chelating agents and include ethylenediaminetetrakis(methylenephosphonate) as a DEQUEST. Those aminophosphonates that do not contain alkyl or alkenyl groups with more than about 6 carbon atoms are preferred.

[0149] Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein, such as those described in U.S. Patent No. 3,812,044. Preferred compounds of this type, in their acid form, are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

[0150] Further suitable polycarboxylate chelating agents for use herein include citric acid, lactic acid, acetic acid, succinic acid, and formic acid, all preferably in the form of their water-soluble salts. Other suitable polycarboxylates are oxodisuccinate, carboxymethyloxysuccinate, and mixtures of tartrate monosuccinate and tartrate disuccinate, as described in U.S. Patent No. 4,663,071.

[0151] Fatty acids and fatty acid surfactants In one aspect of the present invention, the acid component is a fatty acid and / or a fatty acid surfactant. As used herein, the term "fatty acid" includes any of a group of carboxylic acids containing an alkyl chain. In some embodiments, the alkyl group can be straight or branched, saturated or unsaturated. The alkyl group chain can contain any length of carbon atoms. In some embodiments, the alkyl group chain contains 4 to 12 carbon atoms, 5 to 11 carbon atoms, or 8 to 10 carbon atoms. Exemplary fatty acids can be selected from hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, caproic acid, caprylic acid, capric acid, and mixtures thereof. Exemplary longer alkyl chain fatty acids can be selected from, for example, myristic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, decosahexaenoic acid, gadoleic acid, erucic acid, margaric acid, behenic acid, ricinoleic acid, lignoceric acid, licanic acid, eleostearic acid, and mixtures thereof.

[0152] In a further aspect of the invention, the acid component is a fatty acid surfactant. Various exemplary surfactants that are fatty acids are disclosed in the next section.

[0153] Additional surfactants In some embodiments, the compositions of the present invention optionally contain a surfactant. Surfactants suitable for use with the compositions of the present invention include, but are not limited to, nonionic surfactants, anionic surfactants, and amphoteric surfactants. In some embodiments, the concentrated compositions of the present invention contain from about 0% to about 30% by weight of a surfactant. In other embodiments, the concentrated compositions of the present invention contain from about 0.1% to about 30% by weight of a surfactant. In still other embodiments, the concentrated compositions of the present invention contain from about 0.5% to about 10% by weight of a surfactant.

[0154] Nonionic surfactants Useful additional nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically produced by the condensation of an organic aliphatic, alkylaromatic, or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety, typically ethylene oxide or its polyhydration product, polyethylene glycol. Specifically, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can be condensed with ethylene oxide or its polyhydration additive, or its mixture with an alkoxylene, such as propylene oxide, to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be easily adjusted to produce a water-dispersible or water-soluble compound with the desired degree of balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include:

[0155] Examples of initiator reactive hydrogen compounds include block polyoxypropylene-polyoxyethylene polymer compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine. Examples of polymer compounds made from sequential propoxylation and ethoxylation of initiators are commercially available from BASF Corp. One class of compounds is bifunctional (two reactive hydrogen) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule has a molecular weight of about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobic material between the hydrophilic groups, controlled by length to constitute about 10% to about 80% by weight of the final molecule. Another class of compounds is tetrafunctional block copolymers obtained from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotropes ranges from about 500 to about 7,000; the hydrophilic ethylene oxide is added to constitute about 10% to about 80% by weight of the molecule.

[0156] Condensation products of one mole of alkylphenol, in which the alkyl chain, linear or branched, or single or double alkyl member, contains from about 8 to about 18 carbon atoms, with from about 3 to about 50 moles of ethylene oxide. The alkyl group can be represented, for example, by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants can also be polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols. Examples of commercial compounds of this chemical structure are available under the trade names Igepal® from Rhone-Poulenc and Triton® from Union Carbide.

[0157] Condensation products of one mole of a saturated or unsaturated straight- or branched-chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alcohol portion can consist of a mixture of alcohols within the carbon range described above, or it can consist of an alcohol having a specific number of carbon atoms within this range. Examples of similar commercial surfactants are available under the trade names Lutensol™ and Dehydol™ from BASF, Neodol™ from Shell Chemical Co., and Alfonic™ from Vista Chemical Co.

[0158] The condensation product of one mole of a saturated or unsaturated, straight- or branched-chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide. The acid portion can consist of a mixture of acids within the carbon atom range defined above, or it can consist of an acid having a specific number of carbon atoms within this range. Examples of commercial compounds of this chemical structure are available under the trade names Disponil or Agnique from BASF and Lipopeg™ from Lipo Chemicals, Inc.

[0159] In addition to ethoxylated carboxylic acids, commonly referred to as polyethylene glycol esters, glycerides, glycerin, and other alkanoic acid esters formed by reaction with polyhydric (saccharide or sorbitan / sorbitol) alcohols have application herein in specialized embodiments, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecules that can be subjected to further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these materials. Care must be taken when adding these fatty esters or acylated carbohydrates to compositions of the present invention containing amylase and / or lipase enzymes due to potential incompatibilities.

[0160] Examples of nonionic low foaming surfactants include: Compounds from (1) are essentially inverted and modified by adding ethylene oxide to ethylene glycol to provide a hydrophile of a specified molecular weight, followed by the addition of propylene oxide to obtain a hydrophobic block on the outside (end) of the molecule. The hydrophobic portion of the molecule has a molecular weight of about 1,000 to about 3,100, and the central hydrophile comprises 10% to about 80% by weight of the final molecule. These inverted Pluronic™ surfactants are manufactured by BASF Corporation under the trade name Pluronic™ R surfactants. Similarly, Tetronic™ R surfactants are manufactured by BASF Corporation by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of the molecule has a molecular weight of about 2,100 to about 6,700, and the central hydrophile comprises 10% to about 80% by weight of the final molecule.

[0161] Compounds from groups (1), (2), (3), and (4) that have been modified by "capping" or "end-blocking" the terminal hydroxy group(s) (of the polyfunctional moiety) to reduce foaming by reaction with hydrophobic small molecules such as propylene oxide, butylene oxide, benzyl chloride, and short-chain fatty acids, alcohols, or alkyl halides containing 1 to about 5 carbon atoms, and mixtures thereof. Also included are reactants such as thionyl chloride that convert the terminal hydroxy group to a chloride group. Such modifications to the terminal hydroxy group can result in all-block, block-heteric, heteric-block, or all-heteric nonionics.

[0162] Additional examples of effective low foaming nonionics include: U.S. Patent No. 2,903,486 issued to Brown et al. on September 8, 1959. [ka] An alkylphenoxypolyethoxyalkanol represented by the formula: R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.

[0163] Polyalkylene glycol condensates of U.S. Pat. No. 3,048,548, issued Aug. 7, 1962 to Martin et al., having alternating hydrophilic oxyethylene and hydrophobic oxypropylene chains, with the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units, and the weight of the linking hydrophilic units each representing about one-third of the condensate.

[0164] The general formula Z[(OR) (R ... n OH] z The antifoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178, issued May 7, 1968 to Lissant et al., having the formula:

[0165] Y is the residue of an organic compound having about 1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value of at least about 6.4 as determined by the hydroxyl number, and m has a value such that the oxyethylene moieties constitute from about 10% to about 90% by weight of the molecule, of the formula Y(CHO). n (C2H4O) m The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,677,700 issued to Jackson et al. on May 4, 1954, correspond to H.

[0166] and m is a value such that the oxyethylene content of the molecule is from about 10% to about 90% by weight. n (C2H4O) m H] x Conjugated polyoxyalkylene compounds as described in U.S. Patent No. 2,674,619, issued April 6, 1954 to Lundsted et al. Compounds falling within the definition for Y include, for example, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, ethylenediamine, and the like. The oxypropylene chains optionally, but beneficially, contain small amounts of ethylene oxide, and the oxyethylene chains also optionally, but beneficially, contain small amounts of propylene oxide.

[0167] Additional conjugated polyoxyalkylene surfactants advantageously used in the compositions of the present invention have the formula: P[(CHO) n (C2H4O) m H] x where P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, x having a value of 1 or 2, n having a value such that the molecular weight of the polyoxyethylene portion is at least about 44, and m having a value such that the oxypropylene content of the molecule is from about 10% to about 90% by weight. In either case, the oxypropylene chains may optionally, but beneficially, contain small amounts of ethylene oxide, and the oxyethylene chains may also optionally, but beneficially, contain small amounts of propylene oxide.

[0168] Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions have the structural formula R2CON R1Z, where R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy group, or mixtures thereof; R2 is a C5-C 31 Z is a hydrocarbyl; Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z may be obtained from a reducing sugar in a reductive amination reaction, such as a glycityl moiety.

[0169] Alkyl ethoxylate condensation products of aliphatic alcohols with about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.

[0170] Ethoxylated C6~C 18 Fatty alcohols and C6-C 18 Mixed ethoxylated and propoxylated fatty alcohols, especially those that are water soluble, are suitable surfactants for use in the present compositions. Suitable ethoxylated fatty alcohols are C6-C8 fatty acids having a degree of ethoxylation of 3 to 50. 18 Contains ethoxylated fatty alcohols.

[0171] Nonionic alkyl polysaccharide surfactants particularly suitable for use in the present compositions include those disclosed in U.S. Patent No. 4,565,647, issued January 21, 1986, to Llenado. These surfactants contain a hydrophobic group containing about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing about 1.3 to about 10 saccharide units. Any reduced saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose, and galactosyl moieties can be substituted for the glucosyl moiety. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. position, thus resulting in glucose or galactose, as opposed to glucoside or galactoside.) The intersaccharide bond can be, for example, between one position of the additional saccharide unit and the 2-, 3-, 4-, and / or 6-position on the preceding saccharide unit.

[0172] Fatty acid amide surfactants suitable for use in the present compositions include those having the formula: RCON(R) where R is an alkyl group containing 7 to 21 carbon atoms and each R is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or --(CHO). X H, and x is in the range of 1 to 3.

[0173] A useful class of nonionic surfactants includes the class defined as alkoxylated amine or, most specifically, alcohol alkoxylated / aminated / alkoxylated surfactants. These nonionic surfactants can be, at least in part, characterized by the general formula: R 20 --(PO) S N--(EO) t H, R 20 --(PO) S N--(EO) t H(EO) t H, and R 20 --N(EO) t H, where R 20is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5, and u is 1 to 10, preferably 2 to 5. Other variations in the scope of these compounds include those represented by the alternative formula: R 20 --(PO) V --N[(EO) w H][(EO) z H], wherein R 20 is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z are independently 1 to 10, preferably 2 to 5. These compounds are commercially represented by the line of products sold by Huntsman Chemicals as nonionic surfactants. Preferred chemicals in this class include Surfonic™ PEA 25 amine alkoxylate. Preferred nonionic surfactants for the compositions of the present invention include alcohol alkoxylates, EO / PO block copolymers, alkylphenol alkoxylates, and the like.

[0174] The article "Nonionic Surfactants," edited by Schick, MJ, Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983, is an excellent reference for the wide range of nonionic compounds commonly used in the practice of this invention. A typical listing of nonionic classes and species of these surfactants is found in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are found in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch).

[0175] Semi-polar nonionic surfactants Semi-polar nonionic surfactants are another class of additional nonionic surfactants useful in the compositions of the present invention. Generally, semi-polar nonionics are high-foaming agents and foam stabilizers, which can limit their application in CIP systems. However, in compositional embodiments of the present invention designed for high-foam cleaning methods, semi-polar nonionics have immediate practical application. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides, and their alkoxylated derivatives.

[0176] The amine oxide is a tertiary amine oxide corresponding to the general formula: [ka] where the arrow is the conventional representation of a semipolar bond and R 1 , R 2 , and R 3 R can be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. Generally, in detergent-related amine oxides, R 1 is an alkyl radical of about 8 to about 24 carbon atoms, and R 2 and R 3 is alkyl or hydroxyalkyl of 1 to 3 carbon atoms, or a mixture thereof, and R 2 and R 3 can be bonded to each other, for example, via an oxygen or nitrogen atom, to form a ring structure, and R 4 is an alkali or hydroxyalkylene group containing 2-3 carbon atoms, and n ranges from 0 to about 20.

[0177] Useful water-soluble amine oxide surfactants are selected from coconut or tallow alkyl di-(lower alkyl)amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0178] Useful semi-polar nonionic surfactants also include water-soluble phosphine oxides having the structure: [ka] where the arrow is the conventional representation of a semipolar bond and R 1 is an alkyl, alkenyl, or hydroxyalkyl moiety ranging in chain length from 10 to about 24 carbon atoms; R 2 and R 3 are each alkyl moieties independently selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

[0179] Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphonic oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, and bis(hydroxymethyl)tetradecylphosphine oxide.

[0180] Semi-polar nonionic surfactants useful herein also include water-soluble sulfoxide compounds having the structure: [ka] where the arrow is the conventional representation of a semipolar bond and R 1 is an alkyl or hydroxyalkyl moiety of from about 8 to about 28 carbon atoms, 0 to about 5 ether linkages, and 0 to about 2 hydroxyl substituents; R 2 is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

[0181] Useful examples of these sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

[0182] Semi-polar nonionic surfactants for the compositions of the present invention include dimethylamine oxides, such as lauryl dimethylamine oxide, myristyl dimethylamine oxide, cetyl dimethylamine oxide, combinations thereof, etc. Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(lower alkyl)amine oxides, specific examples of which include octyl dimethylamine oxide, nonyl dimethylamine oxide, decyl dimethylamine oxide, undecyl dimethylamine oxide, dodecyl dimethylamine oxide, iso-dodecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, oct ... The following amine oxides are available: octadecyl dimethylamine oxide, dodecyl dipropylamine oxide, tetradecyl dipropylamine oxide, hexadecyl dipropylamine oxide, tetradecyl dibutylamine oxide, octadecyl dibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0183] Suitable nonionic surfactants for use with the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof, and the like. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers, such as Pluronic and reverse Pluronic surfactants, alcohol alkoxylates, such as Dehypon LS-54 (R-(EO)5(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6), and capped alcohol alkoxylates, such as Plurafac LF221 and Tegoten EC11, mixtures thereof, and the like.

[0184] Anionic surfactants Additional surfactants classified as anionic because the charge on the hydrophobic material is negative, or surfactants in which the hydrophobic portion of the molecule does not carry a charge unless the pH is raised above neutral (e.g., carboxylic acids), are also useful in the present invention. Carboxylate, sulfonate, sulfate, and phosphate are polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium, and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; and calcium, barium, and magnesium promote oil solubility. As those skilled in the art will appreciate, anionic materials are excellent detersive surfactants and are therefore preferred additives to heavy-duty detergent compositions.

[0185] Anionic sulfate surfactants suitable for use in the present compositions include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5-C 17Included are alkyl polysaccharide sulfates such as acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates such as the sulfate or condensation products of ethylene oxide and nonylphenol (usually having 1 to 6 oxyethylene groups per molecule).

[0186] Anionic sulfonate surfactants suitable for use in the present compositions also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0187] Anionic carboxylate surfactants suitable for use in the present compositions include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, and sulfonated fatty acids, such as sulfonated oleic acid. Such carboxylates include alkyl ethoxy carboxylates, alkylaryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxyls). Secondary carboxylates useful in the present compositions include those containing a carboxyl unit attached to a secondary carbon. The secondary carbon may be in a ring structure, such as in p-octyl benzoic acid or alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants typically lack ether linkages, ester linkages, and hydroxyl groups. Furthermore, they typically lack a nitrogen atom in the head group (amphiphilic portion). Suitable secondary soap surfactants typically contain 11 to 13 total carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acyl amino acids (and salts), such as acyl glutamates, acyl peptides, sarcosinates (e.g., N-acylsarcosinates), taurates (e.g., N-acyltaurates, and fatty acid amides of methyl tauride), and the like.

[0188] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: RO-(CH2CH2O) n (CH2) m -CO2X (3) In the formula, R is C8 to C 22 alkyl group or [ka] where R 1 C4~C 16In some embodiments, R is an alkyl group, n is an integer from 1 to 20, m is an integer from 1 to 3, and X is a counterion such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10, and m is 1. In some embodiments, R is a C8 to C6 16 In some embodiments, R is a C 12 ~C 14 is an alkyl group, n is 4, and m is 1.

[0189] In other embodiments, R is [ka] and R 1 C6~C 12 In yet another embodiment, R 1 is a C9 alkyl group, n is 10, and m is 1.

[0190] Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are typically available in the acid form, which can be easily converted to the anionic or salt form. Commercially available carboxylates include Neodox 23-4, C 12~13 Carboxylate compounds include alkyl polyethoxy (4) carboxylic acids (Shell Chemical), and Emcol CNP-110, C alkylaryl polyethoxy (10) carboxylic acids (Witco Chemical). Carboxylate compounds are also available, for example, in the products Sandopan® DTC, C 13 Alkylpolyethoxy(7)carboxylic acids are available from Clariant.

[0191] amphoteric surfactants Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups, as well as organic hydrophobic groups. These ionic entities can be either anionic or cationic groups, as described herein for other types of surfactants. A basic nitrogen and an acidic carboxylate group are typical functional groups used as basic and acidic hydrophilic groups. In some surfactants, sulfonates, sulfates, phosphonates, or phosphates provide the negative charge.

[0192] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, where the aliphatic radical may be straight or branched, and one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, such as carboxy, sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are subdivided into two main classes known to those skilled in the art and are described in the "Surfactant Encyclopedia": Cosmetics & Toiletries , Vol. 104(2)69-71 (1989), which is incorporated herein by reference in its entirety. The first class includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second class includes N-alkylamino acids and their salts. Some amphoteric surfactants may be considered to fall into both classes.

[0193] Amphoteric surfactants can be synthesized by methods known to those skilled in the art.For example, 2-alkylhydroxyethyl imidazoline is synthesized by condensation and ring closure of long-chain carboxylic acid (or derivative) with dialkylethylenediamine.Commercial amphoteric surfactants are derivatized by subsequent hydrolysis and ring opening of the imidazoline ring by alkylation with, for example, chloroacetic acid or ethyl acetate.During alkylation, one or two carboxy-alkyl groups react to form tertiary amines, and different alkylating agents produce tertiary amines with different ether bonds.

[0194] Long chain imidazole derivatives having use in the present invention generally have the general formula: [ka] wherein R is an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation, typically sodium, to neutralize the charge of the anion. Commercially known imidazoline-derived amphoterics that can be used in the present compositions include, for example, cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropylsulfonate, and cocoamphocarboxypropionic acid. Amphocarboxylic acids can be produced from fatty imidazolines in which the dicarboxylic acid functional group of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

[0195] The carboxymethylated compounds (glycinates) described herein above are often called betaines, which are a special class of amphoteric substances discussed herein below in the section entitled Zwitterionic Surfactants.

[0196] Long-chain N-alkyl amino acids are easily prepared by the reaction RNH2, where R = C8-C 18 These are aliphatic amines with straight-chain or branched alkyl or halogenated carboxylic acids. Alkylation of the primary amino group of an amino acid results in secondary and tertiary amines. The alkyl substituent may have additional amino groups providing two or more reactive nitrogen centers. Most commercially available N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercial N-alkylamino acid ampholytes that have application in the present invention include alkyl beta-aminodipropionates, RN(C2H4COOM)2, and RNHC2H4COOM. In one embodiment, R can be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.

[0197] Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut-derived surfactants include, as part of their structure, an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety such as glycine, or a combination thereof, and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants can also be considered alkyl amphodicarboxylic acids. These amphoteric surfactants include C 12 -Alkyl-C(O)-NH-CH2-CH2-N + (CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -Alkyl-C(O)-N(H)-CH2-CH2-N + The amphoteric surfactant may include a compound having the chemical structure represented as (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is one suitable amphoteric surfactant and is commercially available from Rhodia Inc., Cranbury, NJ under the trade name Miranol™ FBS. Another suitable coconut-derived amphoteric surfactant having the chemical name disodium cocoamphodiacetate is sold under the trade name Mirataine™ JCHA, also from Rhodia Inc., Cranbury, NJ.

[0198] A typical listing of amphoteric classes and species of these surfactants is found in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are found in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). Each of these references is incorporated herein by reference in its entirety.

[0199] Zwitterionic surfactants Zwitterionic surfactants can be considered a subset of amphoteric surfactants and can contain an anionic charge. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants contain a positively charged quaternary ammonium or, in some cases, sulfonium or phosphonium ion, a negatively charged carboxyl group, and an alkyl group. Zwitterionic substances generally contain cationic and anionic groups that ionize to approximately equal degrees in the isoelectric region of the molecule, which can generate strong "inner salt" attraction between the positive and negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight-chain or branched, and in which one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0200] Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. The general formula for these compounds is: [ka] where R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moiety, Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms, and R 2 is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms, x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R 3is an alkylene or hydroxyalkylene or hydroxyalkylene of 1 to 4 carbon atoms, and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

[0201] Examples of zwitterionic surfactants having the structures listed above include 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate, 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate, 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate, 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate, 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate ... Examples of suitable surfactants include S-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in such detergent surfactants can be straight or branched and saturated or unsaturated.

[0202] Zwitterionic surfactants suitable for use in the present compositions include betaines of the general structure: [ka] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH or reduced water solubility within their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic materials. Examples of suitable betaines include acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C 12~14 Acylamidopropyl betaine, C 8~14 Acylamidohexyldiethylbetaine, 4-C 14~16 Acylmethylamidodiethylammonio-1-carboxybutane, C 16~18 Acylamide dimethyl betaine, C 12~16 Acylamidopentanediethyl betaine, and C 12~16 Acylmethylamidodimethylbetaine is an example.

[0203] Sultanes useful in the present invention include those having the formula (R(R 1 )2N + R 2 SO 3- wherein R is a C6-C 18 is a hydrocarbyl group, and each R 1 are typically independently C1-C3 alkyl, e.g., methyl, and R 2 is a C1-C6 hydrocarbyl group, for example a C1-C3 alkylene or hydroxyalkylene group.

[0204] A representative list of zwitterionic classes and species of these surfactants is described in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Further examples are found in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). Each of these references is incorporated herein in its entirety.

[0205] Additional Functional Ingredients The components of the cleaning composition can be further combined with various functional ingredients suitable for use in sanitizing and disinfecting applications, for example, in some embodiments, little or no additional functional ingredients are incorporated therein.

[0206] In other embodiments, additional functional ingredients may be included in the composition. The functional ingredient provides the composition with desired properties and functionality. For purposes of this application, the term "functional ingredient" includes materials that, when used and / or dispersed or dissolved in a concentrated solution, provide beneficial properties in a particular use. Some specific examples of functional materials are described in more detail below, although the specific materials described are provided merely as examples, and a variety of other functional ingredients may be used. For example, many of the functional materials discussed below relate to materials used in cleaning. However, other embodiments may include functional ingredients for use in other applications.

[0207] In other embodiments, the compositions may include antifoaming agents, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, metal protecting agents, stabilizing agents, corrosion inhibitors, additional sequestering and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, hydrotropes or couplers, buffers, solvents, and the like.

[0208] Illustrative Embodiments Exemplary ranges of cleaning compositions according to the present invention in concentrated compositions, each in weight percent, are shown in Table 3. [Table 3]

[0209] In accordance with the present invention, the concentrated cleaning compositions set forth in Table 3 have any suitable pH for their intended use, including from about 1 to 12. However, in accordance with embodiments of the present invention, the concentrated solutions preferably have an acidic to neutral pH depending on their particular intended use, including from about 0 to 6. Without limiting the scope of the present invention, numerical ranges set forth herein are inclusive of the numbers defining the range and include each integer within the defined range.

[0210] The cleaning composition may include a concentrate composition or may be diluted to form a use composition. Generally, a concentrate refers to a composition that is intended to be diluted with water to provide a use solution that contacts an object to provide the desired cleaning, rinsing, etc. The cleaning composition that contacts the item to be cleaned or washed may be referred to as a concentrate or a use composition (or use solution) depending on the formulation used in the method according to the present invention. It should be understood that the concentrations of the quaternary ammonium compound, acid component, surfactant, and other optional functional ingredients in the detergent composition will vary depending on whether the cleaning composition is provided as a concentrate or a use solution.

[0211] Use solutions can be prepared from concentrates by diluting the concentrate with water at a dilution ratio that provides a use solution with the desired cleaning properties. The water used to dilute the concentrate to form the use composition may be referred to as dilution water or diluent and may vary from location to location. Typical dilution factors are approximately 1 to approximately 10,000, but will depend on factors such as water hardness and the amount of soil to be removed. In one embodiment, the concentrate is diluted at a ratio of about 1:10 to about 1:10,000 concentrate to water. Specifically, the concentrate is diluted at a ratio of about 1:100 to about 1:5,000 concentrate to water. More specifically, the concentrate is diluted at a ratio of about 1:250 to about 1:2,000 concentrate to water.

[0212] Manufacturing method The compositions of the present invention are prepared by adding an anionic surfactant to a quaternary ammonium compound, which readily couples more hydrophobic organic acids into solution with minimal or no agitation.

[0213] In some embodiments, the compositions according to the present invention can be prepared by combining the components in an aqueous diluent using commonly available containers and blending equipment.Advantageously, no special manufacturing equipment is required to prepare compositions using quaternary ammonium compounds and anionic surfactants.A preferred method for preparing the cleaning compositions of the present invention includes introducing the components into a stirred production vessel.

[0214] Cleaning compositions according to the present invention can be provided as single use or multi-use compositions. In a preferred embodiment, the composition is a concentrated liquid composition.

[0215] Methods of Using the Cleaning Compositions of the Present Invention The present invention includes methods of using the cleaning compositions of the present invention for various applications. The present invention includes methods for reducing microbial populations, methods for reducing microbial populations on skin, and methods for treating skin disorders. These methods can be effected on an article, on a surface, within the body, or in a water or gas stream by contacting the article, surface, body, or stream with the compositions of the present invention. Contacting can include any of a number of methods for applying the compositions of the present invention, such as spraying the composition, immersing the article in the composition, foaming or gel-treating the article with a compound or composition, or a combination thereof.

[0216] In some embodiments, the compositions of the present invention kill one or more pathogenic bacteria associated with healthcare surfaces and environments, including, but not limited to, Salmonella typhimurium, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, Salmonella choleraesurus, Pseudomonas aeruginosa, Escherichia coli, mycobacteria, yeast, and mold. The compositions of the present invention are active against a wide variety of microorganisms, such as gram-positive (e.g., Listeria monocytogenes or Staphylococcus aureus) and gram-negative (e.g., Escherichia coli or Pseudomonas aeruginosa) bacteria, yeast, mold, bacterial spores, viruses, and the like. The compounds and compositions of the present invention, as described above, are active against a wide variety of human pathogens. The compounds and compositions can kill a wide variety of microorganisms on food processing surfaces, on the surfaces of food products, in water used to clean or process food products, on healthcare surfaces, or in healthcare environments.

[0217] The methods of the present invention can be used to achieve any suitable reduction in microbial populations in and / or on a target or treated target composition. In some embodiments, the methods of the present invention can be used to reduce microbial populations in and / or on a target or treated target composition by at least 1 log 10. In other embodiments, the methods of the present invention can be used to reduce microbial populations in and / or on a target or treated target composition by at least 2 log 10. In yet other embodiments, the methods of the present invention can be used to reduce microbial populations in and / or on a target or treated target composition by at least 3 log 10. In still other embodiments, the methods of the present invention can be used to reduce microbial populations in and / or on a target or treated target composition by at least 5 log 10. Without limiting the scope of the invention, numerical ranges recited herein are inclusive of the numbers defining the range and include each integer within the defined range.

[0218] The compositions of the present invention can be used in various household or industrial applications, such as to reduce microbial or viral populations on surfaces or objects, or within the body or in water streams. The compounds can be applied in various areas, including kitchens, bathrooms, factories, hospitals, dental clinics, and food processing plants, and can be applied to various hard or soft surfaces with smooth, irregular, or porous topography. Suitable hard surfaces include, for example, architectural surfaces (e.g., floors, walls, windows, sinks, tables, counters, and signs), eating utensils, hard-surfaced medical or surgical instruments and equipment, and hard-surfaced packaging. Such hard surfaces can be made from various materials, including, for example, ceramic, metal, glass, wood, or hard plastic. Suitable soft surfaces include, for example, paper, filtration media, hospital and surgical linens and clothing, soft-surfaced medical or surgical instruments and equipment, and soft-surfaced packaging. Such soft surfaces can be made from various materials, including, for example, paper, fiber, woven or nonwoven fabrics, soft plastics, and elastomers. The compositions of the present invention can also be applied to soft surfaces, such as food and skin (e.g., hands). The compounds can be used as foaming or non-foaming environmental disinfectants or sanitizers.

[0219] The compositions of the present invention can be included in products such as sterilants, sanitizers, disinfectants, antiseptics, deodorizers, antiseptics, fungicides, germicides, sporicides, virucides, detergents, bleaches, hard surface cleaners, hand soaps, waterless hand sanitizers, lubricants, rinse aids, 2-in-1 and / or 3-in-1 products, e.g., insecticide / cleaner / disinfectant, 3-sink applications, and pre- or post-surgical scrubs.

[0220] The compositions can also be used in veterinary products, such as mammalian skin treatments, or in products for disinfecting or sterilizing animal enclosures, pens, watering stations, and veterinary treatment areas, such as examination tables and operating rooms. The compositions can be used in antimicrobial foot baths for livestock or people.

[0221] In some embodiments, the compositions of the present invention can be used to reduce the population of pathogenic microorganisms, e.g., pathogens of humans, animals, etc. The compounds exhibit activity against pathogens including fungi, molds, bacteria, spores, and viruses, such as S. aureus, E. coli, Streptococci, Legionella, Pseudomonas aeruginosa, mycobacteria, Mycobacterium tuberculosis, phages, etc. Such pathogens can cause a variety of diseases and disorders, including mastitis or other mammalian milking diseases, tuberculosis, etc. The compositions of the present invention can reduce the population of microorganisms on an animal's skin or other external or mucosal surfaces. In addition, the compounds can kill pathogenic microorganisms that spread through water, air, or surface substrate transmission. The compositions need only be applied to an animal's skin, other external or mucosal surfaces, water, air, or surfaces.

[0222] The cleaning compositions can also be used on food and plant species to reduce surface microbial populations, in manufacturing or processing sites that handle such foods and plant species, or to treat process water around such sites. For example, the compounds can be used in food transport lines (e.g., as belt sprays), shoe and hand-washing dip pans, food storage facilities, spoilage prevention air circulation systems, refrigeration and cooler equipment, beverage chillers and warmers, blanchers, cutting boards, third sink areas, and meat chillers or boiling sanitizers. The compositions of the present invention can be used to treat produce transport water such as that found in flumes, pipe transport, cutters, slicers, blanchers, retort systems, washers, etc. Specific foodstuffs that can be treated with the compounds of the present invention include eggs, meat, seeds, leaves, fruits, and vegetables. Specific plant surfaces include leaves, roots, seeds, skins or shells, stems, stalks, tubers, corms, fruits, and the like, both harvested and growing.

[0223] In some embodiments, the compositions of the present invention are useful for cleaning or disinfecting containers, processing facilities, or equipment in food service or food processing industries.The compositions are particularly valuable for use in food packaging materials and equipment, and especially for low-temperature or high-temperature sterilization packaging.Examples of process facilities that can use the compounds of the present invention include dairy factories, continuous brewing systems, food processing lines, such as pumpable food systems and beverage lines.Food service ware can be sterilized with the compounds of the present invention.For example, the compounds can also be used on or in warewashing machines, low-temperature warewashing machines, dishware, bottle washing machines, bottle chillers, warmers, third sink washing machines, cutting areas (such as water knives, slicers, cutters, and saws), and egg washing machines. Specific treatable surfaces include packaging such as cartons, bottles, films, and resins; tableware such as glasses, plates, utensils, pots, and pans; warewashing and low-temperature warewashing equipment; exposed food preparation area surfaces such as sinks, counters, tables, floors, and walls; processing equipment such as tanks, vats, lines, pumps, and hoses (e.g., dairy processing equipment for processing milk, cheese, ice cream, and other dairy products); and transportation vehicles. Containers include glass bottles, PVC or polyolefin film bags, cans, polyester, PEN or PET bottles of various volumes (e.g., 100 mL to 2 liters), one-gallon milk jugs, paperboard juice or milk containers, and the like.

[0224] The compositions of the present invention can also be used by immersing food processing equipment in the use solution, allowing the equipment to soak for a time sufficient to sanitize the equipment, and wiping or draining excess solution from the equipment. The compounds can further be used by spraying or wiping food processing surfaces with the use solution, keeping the surfaces wet for a time sufficient to sanitize the surfaces, and removing excess solution by wiping, vertical draining, vacuuming, etc.

[0225] The compositions of the present invention may also be used in methods of disinfecting hard surfaces such as institutional-type equipment, utensils, dishware, healthcare equipment or tools, implements, and other hard surfaces.

[0226] The cleaning compositions can be applied to microorganisms or to soiled or cleaned surfaces using a variety of methods. These methods can be effected on an object, on a surface, in a body, or in a water or gas stream, etc., by contacting the object, surface, body, or stream with a compound of the present invention. Contacting can include any of a number of methods for applying the compound, such as spraying the compound, immersing the object, treating the object with a foam or gel with the compound, or a combination thereof.

[0227] The concentrate or use concentrate of the compound of the present invention can be applied to or contacted with an object by any conventional method or device for applying antimicrobial or cleaning compounds to an object. For example, the object can be wiped, sprayed, foamed, and / or immersed with the compound or a use solution made from the composition. The composition can be sprayed, foamed, or wiped onto the surface, the composition can be flowed onto the surface, or the surface can be immersed in the composition. Contact can be manual or mechanical. Food processing surfaces, food products, food processing or transport water, etc. can be treated with the liquid, foam, gel, aerosol, gas, wax, solid, or powder stabilized compound of the present invention, or a solution containing these compounds.

[0228] Various treatment methods according to the present invention can include the use of any suitable level of cleaning composition. In some embodiments, the treated target composition, when diluted for use, contains from about 1 ppm to about 1000 ppm of cleaning composition. In further embodiments, the treated target composition, when diluted for use, contains from about 1 ppm to about 500 ppm, 5 ppm to about 400 ppm, 10 ppm to about 100 ppm, 20 ppm to about 100 ppm, 25 ppm to about 100 ppm, 10 ppm to about 75 ppm, 20 ppm to about 75 ppm, 25 ppm to about 75 ppm, or about 50 ppm of cleaning composition.

[0229] In one aspect, the method of the present invention includes producing a use solution from the concentrated solid or liquid composition of the present invention. The use solution can be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution with the desired disinfecting and / or other antimicrobial properties. The water used to dilute the concentrate to form the use composition can be referred to as dilution water or diluent and can vary depending on the location. Typical dilution ratios are between about 1:10 and about 1:10,000. In one embodiment, the concentrate is diluted at a ratio of concentrate to water of about 1:100 to about 1:5,000. More specifically, the concentrate is diluted at a ratio of concentrate to water of about 1:250 to about 1:2,000.

[0230] In one embodiment, the concentrated cleaning composition is diluted to a use solution concentration of about 0.001% (w / v) to about 10% (w / v), or about 0.001% (w / v) to about 5% (w / v), or about 0.001% (w / v) to about 2% (w / v), or about 0.01% (w / v) to about 1% (w / v). Without limiting the scope of the invention, numerical ranges recited herein are inclusive of the numbers defining the range and include each integer within the defined range.

[0231] The compositions of the present invention can be formulated and sold for use as is or as a solvent or solid concentrate. If desired, such concentrates can be used at full strength as disinfectant rinse compositions. However, concentrates will typically be diluted with a fluid (e.g., water) to form a dilute phase or use solution thereafter. Preferably, the concentrate forms a single phase prior to such dilution and remains so while stored in the container in which it is sold. When combined with water or other desired dilution fluid at an appropriate dilution level and subjected to gentle agitation (e.g., by stirring or pumping the composition), some compositions of the present invention will form pseudo-stable dispersions, while other compositions of the present invention will form clear or meta-stable solutions or dispersions. If a pseudo-stable composition is formed, the composition preferably remains pseudo-stable for a sufficiently long period of time so that the composition can be applied to a surface before the onset of phase separation. The pseudo-stable state need only last for a few seconds if a suitably rapid application technique, such as spraying, is used, or if agitation during application is used. The pseudo-stable state desirably lasts for at least 1 minute after mixing and while the composition is stored in a suitable container, preferably for 5 minutes or more after mixing. In many cases, regular refilling or recharging of the applicator (e.g., by dipping the applicator into the composition) will provide sufficient agitation to preserve the pseudo-stable state of the composition during application.

[0232] The various uses described herein provide a cleaning composition to a surface and / or water source. Advantageously, the compositions of the present invention are fast-acting. However, the present methods require a certain minimum contact time between the composition and the surface or product requiring treatment for sufficient antimicrobial efficacy to occur. Contact time can vary depending on the concentration of the use composition, the method of application of the use composition, the temperature of the use composition, the pH of the use composition, the amount of surface or product being treated, the amount of soil or substrate on / in the surface or product being treated, and the like. Contact or exposure time can be about 15 seconds, at least about 15 seconds, about 30 seconds, or greater than 30 seconds. In some embodiments, the exposure time is about 1 to 5 minutes. In other embodiments, the exposure time is from several minutes to several hours. In other embodiments, the exposure time is from several hours to several days. Contact time will further vary based on the use concentration of the active ingredient of the compositions of the present invention.

[0233] Kit for use According to various uses of the composition of the present invention, a kit for administering the composition of the present invention may be provided. In certain uses, the composition may be provided by using a kit according to an embodiment of the present invention. A kit for administering and / or providing a cleaning composition of the present invention may comprise, consist of, and / or essentially consist of a cleaning component and a polymer component (and / or a surfactant and / or an acid component). Alternatively, the kit may comprise, consist of, and / or essentially consist of a polymer component (and / or a surfactant and / or an acid component) for administration together with the cleaning component in the application of use. The kit may further comprise a measuring means and / or an administration means.

[0234] The kit may further include additional components. For example, the kit may also include instructions for using the cleaning composition. The instructions included in the kit can be affixed to packaging materials or included as a package insert. The instructions are typically written or printed, but are not limited to such. Any medium capable of storing such instructions and transmitting them to an end user is contemplated by the present disclosure. Such media include, but are not limited to, electronic storage media (e.g., magnetic disks, tapes, cartridges, chips), optical media (e.g., CDs, DVDs), etc. As used herein, the term "instructions" can include the address of an internet site that provides the instructions. The various components of the kit are optionally provided in suitable containers, such as bottles, jars, or vials, as needed.

[0235] All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. [Example]

[0236] Embodiments of the present invention are further defined in the following non-limiting examples. It should be understood that these examples, while indicating specific embodiments of the present invention, are given by way of illustration only. From the above discussion and these examples, one skilled in the art will be able to ascertain the essential features of the present invention and will be able to make various changes and modifications to the embodiments of the present invention to adapt them to various uses and conditions without departing from the spirit and scope thereof. Accordingly, various modifications of the embodiments of the present invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. Commercial Product A is formulated to contain the following ingredients:

[0237] The materials used in the following examples are provided herein. Commercially available product A: A mixture of alkylbenzylammonium chloride and dialkyldimethylammonium chloride Polymer component A: Cationic flocculant Commercially available product B: A mixture of alkylbenzylammonium chloride and dialkyldimethylammonium chloride

[0238] Example 1 Comparative study of spray patterns of commercially available quaternary ammonium chlorides with and without added polymer. The test compositions are shown in Table 4. Composition A is formulated according to the present invention. [Table 4]

[0239] The results from the spray pattern comparison showed that the formulation according to the present invention provides a stream with a broad spray pattern as opposed to a fine mist with a broad spray pattern. Thus, the presence of the polymer component reduces the mist particles, thereby reducing the inhalation risk.

[0240] Example 2 A commercially available quat disinfectant was tested against compositions according to the claimed invention. Testing was carried out in water with 500 ppm hardness at a temperature of 77°F. Samples contaminated with E. coli and Staph were contacted with each of the compositions for 30 seconds. Composition B is formulated according to the invention. The results are shown in Table 5. [Table 5]

[0241] From the results shown in Table 5, the inclusion of the polymer component does not adversely affect microbial efficacy. The inclusion of the polymer component provides a reduced misting profile, allowing the quat to remain on the treated surface longer. As such, the addition of the polymer component results in improved residual kill.

[0242] The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims. The above specification provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the invention, the invention resides in the claims.

Claims

1. A method for killing microorganisms, said method comprising: dissolving a concentrated cleaning composition into a use solution; contacting the use solution with a surface; The concentrated cleaning composition comprises: 1% to 15% by weight of a quaternary ammonium compound having the formula: 【Chemistry 1】 a quaternary ammonium compound wherein the R1, R2, R3, and R4 groups each have a chain length of less than C20 and X- is an anionic counterion; a cationic inverse emulsion polymer component; 0.1% to 30% by weight of an acid component comprising a mineral acid, an organic acid, a carboxylic acid, an amino acid, a fatty acid, or a combination thereof; a solvent comprising an EO / PO block copolymer, an alcohol alkoxylate, water, or a combination thereof; the acid component provides pH control such that the concentrated cleaning composition has a pH of from about 0 to about 6; the polymer component has a viscosity of 50 to 5000 cPs; the composition does not contain an additional cationic surfactant; the use solution has a median particle size of 11 microns or greater; the concentration of the quaternary ammonium compound in the use solution is between 10 ppm and 300 ppm; 1. A method wherein the use solution provides at least a 99.99% reduction in microbial counts against Escherichia coli and Staphylococcus aureus on treated surfaces within 30 seconds at room temperature of 25±2° C. using the procedure set forth in the A.O.A.C. Use Dilution Method, Official Methods of Analysis of the Association of Official Analytical Chemistry, paragraph 955.14 and relevant portions, 15th Edition, 1990 (EPA Guideline 91-2), while providing a reduced inhalation risk.

2. The method described in claim 1, wherein the concentration of the quaternary ammonium compound in the use solution is less than 150 ppm.

3. A method according to claim 1 or 2, wherein the concentration of the quaternary ammonium compound in the use solution is less than 100 ppm.

4. A method according to claim 1 or 2, wherein the concentration of the quaternary ammonium compound in the use solution is 100 ppm to 300 ppm.

5. The method of claim 1, wherein the polymer component has a particle size of 0.1 to 10 microns.

6. The method of any one of claims 1 to 5, wherein the concentrated cleaning composition further comprises at least one additional functional ingredient selected from the group consisting of additional surfactants, thickeners and / or viscosity modifiers, solubility modifiers, wetting agents, metal protecting agents, stabilizers, corrosion inhibitors, sequestering agents and / or chelating agents, coagulants, coating agents, fragrances and / or dyes, hydrotropes or couplers, buffers, and combinations thereof.

7. The method described in any one of claims 1 to 6, wherein the quaternary ammonium compound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, polysubstituted quaternary ammonium salts, bisquaternary ammonium salts, and combinations thereof.

8. The method of any one of claims 1 to 7, wherein the concentrated cleaning composition further comprises at least one anionic surfactant, nonionic surfactant, amphoteric surfactant, or a combination thereof, and the at least one surfactant is present in an amount of 0.1% to 30% by weight based on the total weight of the concentrated cleaning composition.

9. The method of claim 1, wherein the contacting comprises spraying the use solution onto the surface.

10. The method of claim 1, wherein the surface is a hard surface.

11. The method of any one of claims 1 to 10, wherein the hard surface is a countertop, tile, floor, wall, panel, window, plumbing fixture, kitchen surface, bathroom surface, appliance, engine, circuit board, healthcare surface, food processing surface, construction surface, clothing, and / or packaging.

12. A method according to any one of claims 1 to 9, wherein the surface is a soft surface.

13. The method of claim 1, wherein the surface is a food product or a plant surface.

14. A method described in any one of claims 1 to 13, wherein the contact is for at least 15 seconds.

15. A method described in any one of claims 1 to 14, wherein the contact is for 1 to 5 minutes.

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