Low-foam cleaning compositions

Abstract

To provide low-foam cleaning compositions comprising quaternary ammonium compounds, and methods of manufacturing and using the low-foam cleaning compositions.SOLUTION: Beneficially, the cleaning compositions are compatible with cleaning methods and cleaning apparatuses requiring low foam, including, but not limited to, machine dishwashing and clean-in-place. The cleaning compositions are particularly suitable for low-temperature sanitizing applications.SELECTED DRAWING: Figure 2A

Description

[Technical field]

[0001] cross reference This application claims priority under 35 U.S.C. § 119 to U.S. Provisional Patent Application No. 62 / 704,256, filed April 30, 2020, entitled “LOW FOAM CLEANING COMPOSITION,” which is incorporated by reference in its entirety, including without limitation the specification, claims, drawings, and examples.

[0002] The present invention relates to cleaning compositions having reduced foaming, particularly cleaning compositions comprising a quaternary ammonium compound, the compositions having reduced foaming. [Background technology]

[0003] Quaternary ammonium compounds are recognized for their disinfecting properties. However, they have not been traditionally incorporated into areas requiring low foaming properties, including but not limited to machine dishwashing and cleaning in place. This is because quaternary ammonium compounds are known to have high foaming properties, especially under agitation or shear forces. High foaming compositions are known to interfere with the operation of machine dishwashing and cleaning in place. For example, foam buildup can cause pump cavitation and prevent proper mechanical functioning of the spray arm. In addition, foam can dry and leave residue on the items being washed (such as dishes). In applications where low foaming compositions are preferred or required, the compositions have relied on other active compounds for germicidal activity. For example, in such situations, chlorine and / or peroxide-based disinfectants are often relied on. Accordingly, there is a need for quaternary ammonium-based disinfecting compositions that are suitable for low foaming applications. Summary of the Invention [Problem to be solved by the invention]

[0004] It is therefore an object of the present invention to provide a low foaming cleaning composition incorporating a quaternary ammonium compound.

[0005] A further object of the present invention is a composition suitable for use in machine dishwashing and cleaning in place.

[0006] Yet a further object of the present invention is to provide a composition suitable for use as a low temperature disinfection composition.

[0007] 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]

[0008] The advantage of the cleaning compositions described herein is that they incorporate quaternary ammonium compounds and have low foaming properties.The advantage of these compositions is that they are suitable for use in machine dishwashing and in-place cleaning.Another advantage of these compositions is that they provide effective disinfection under low temperature conditions.Yet another advantage of these compositions is that they have low odor properties.

[0009] As disclosed herein, a preferred embodiment is a cleaning composition comprising a quaternary ammonium compound and a polycarboxylic acid and / or a salt thereof, wherein the polycarboxylic acid has at least two pKa values, each of the pKa values ​​being less than about 7.

[0010] Also disclosed herein is a preferred method of cleaning an article, comprising contacting the article with a cleaning composition comprising a quaternary ammonium compound and a polycarboxylic acid and / or a salt thereof, wherein the polycarboxylic acid has at least two pKa values, each of the pKa values ​​being less than about 7.

[0011] In a preferred embodiment, the polycarboxylic acid comprises one or more of citric acid, succinic acid, malic acid, N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), N,N-dicarboxymethylglutamic acid tetrasodium salt (GLDA), methylglycinediacetic acid (MGDA), a salt of any of the foregoing, or sodium xylenesulfonate. In a preferred embodiment, the quaternary ammonium compound is alkyl(C8-C16)dimethylbenzylammonium chloride (ADBAC), alkyl(C8-16)dimethylethylbenzylammonium chloride (ADEBAC), dialkyl(C8-C16)dimethylammonium chloride (DAAC), or a mixture thereof. As disclosed herein, the composition may be solid or liquid and may further comprise one or more of a dye, an odorant, a pH adjuster, a coating agent, and a surfactant. Also disclosed herein is a preferred method of making the cleaning composition.

[0012] While multiple embodiments of the invention are disclosed, still other embodiments 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 examples, drawings, and detailed description are to be regarded as illustrative in nature and not restrictive. [Brief description of the drawings]

[0013] [Figure 1A] 1 shows a bar graph comparing the foam properties of various quaternary ammonium compounds, both alone and in the presence of a traditional antifoam surfactant, immediately after mixing in solution, about 15 seconds after mixing, and about 1 minute after mixing. Foam height measurements are shown in inches. [Figure 1B] 1 shows a bar graph comparing the foam properties of various quaternary ammonium compounds, both alone and in the presence of a traditional antifoam surfactant, immediately after mixing in solution, about 15 seconds after mixing, and about 1 minute after mixing. Foam height measurements are shown in inches. [Figure 2A]1 shows a bar graph comparing the foam properties of various quaternary ammonium compounds, both alone and in the presence of polycarboxylic acids and / or salts, immediately after mixing in solution, about 15 seconds after mixing, and about 1 minute after mixing. Foam height measurements are shown in inches. [Figure 2B] 1 shows a bar graph comparing the foam properties of various quaternary ammonium compounds, both alone and in the presence of polycarboxylic acids and / or salts, immediately after mixing in solution, about 15 seconds after mixing, and about 1 minute after mixing. Foam height measurements are shown in inches.

[0014] Various embodiments of the present invention will now be described in detail with reference to the drawings. Reference to the various embodiments is not intended to limit the scope of the present invention. The figures presented herein are presented for illustrative purposes only and are not intended to limit the various embodiments according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present disclosure relates to a low-foam cleaning composition comprising a quaternary ammonium compound. The cleaning composition has many advantages over existing low-foam cleaning compositions. For example, the low-foam cleaning composition incorporates a quaternary ammonium compound while retaining low-foam properties. Therefore, these compositions are suitable for applications that require low foam, such as machine dishwashing and cleaning in place. In addition, these compositions provide effective germicidal activity under low temperature conditions. In a preferred embodiment, the cleaning composition can be used as a disinfecting composition.

[0016] The embodiments of the present invention are not limited to particular cleaning conditions, soils, or cleaning equipment, which may vary and are understood by those skilled in the art. Further, it is to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope.

[0017] 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 a 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. Thus, the description of a range should be considered to have specifically disclosed all possible subranges, fractions, and individual numbers within that range. For example, the description of a range such as 1-6 should be considered to have specifically disclosed subranges such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc., as well as individual numbers within that range, such as 1, 2, 3, 4, 5, and 6, and decimals and fractions, such as 1.2, 3.8, 1 and 1 / 2, and 4 and 3 / 4. This applies regardless of the breadth of the range.

[0018] definition 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 embodiments of the present invention pertain. Many methods and materials similar, modified, or equivalent to those described herein can be used to implement the embodiments of the present invention without undue experimentation, and preferred materials and methods are described herein. In describing and claiming the embodiments of the present invention, the following terminology is used in accordance with the definitions set forth below.

[0019] As used herein, the term "about" refers to variations in quantity that can be made, for example, through typical measurement techniques and equipment, for any quantifiable variable, including, but not limited to, mass, volume, time, temperature, pH, and bacterial or viral log counts. Furthermore, given the solid and liquid handling procedures used in the real world, there are certain inadvertent errors and variations that are likely through differences in manufacture, source, or purity of ingredients used to make compositions or perform methods, etc. The term "about" also encompasses these variations. Whether or not modified by the term "about," the claims include the equivalent to the amount.

[0020] The terms "actives" or "percent actives" or "percent actives by weight" or "actives concentration" are used interchangeably herein and refer to the concentration of the components involved in purification expressed as a percentage minus inactive ingredients such as water or salt.

[0021] 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).

[0022] 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 a substituent 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, Included may be cyano, 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.

[0023] In some embodiments, substituted alkyls may include heterocyclic groups. As used herein, the term "heterocyclic group" includes closed ring structures similar to carbocyclic groups in which one or more of the carbon atoms in the ring are elements other than carbon, such as nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0024] 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.

[0025] As used herein, the term "bactericide" refers to an agent that kills all vegetative cells, including most recognized pathogenic microorganisms, using the procedures described in 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). As used herein, the term "high-level bactericide" or "high-level bactericide" refers to a compound or composition that kills substantially all living organisms, except high levels of bacterial spores, and is effective with a chemical bactericide approved for marketing as a sterilant by the Food and Drug Administration. As used herein, the term "intermediate-level bactericide" or "intermediate-level bactericide" refers to a compound or composition that is a chemical bactericide registered by the Environmental Protection Agency (EPA) as a tuberculocide and kills mycobacteria, most viruses, and bacteria. As used herein, the term "low-level bactericide" or "low-level bactericide" refers to a compound or composition that is a chemical bactericide registered by the EPA as a hospital bactericide and kills some viruses and bacteria.

[0026] As used herein, the phrase "food processing surfaces" refers to surfaces of utensils, machines, equipment, structures, buildings, etc., used as part of food processing, preparation, or storage activities. Examples of food processing surfaces include surfaces of food processing or preparation 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 sanitization, food refrigeration and cooler cleaners and sanitizers, utensil washing sanitization, blancher cleaning and sanitization, food packaging materials, cutting board additives, third-sink sanitization, beverage chillers and warmers, meat cooling or scalding water, automatic dish sanitizers, sanitizing gels, cooling towers, antimicrobial clothing sprays for food processing, and non-aqueous to low-aqueous food preparation lubricants, oils, and rinse additives.

[0027] As used herein, the phrase "food" includes any food substance that may require treatment with an antimicrobial agent or composition and may be eaten with or without further cooking. Foods include meat (e.g., red meat and pork), seafood, poultry, produce (e.g., fruits and vegetables), eggs, live eggs, egg products, ready-to-eat meals, wheat, seeds, roots, tubers, leaves, stems, corn, flowers, sprouts, seasonings, or combinations thereof. The term "produce" refers to foods such as fruits and vegetables and plants or plant-derived materials that are typically sold uncooked, often unpackaged, and can sometimes be eaten raw.

[0028] The term "hard surface" refers to substantially inflexible solid surfaces such as countertops, tiles, floors, walls, paneling, windows, plumbing fixtures, kitchen and bathroom furniture, appliances, engines, circuit boards, and dishes. Hard surfaces can include, for example, healthcare surfaces and food processing surfaces.

[0029] As used herein, the phrase "healthcare surfaces" refers to surfaces of instruments, devices, carts, cages, furniture, structures, buildings, and the like, that are used as part of a healthcare operation. Examples of healthcare surfaces include surfaces of medical or dental instruments, surfaces of medical or dental devices, surfaces of electronic equipment used to monitor the health of patients, and surfaces of floors, walls, or fixtures of structures in which healthcare is performed. Healthcare surfaces are found in hospitals, surgical, infirmary, birthing, funeral homes, and clinical diagnostic rooms. These surfaces may be typified as "hard surfaces" (walls, floors, bedpans, etc.), or textile surfaces, such as knitted, woven, and nonwoven surfaces (surgical garments, curtains, bed linens, bandages, etc.), or patient care equipment (respirators, diagnostic instruments, shunts, body scopes, wheelchairs, beds, etc.), or surgical and diagnostic equipment. Healthcare surfaces include articles and surfaces used in animal healthcare.

[0030] 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.

[0031] The term "laundry" refers to items or articles that are washed in a laundry washing machine. In general, laundry refers to any item or article made from or including textile materials, woven fabrics, nonwoven fabrics, and knitted fabrics. Textile materials can include natural or synthetic fibers, such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. The fibers can be treated or untreated. Exemplary treated fibers include those that have been treated for flame retardancy. It should be understood that the term "linen" is often used to describe certain types of laundry items, including bed sheets, pillowcases, towels, table linens, tablecloths, bar mops, and uniforms. The present invention additionally provides compositions and methods for treating surfaces, including non-laundry articles and hard surfaces such as dishes, glasses, and other vessels.

[0032] As used herein, the phrases "medical instruments," "dental instruments," "medical devices," "dental devices," "medical equipment," or "dental equipment" refer to instruments, devices, tools, appliances, apparatus, and equipment used in medicine or dentistry. Such instruments, devices, and equipment may be cold sterilized, soaked, or washed and then heat sterilized, or may otherwise benefit from cleaning with the compositions of the present invention. These various instruments, devices, and equipment include, but are not limited to, diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g., bone saws and their blades), hemostats, knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burrs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, retractors, straighteners, punches, extractors, scoops, keratomes, spatulas, expressors, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthroscopes), and related instruments, and the like, or combinations thereof.

[0033] As used herein, the phrases "unpleasant odor", "unpleasant odor", or "malodor" refer to an acrid, pungent, or stinging odor or atmospheric environment that a typical person would be put off by, if possible. Hedonic tone provides a measure of whether an odor is pleasant or unpleasant. An "unpleasant odor", "unpleasant odor", or "malodor" has a hedonic tone that is rated as unpleasant or more unpleasant than a 5% by weight solution of acetic acid, propionic acid, butyric acid, or mixtures thereof.

[0034] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as block, graft, random and alternating copolymers, terpolymers, and higher order "x"-mers, and further includes derivatives, combinations, and blends thereof. Furthermore, unless specifically limited otherwise, the term "polymer" is intended to include all possible isomeric configurations of the molecule, including, but not limited to, isotactic, syndiotactic, and random symmetries, and combinations thereof. Furthermore, unless specifically limited otherwise, the term "polymer" is intended to include all possible geometric configurations of the molecule.

[0035] 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 is achieved by washing with water. The greater the reduction in microbial population, the greater the level of protection.

[0036] 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 3 log reduction, and more preferably a 5 log order reduction. These reductions can be evaluated using the procedures described in Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and relevant portions, 15th Edition, 1990 (EPA Guideline 91-2). According to this reference, disinfectants should provide a 99.999% reduction (5 log order reduction) against several test organisms within 30 seconds at room temperature, 25±2°C.

[0037] As used herein, the term "soil" or "stain" refers to non-polar, oily materials, which may or may not contain particulate matter such as mineral clays, sand, natural minerals, carbon black, graphite, kaolin, environmental dust, and the like.

[0038] The distinction between antimicrobial "-cidal" or "-static" activity, definitions describing the degree of effectiveness, and official laboratory protocols for measuring this effectiveness are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can produce two types of microbial cell damage. The first is a lethal and irreversible action, resulting in the complete destruction or incapacitation of the microbial cell. The second type of cell damage is reversible, so that once the organism is freed from the agent, it can grow again. The former is termed bactericidal and the latter bacteriostatic. Disinfectants and disinfectants are, by definition, agents that provide antimicrobial or bactericidal activity. In contrast, preservatives are generally described as inhibitors or bacteriostatic compositions.

[0039] As used herein, the term "substantially free" refers to a composition that is completely devoid of the component or has such a small amount of the component that it does not affect the performance of the composition. The component may be present as an impurity or contaminant and should be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1% by weight, and in yet another embodiment, the amount of the component is less than 0.01% by weight.

[0040] As used herein, the term "ware" refers to items such as 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 "ware washing" refers to washing, cleaning, or rinsing of ware. Ware also refers to items made of plastic. Types of plastics that can be cleaned with the composition according to the present invention include, but are not limited to, those that include 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).

[0041] The terms "weight percent," "wt%," "percent by weight," "% by weight," and variations thereof, as used herein, refer to the concentration of a substance obtained by dividing the weight of that substance by the total weight of the composition and multiplying by 100. As used herein, it is understood that "percent," "%," and the like are intended to be synonymous with "weight percent," "% by weight," and the like.

[0042] The methods, systems, devices, 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, systems, devices, and compositions may include additional steps, components, or ingredients only if the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, devices, and compositions.

[0043] Low-foam cleaning composition The low foam cleaning composition according to the present application can be liquid or solid. Solid compositions are concentrated and need to be dissolved with a sufficient amount of carrier to achieve the desired concentration of active ingredients. Liquid compositions can be concentrated (which needs to be further dissolved before use) or ready-to-use solutions. The desired concentration for a ready-to-use solution can depend on its end use and application. Furthermore, it should be understood that concentrates can vary in their concentration based on the final dilution ratio and whether the concentrate is formulated as an anhydrous or aqueous formulation.

[0044] The pH of a liquid composition or a solid composition upon dilution may range from about 4.5 to about 10, preferably from about 4.5 to about 9, more preferably from about 5 to about 8.5. For concentrated compositions, the pH is preferably from about 5 to about 10, more preferably from about 5.5 to about 9.5. For ready-to-use compositions, the pH is preferably from about 4.5 to about 9.5, more preferably from about 5 to about 8.5, most preferably from about 5 to about 7.

[0045] Preferably, the low foaming cleaning composition comprises a quaternary ammonium compound, a polycarboxylic acid and / or its salt.The low foaming cleaning composition may further comprise a carrier, a dye, an odorant, a pH adjuster, a coating agent, a solidification aid, a surfactant, or a combination thereof.The low foaming cleaning composition may be suitable for use as dishwashing detergent, a rinse aid, a disinfectant detergent, a disinfectant rinse aid, a hard surface cleaner, a laundry detergent, and a laundry disinfectant.

[0046] Quaternary Ammonium Compounds The low foaming cleaning compositions described herein include a quaternary ammonium compound. The term "quaternary ammonium compound" generally refers to any composition having the formula: [ka] wherein R1-R4 each have a chain length less than C16, and X- is an anionic counterion. In embodiments, the alkyl groups may be the same or different, substituted or unsubstituted, saturated or unsaturated, branched or unbranched, and cyclic or acyclic, may have ether, ester, or amide bonds, and may be aromatic or substituted aromatic groups. The term "anionic counterion" includes any ion capable of forming a salt with a quaternary ammonium. Examples of suitable counterions include halides, such as chloride and bromide, methyl sulfate, carbonate, and bicarbonate. Preferably, the anionic counterion is chloride. In some embodiments, a quaternary ammonium having a carbon chain of about 8-6, preferably 8-12, or more preferably 8-10 carbons is included in the composition.

[0047] Preferred quaternary ammonium compounds are water-soluble compounds and may further include salts of the compounds described herein. Suitable salts include, but are not limited to, salts of both organic and inorganic acids, such as nitrates, sulfates, chlorides, bromides, iodides, methyl sulfates, methyl sulfonates, carbonates, bicarbonates, carboxylates, polycarboxylates, phosphates, phosphonates, and the like.

[0048] Preferred quaternary ammonium compounds include, but are not limited to, alkyl (C8-C16) dimethyl benzyl ammonium chloride (ADBAC), alkyl (C8-16) dimethyl ethyl benzyl ammonium chloride (ADEBAC), and dialkyl (C8-C16) dimethyl ammonium chloride (DAAC), including octyl decyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, and didecyl dimethyl ammonium chloride. In a preferred embodiment, the dialkyl dimethyl ammonium chloride (DAAC) is a dialkyl having C10 or less (C8-C10). In a preferred embodiment, the quaternary ammonium compound is a blend of octyl decyl dimethyl, dioctyl dimethyl, and didecyl dimethyl ammonium chloride. A single quaternary ammonium or a combination of more than one quaternary ammonium may be included in the low foaming cleaning composition.

[0049] In some embodiments, depending on the R group, the nature of the anion, and the number of quaternary nitrogen atoms present, the 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 is further described below.

[0050] Monoalkyltrimethylammonium salts contain one R group that is a long chain alkyl group and the remaining R groups are short chain alkyl groups such as methyl or ethyl groups. Some non-limiting examples of monoalkyltrimethylammonium salts include cetyltrimethylammonium bromide, available commercially under the trade names Rhodaquat M242C / 29 and Dehyquart A; alkyltrimethylammonium chloride, available commercially as Arquad 16; alkylaryltrimethylammonium chloride; and cetyldimethylethylammonium bromide, available commercially as Ammonyx DME.

[0051] 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, available as Barquat from Lonza Inc., and benzethonium chloride, available as Lonzagard from Lonza Inc. 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 available as BTC 2125M from Stepan Company and Barquat 4250 from Lonza Inc.

[0052] 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 as Bardac 22 from Lonza Inc; didecyldimethylammonium chloride, commercially available as Bardac 2250 from Lonza Inc; dioctyldimethylammonium chloride, commercially available as Bardac LF and Bardac LF-80 from Lonza Inc; and didecyldimethylammonium chloride, commercially available as Bardac 2050 and 2080 from Lonza Inc, and octyldecyldimethylammonium chloride, sold as a mixture with dioctyldimethylammonium chloride.

[0053] In a preferred embodiment, the low foaming cleaning composition comprises from about 10 ppm to about 40% by weight of a quaternary ammonium compound, more preferably from about 15 ppm to about 30% by weight of a quaternary ammonium compound, or most preferably from about 20 ppm to about 25% by weight of a quaternary ammonium compound.

[0054] In a preferred embodiment, the concentrated low-foam cleaning composition comprises from about 1% to about 40% by weight of a quaternary ammonium compound, more preferably from about 5% to about 35% by weight of a quaternary ammonium compound, or most preferably from about 10% to about 25% by weight of a quaternary ammonium compound.

[0055] In a preferred embodiment, the low foaming cleaning composition comprises from about 10 ppm to about 1000 ppm of a quaternary ammonium compound, more preferably from about 15 ppm to about 500 ppm of a quaternary ammonium compound, or most preferably from about 20 ppm to about 250 ppm of a quaternary ammonium compound.

[0056] Polycarboxylic acids and / or salts The low foaming cleaning composition preferably comprises polycarboxylic acid and / or its salt.Without wishing to be bound by theory, it is believed that polycarboxylic acid and / or its salt partially neutralizes (i.e. masks) the charge of quaternary ammonium compound by providing counter ions, and this charge masking reduces, more preferably prevents, foam formation and / or stability.It has been found that the electronegativity of polycarboxylic acid and / or salt is important for charge masking to occur.In this respect, it is important to select polycarboxylic acid and / or its salt with appropriate pKa value.

[0057] The polycarboxylic acid has at least two pKa values, and in a most preferred embodiment, the polycarboxylic acid has three pKa values. Preferably, each pKa value is less than about 7, more preferably less than about 6.5. In a preferred embodiment, the polycarboxylic acid has at least two pKa values ​​less than about 7, more preferably less than about 6.5, and most preferably less than about 6. In a preferred embodiment, the polycarboxylic acid has at least one pKa value less than about 6, more preferably less than about 5.5, and most preferably less than about 5. In a preferred embodiment, each of the pKa values ​​is from about 2 to about 7, more preferably from about 2.5 to about 6.5. In a preferred embodiment, at least two of the pKa values ​​are from about 2 to about 7, more preferably from about 2.5 to about 6.5, and most preferably from about 3 to about 6. In a preferred embodiment, the polycarboxylic acid has at least one pKa value from about 2 to about 6, more preferably from about 2.5 to about 5.5, and most preferably from about 3 to about 5.

[0058] In a preferred embodiment, the polycarboxylic acid is citric acid, succinic acid, malic acid, N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), N,N-dicarboxymethylglutamic acid tetrasodium salt (GLDA), methylglycine diacetic acid (MGDA), a salt of any of the foregoing, sodium xylene sulfonate, or a mixture thereof.

[0059] In a preferred embodiment, the low-foam cleaning composition contains from about 25 ppm to about 50 wt. % of a polycarboxylic acid or its salt, more preferably from about 50 ppm to about 40 wt. % of a polycarboxylic acid or its salt, or most preferably from about 100 ppm to about 35 wt. % of a polycarboxylic acid or its salt.

[0060] In a preferred embodiment, the concentrated low-foam cleaning composition comprises from about 1% to about 50% by weight of a polycarboxylic acid or its salt, more preferably from about 5% to about 40% by weight of a polycarboxylic acid or its salt, or most preferably from about 10% to about 35% by weight of a polycarboxylic acid or its salt.

[0061] In a preferred embodiment, the low-foam cleaning composition contains from about 25 ppm to about 10,000 ppm of a polycarboxylic acid or its salt, more preferably from about 50 ppm to about 5000 ppm of a polycarboxylic acid or its salt, or most preferably from 100 ppm to about 2500 ppm of a polycarboxylic acid or its salt.

[0062] Carrier The low foaming cleaning composition may include a carrier. Preferred carriers include water and / or water-miscible solvents. As used herein, the term "water-miscible" means that a component (e.g., carrier or solvent) is soluble or dispersible in water at a concentration of more than about 0.2 g / L, preferably about 1 g / L or more, more preferably 10 g / L or more, and most preferably about 50 g / L or more at about 20°C.

[0063] In concentrated liquid compositions, the carrier is preferably at a concentration of about 5% to about 50% by weight, more preferably about 10% to about 40% by weight, and most preferably about 15% to about 35% by weight.

[0064] In the ready-to-use solution, the carrier may be present in an amount appropriate to reach the desired concentration of the active ingredient. In a preferred embodiment, the amount of carrier in the ready-to-use solution is about 20% to about 95% by weight, more preferably 30% to about 92% by weight, and most preferably about 40% to about 90% by weight.

[0065] Dyes / Odors The low foam cleaning composition may optionally include dyes, odorants, including fragrances, and other aesthetic enhancers. Dyes may be included to modify the appearance of the composition, such as, for example, FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keystone Analine and Chemical), Metanil Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue / Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), and the like.

[0066] Preferred odorants, including fragrances or flavorings, include, but are not limited to, terpenoids such as citronellol, aldehydes such as amylcinnamaldehyde, jasmines such as C1S-jasmine or jasmal, vanillin, and the like.

[0067] When the low foam cleaning composition includes a dye and / or odorant, such can be added in any amount to achieve the desired aesthetic enhancement. Preferably, the dye or odorant will be in an amount of from about 0.001% to about 5% by weight.

[0068] pH adjuster The low foam cleaning composition may optionally include a pH adjuster. The pH adjuster is used to adjust the pH of the low foam cleaning composition. Suitable pH adjusters may be acids and bases, including but not limited to strong acids, weak acids, strong bases, and weak bases. Suitable acids may include organic acids and inorganic acids. Examples of preferred organic acids include, but are not limited to, carboxylic acids such as hydroxyacetic acid (glycolic acid), citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid, among others. Organic dicarboxylic acids such as oxalic acid, malonic acid, gluconic acid, itaconic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid, among others, are also useful according to the present invention.

[0069] Preferred inorganic acids include, but are not limited to, sulfuric acid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromic acid, and nitric acid, among others. These acids may also be used in combination with other inorganic acids or those organic acids mentioned above.

[0070] Preferred bases include, but are not limited to, ammonia, ammonium hydroxide, amines, alkanolamines, aminoalcohols, borates, carbonates, hydroxides, silicates, or mixtures thereof.

[0071] If the low foaming cleaning composition includes a pH adjuster, such may be added in any amount to achieve the desired pH. Preferably, the pH adjuster will be in an amount of about 0.001% to about 10% by weight.

[0072] Coating material The low foaming cleaning composition may optionally include a coating agent. In embodiments where the low foaming cleaning composition is a rinse aid or a disinfectant rinse aid, a coating agent is preferably present. Coating agents may optionally be included in other low foaming cleaning compositions as well.

[0073] Preferred coating agents include alcohol ethoxylate compounds containing alkyl groups having 12 or fewer carbon atoms and have the formula I: RO-(CH 2 CH 2 O) n —H(I), wherein R is (C 1 ~C 12 ) alkyl group, and n is an integer ranging from 1 to 100. In some embodiments, R is a (C 8 ~C 12 ) alkyl group, or (C 8 ~C 10 ) alkyl group. Similarly, in some embodiments, n is an integer ranging from 10 to 50, or ranging from 15 to 30, or ranging from 20 to 25. In some embodiments, the alcohol ethoxylate has a low EO content, such as n of 6 or less.

[0074] In a more preferred embodiment, the coating may include at least two different alcohol ethoxylate compounds, each having a structure represented by Formula I. That is, the R and / or n variables of Formula I, or both, may be different in the two or more different alcohol ethoxylate compounds present in the coating. For example, the coating may include at least two different alcohol ethoxylate compounds, each having a structure represented by Formula I. 8 ~C 10 a first alcohol ethoxylate compound in which R is an alkyl group; and 10 ~C 12 ) alkyl group. In a preferred embodiment, the coating agent does not include alcohol ethoxylate compounds that include alkyl groups with more than 12 carbon atoms. In a preferred embodiment, the coating agent includes only alcohol ethoxylate compounds that include alkyl groups with 12 or fewer carbon atoms.

[0075] When the low foam cleaning composition includes a coating, the alcohol ethoxylate used in the coating can be selected to have certain characteristics, such as being environmentally friendly and suitable for use in the food service industry. For example, the particular alcohol ethoxylate used in the coating can meet environmental or food service regulatory requirements, such as biodegradability requirements.

[0076] In a preferred embodiment, the low foaming cleaning composition comprises from about 10 ppm to about 40% by weight of the coating agent, more preferably from about 25 ppm to about 35% by weight of the coating agent, or most preferably from about 50 ppm to about 30% by weight of the coating agent.

[0077] In a preferred embodiment, the concentrated low-foam cleaning composition comprises from about 1% to about 40% by weight of the coating agent, more preferably from about 5% to about 35% by weight of the coating agent, or most preferably from about 10% to about 30% by weight of the coating agent.

[0078] In a preferred embodiment, the low foaming cleaning composition comprises from about 10 ppm to about 10,000 ppm of the coating agent, more preferably from about 25 ppm to about 7500 ppm of the coating agent, or most preferably from about 50 ppm to about 5000 ppm of the coating agent.

[0079] Solidification aid In a preferred embodiment, the low foam cleaning composition may optionally include one or more solidification aids. Examples of solidification aids include, but are not limited to, urea, amides, such as stearic monoethanolamide or lauric diethanolamide or alkylamides, sulfates or sulfated surfactants, and aromatic sulfonates, solid polyethylene glycols, solid EO / PO block copolymers, starches that are rendered water-soluble through acid or alkali treatment processes, and various inorganics that impart solidification properties to heated compositions upon cooling. Such compounds can also change the solubility of the low foam cleaning composition in aqueous media during use, so that active ingredients can be dispensed from the solid composition over a long period of time. In a preferred embodiment, the solidification aid can also act as a builder.

[0080] Suitable aromatic sulfonates include, but are not limited to, sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and / or sodium butyl naphthalene sulfonate. Preferred aromatic sulfonates include sodium xylene sulfonate and sodium cumene sulfonate.

[0081] In a preferred embodiment of the solid low-foam cleaning composition, the solidification aid comprises sodium chloride, starch, sugars, C1-C10 alkylene glycols such as propylene glycol, solid PEG, solid PPG, solid EP / PO, amides, ureas, acetates, borates, phosphates, silicates, sulfonates, or mixtures thereof.

[0082] The amount of solidification aid included in the low foam cleaning composition can be influenced by the desired effect. In general, an effective amount of solidification aid is considered to be an amount that acts to solidify the low foam cleaning composition with or without other materials. Typically, for solid embodiments, the amount of solidification aid in the low foam cleaning composition is about 10% to about 80% by weight, preferably about 20% to about 75% by weight, more preferably about 20% to about 70% by weight.

[0083] In a preferred embodiment, the solidification aid is substantially free of sulfate. For example, the cleaning composition may have less than 1% by weight of sulfate, preferably less than 0.5% by weight, more preferably less than 0.1% by weight. In a preferred embodiment, the cleaning composition is free of sulfate.

[0084] Surfactants In some embodiments, the low foam cleaning composition may optionally include a surfactant. Depending on the desired role of the surfactant and the end use of the low foam cleaning composition, suitable surfactants may be nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, or mixtures thereof. When a surfactant is included in the low foam cleaning composition, in some embodiments, the surfactant is preferably at a concentration of about 10 ppm to about 50 wt. %, more preferably about 25 ppm to about 45 wt. % of surfactant, or most preferably about 50 ppm to about 35 wt. % of surfactant.

[0085] In a preferred embodiment, the concentrated low-foam cleaning composition comprises from about 1% to about 50% by weight of a surfactant, more preferably from about 5% to about 45% by weight of a surfactant, or most preferably from about 10% to about 35% by weight of a surfactant.

[0086] In a preferred embodiment, the low foaming cleaning composition comprises from about 10 ppm to about 10,000 ppm of surfactant, more preferably from about 25 ppm to about 7500 ppm of surfactant, or most preferably from about 50 ppm to about 5000 ppm of surfactant.

[0087] Nonionic Surfactants Useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically prepared by condensation of an organic aliphatic, alkylaromatic, or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety, the common practice being ethylene oxide or its polyhydration products, polyethylene glycol. In fact, 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 adducts, or mixtures thereof with 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 block polyoxypropylene-polyoxyethylene polymer compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. One class of compounds are difunctional (two reactive hydrogens) 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 the hydrophobe between the hydrophilic groups, controlled by length to constitute about 10% to about 80% by weight of the final molecule. Another class of compounds are trifunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from about 500 to about 7,000, and the hydrophile ethylene oxide is added to constitute about 10% to about 80% by weight of the molecule.

[0088] Condensation products of one mole of alkylphenols, the alkyl chain of which may be of linear or branched configuration, or of single or double alkyl constituents, containing from about 8 to about 18 carbon atoms, with from about 3 to about 50 moles of ethylene oxide. The alkyl groups may be represented, for example, by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants may also be polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols. Examples of commercial compounds of this chemistry are available under the trade names Igepal® manufactured by Rhone-Poulenc, and Triton® manufactured by Union Carbide.

[0089] A condensation product 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 may consist of a mixture of alcohols within the carbon range set forth above, or may consist of an alcohol having a specific number of carbon atoms within this range. Examples of equivalent commercially available surfactants are available under the trade name Neodol™ manufactured by Shell Chemical Co. and Alfonic™ manufactured by Vista Chemical Co.

[0090] 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 may consist of a mixture of acids within the carbon atom range defined above, or may consist of an acid having a specific number of carbon atoms within this range. An example of a commercial compound of this chemical is available under the trade name Lipopeg™ from Lipo Chemicals, Inc.

[0091] 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 in the present invention for 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.

[0092] Examples of non-ionic low foaming surfactants include: A compound from (1) modified, essentially inverted, by adding ethylene oxide to ethylene glycol to provide a hydrophile of specified molecular weight, and then adding 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, with the central hydrophile comprising 10% to about 80% by weight of the final molecule. The hydrophobic portion of the molecule has a molecular weight of about 2,100 to about 6,700, with the central hydrophile comprising 10% to 80% by weight of the final molecule.

[0093] Compounds from groups (1), (2), (3) and (4) that have been modified by "capping" or "end blocking" the terminal hydroxy groups (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 groups to chloride groups. Such modifications to the terminal hydroxy groups can result in all-block, block-heteric, heteric-block, or all-heteric nonionics.

[0094] Further examples of useful low foaming nonionics include: No. 2,903,486 issued to Brown et al. on September 8, 1959, the formula: [ka] where 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.

[0095] Polyalkylene glycol condensates of U.S. Pat. No. 3,048,548, issued Aug. 7, 1962 to Martin et al., having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains, wherein the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units, and the weight of the linking hydrophilic units each represent about one-third of the condensate.

[0096] General formula Z[(OR) n OH] z wherein Z is an alkoxylatable material, R is a radical derived from an alkylene oxide which may be ethylene and propylene, n is an integer, for example, from 10 to 2,000 or more, and z is an integer determined by the number of reactive oxyalkylatable groups.

[0097] Formula Y(C 3 H 6 O) n (C 2 H 4 O) mNo. 2,677,700 issued May 4, 1954 to Jackson et al., corresponding to H, wherein Y is the residue of an organic compound having from 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.

[0098] The formula Y[(C 3 H 6 O n (C 2 H 4 O) m H] x Conjugated polyoxyalkylene compounds as described in U.S. Patent No. 2,674,619 issued to Lundsted et al. on April 6, 1954, having the formula: Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, with x having a value of at least about 2, n has a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least about 900, and m has a value such that the oxyethylene content of the molecule is from about 10% to about 90% by weight. Compounds falling within the definition for Y include, for example, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, ethylenediamine, and the like. The oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide, and the oxyethylene chains also optionally, but advantageously, contain small amounts of propylene oxide.

[0099] Further conjugated polyoxyalkylene surfactants which may be advantageously used in the compositions of the present invention have the formula: P[(C 3 H 6 O) n (C 2 H 4 O) m H] xwhere P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44, and m has 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 advantageously, contain small amounts of ethylene oxide, and the oxyethylene chains may optionally, but advantageously, contain small amounts of propylene oxide.

[0100] Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions have the structural formula R 2 CON R1 Z (wherein R1 is H, C 1 ~C 4 R is a hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy group, or mixtures thereof; 2 may be linear C 5 ~C 31 Z is a hydrocarbyl, including those having Z being 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 derived from a reducing sugar in a reductive amination reaction, such as a glycityl moiety.

[0101] Alkyl ethoxylate condensation products of aliphatic alcohols with from 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.

[0102] Ethoxylated C 6 ~C 18 Fatty alcohols and C 6 ~C 18Mixed 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 C 6 ~C 18 Contains ethoxylated fatty alcohols.

[0103] 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, Llenado. These surfactants contain a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing from 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 glucosyl moieties. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. position, thus resulting in glucose or galactose as opposed to a 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.

[0104] Suitable fatty acid amide surfactants for use in the present compositions have the formula: 6 CON(R 7 ) 2 wherein R 6 is an alkyl group containing 7 to 21 carbon atoms, and each R 7 are independently hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Hydroxyalkyl, or -(C 2 H 4 O) X H, and x is in the range of 1 to 3.

[0105] A useful class of nonionic surfactants includes the class defined, at least in part, as alkoxylated amine or, most specifically, alcohol alkoxylated / aminated / alkoxylated surfactants. These nonionic surfactants can be represented by the general formula: 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 20 is 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 the alternative formula: R 20 -(PO) V -N[(EO) w H][(EO) z H], where 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 alkoxylates. Preferred nonionic surfactants for the compositions of the present invention include alcohol alkoxylates, EO / PO block copolymers, alkylphenol alkoxylates, and the like.

[0106] 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 the present invention. A typical listing of nonionic classes and species of these surfactants is given 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" (Vol. I and Vol. II, Schwartz, Perry and Berch).

[0107] Semi-polar nonionic surfactants Semi-polar nonionic surfactants are another class of nonionic surfactants that are useful in the compositions of the present invention.In general, semi-polar nonionics are high foaming agents and foam stabilizers, which may limit their application in CIP systems.However, within the compositional embodiments of the present invention designed for high foaming cleaning methodologies, semi-polar nonionics will have immediate utility.Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides, and their alkoxylated derivatives.

[0108] 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, and combinations thereof. In general, for detergent-related amine oxides, R 1 is an alkyl radical of about 8 to about 24 carbon atoms; R 2 and R 3is alkyl or hydroxyalkyl of 1 to 3 carbon atoms, or a mixture thereof; R 2 and R 3 can be bonded to each other through, for example, an oxygen or nitrogen atom to form a ring structure; R 4 is an alkyl or hydroxyalkylene group containing 2-3 carbon atoms, and n ranges from 0 to about 20.

[0109] 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, octadecyldimethylaine 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.

[0110] 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 3are each alkyl moieties independently selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

[0111] 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.

[0112] 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.

[0113] Useful examples of these sulfoxides include dodecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

[0114] 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 are octyl dimethylamine oxide, nonyl dimethylamine oxide, decyl dimethylamine oxide, undecyl dimethylamine oxide, dodecyl dimethylamine oxide, isododecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, These are 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.

[0115] 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, Dehypon LS-54 (R-(EO) 5 (PO) 4 ) and Dehypon LS-36 (R-(EO) 3 (PO)6 ), and end-capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC11, mixtures thereof, or the like.

[0116] Anionic Surfactants Surfactants classified as anionic because the charge on the hydrophobe 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 one skilled in the art will appreciate, anionic materials are excellent detersive surfactants and are therefore preferred additives to heavy duty detergent compositions.

[0117] 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, C 5 ~C 17 Acyl-N-(C 1 ~C 4 alkyl), and -N-(C 1 ~C 2hydroxyalkyl)glucamine sulfates, and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethyleneoxy)ether sulfates, and aromatic poly(ethyleneoxy)sulfates, such as the sulfates or condensation products of ethylene oxide and nonylphenol (usually having 1 to 6 oxyethylene groups per molecule).

[0118] 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 substitution.

[0119] 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, sulfonated fatty acids, such as sulfonated oleic acid, and the like. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxyls). Secondary carboxylates useful in the present compositions include those that contain a carboxyl unit connected to a secondary carbon. The secondary carbon may be in a ring structure, such as in p-octyl benzoic acid, or in alkyl substituted cyclohexyl carboxylates. Secondary carboxylate surfactants typically do not contain ether linkages, ester linkages, and hydroxyl groups. Additionally, they typically lack a nitrogen atom in the head group (amphiphilic portion). Suitable secondary soap surfactants typically contain 11-13 total carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acylamino acids (and salts), such as, for example, acyl glutamates, acyl peptides, sarcosinates (eg, N-acylsarcosinates), taurates (eg, N-acyltaurates and fatty acid amides of methyl tauride).

[0120] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: RO-(CH 2 CH2O) n (CH 2 ) m -CO 2 X(3) In the formula, R is C 8 ~C 22 is an alkyl group, or [ka] R 1 is C 4 ~C 16R 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 C 8 ~C 16 In some embodiments, R is an alkyl group. 12 ~C 14 It is an alkyl group, n is 4, and m is 1.

[0121] In other embodiments, R is [ka] and R 1 is C 6 ~C 12 In yet another embodiment, R 1 is C 9 It is an alkyl group, n is 10 and m is 1.

[0122] Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are usually 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 Alkylpolyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, C 9 Alkylarylpolyethoxy(10) carboxylic acids (Witco Chemical). Carboxylates, such as the products Sandopan® DTC, C 13 Alkylpolyethoxy(7) carboxylic acids are also available from Clariant.

[0123] Cationic Surfactants A surface active material is classified as cationic if the charge on the hydrotrope portion of the molecule is positive. Surfactants that do not carry a charge unless the hydrotrope is lowered to near neutral or below pH, in which case they are cationic (e.g., alkylamines), are also included in this group. In theory, cationic surfactants can be synthesized from any combination of elements that contain the "onium" structure RnX+Y-, and can include compounds other than nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, the cationic surfactant field is dominated by nitrogen-containing compounds, probably because the synthetic route to nitrogenous cationic materials is simple and easy, and gives high product yields, which can make them less expensive.

[0124] Cationic surfactants preferably include and more preferably refer to compounds that contain at least one long carbon chain hydrophobic group and at least one positively charged nitrogen. The long carbon chain group can be directly attached to the nitrogen atom by simple substitution, or more preferably, indirectly attached by a bridging functional group in so-called interrupted alkylamines and amidoamines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, more easily dissolved in water by co-surfactant mixtures, and / or water-soluble. To increase water solubility, additional primary, secondary, or tertiary amino groups can be introduced, or the amino nitrogen can be quaternized with low molecular weight alkyl groups. Furthermore, the nitrogen can be part of a branched or straight chain moiety with various degrees of unsaturation, or part of a saturated or unsaturated heterocyclic ring. In addition, cationic surfactants may contain complex bonds with two or more cationic nitrogen atoms.

[0125] Surfactant compounds classified as amine oxides, amphoterics, and zwitterions are themselves generally cationic in solutions at near-neutral to acidic pH and overlap with the surfactant classification. Polyoxyethylated cationic surfactants generally behave like nonionic surfactants in alkaline solutions and like cationic surfactants in acidic solutions.

[0126] The simplest cationic amines, amine salts and quaternary ammonium compounds are depicted diagrammatically as follows: [ka] where R represents an alkyl chain, R', R'', and R''' can be either an alkyl chain or an aryl group or hydrogen, and X represents an anion. Amine salts and quaternary ammonium compounds are preferred for practical use in the present invention due to their high degree of water solubility.

[0127] The majority of the bulk commercial cationic surfactants can be subdivided into four major classes and additional subgroups known to those skilled in the art and described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Vol. 104(2)86-96 (1989). The first class includes alkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourth class includes quaternaries such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkylammonium salts, etc. Cationic surfactants are known to have a variety of properties that can be beneficial in the present compositions. These desirable properties can include detergency in compositions below neutral pH, antimicrobial efficacy, thickening or gelling in conjunction with other agents, etc.

[0128] Cationic surfactants useful in the compositions of the present invention include those having the formula R 1 m R 2 x Y L Z, wherein each R 1 contains a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxy groups, and has up to four of the following structures: [ka] or an organic group containing a straight or branched chain alkyl or alkenyl group optionally interrupted by an isomer or mixture of these structures, which contains from about 8 to 22 carbon atoms. 1 The group may further include up to 12 ethoxy groups. m is a number from 1 to 3. Preferably, there is no more than one R 1 The group has 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3. Each R 2 is an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or a benzyl group, and there is not more than one R 2 is benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group are filled with hydrogen.

[0129] Y is [ka] or a mixture thereof. Preferably, L is 1 or 2, and the Y group is an R group having 1 to about 22 carbon atoms and 2 free carbon single bonds when L is 2. 1 and R 2 Z is a water-soluble anion such as a halide, sulfate, methyl sulfate, hydroxide, or nitrate, with chloride, bromide, iodide, sulfate, or methyl sulfate being preferred in number to provide electrical neutrality of the cationic component.

[0130] Amphoteric surfactants Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups.These ionic entities can be either anionic or cationic groups as described herein for other types of surfactants.Basic nitrogen and acidic carboxylate groups are typical functional groups employed as basic and acidic hydrophilic groups.In some surfactants, sulfonate, sulfate, phosphonate, or phosphate provide negative charge.

[0131] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, where the aliphatic radicals may be linear or branched, one of the aliphatic substituents contains about 8-18 carbon atoms, and one contains an anionic water-solubilizing group, such as carboxy, sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are known to those skilled in the art and are subdivided into two major classes described in "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 envisioned as falling into both classes.

[0132] 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 successive 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 a tertiary amine and an ether bond, and different alkylating agents produce different tertiary amines.

[0133] Long chain imidazole derivatives having utility in the present invention generally have the general formula: [ka] In the formula, R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation, typically sodium, for neutralizing the charge of the anion. Commercially well-known imidazoline-derived amphoteric compounds that can be used in the present composition include, for example, cocoamphopropionate, cocoamphocarboxy-propionate, cocoamphoglycinate, cocoamphocarboxy-glycinate, cocoamphopropyl-sulfonate, and cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be generated from aliphatic imidazolines, where the dicarboxylic acid functional group of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

[0134] The carboxymethylated compounds (glycinates) described herein above are often referred to as betaines, which are a special class of amphoteric compounds described herein below in the section entitled Zwitterionic Surfactants.

[0135] Long-chain N-alkyl amino acids are synthesized by the reaction RNH 2 R is easily prepared by 8 ~C 18 They are fatty amines with straight or branched chain alkyl, halogenated carboxylic acids. Alkylation of the primary amino group of the amino acid results in secondary and tertiary amines. The alkyl substituent may have additional amino groups providing multiple reactive nitrogen centers. Most commercial N-alkyl amine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercial N-alkyl amino acid ampholytes that have application in the present invention are alkyl beta-amino dipropionates, RN(C 2 H 4 COOM) 2 and RNHC 2 H 4COOM. In one embodiment, R can be an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms and M is a cation to neutralize the charge of the anion.

[0136] 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 combinations thereof, and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants may also be considered alkyl amphodicarboxylic acids. These 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 combinations thereof, and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants may also be considered alkyl amphodicarboxylic acids. 12 -Alkyl-C(O)-NH-CH 2 -CH 2 -N + (CH 2 -CH 2 -CO 2 Na) 2 -CH 2 -CH 2 -OH or C 12 -Alkyl-C(O)-N(H)-CH 2 -CH 2 -N + (CH 2 -CO 2 Na) 2 -CH 2 -CH 2 -OH. Disodium cocoamphodipropionate is one suitable amphoteric surfactant, available from Rhodia Inc., Cranberry, New Jersey, under the trade name Miranol™ FBS. Another suitable coconut-derived amphoteric surfactant, having the chemical name disodium cocoamphodiacetate, is available from Rhodia Inc., Cranberry, New Jersey, under the trade name Mirataine™ JCHA.

[0137] A representative listing of amphoteric classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). Each of these references is incorporated herein by reference in their entirety.

[0138] Zwitterionic Surfactants Zwitterionic surfactants can be considered a subset of amphoteric surfactants and can include anionic charges. 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 sometimes sulfonium or phosphonium ion, a negatively charged carboxyl group, and an alkyl group. Zwitterions generally contain cationic and anionic groups that ionize to about the same extent in the isoelectric region of the molecule, which can create a strong "inner salt" attraction between the positive-negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radical may be straight-chained or branched, one of the aliphatic substituents containing from 8 to 18 carbon atoms, and one containing an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0139] Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. The general formula for these compounds is: [ka] In the formula, R 1comprises 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 atoms, phosphorus atoms, and sulfur atoms, R 2 is an alkyl group or a monohydroxyalkyl group having 1 to 3 carbon atoms, x is 1 when Y is a sulfur atom, and is 2 when Y is a nitrogen atom or a phosphorus atom, R 3 is an alkylene or hydroxyalkylene or hydroxyalkylene of 1 to 4 carbon atoms and Z is a radical selected from the group consisting of carboxylic acid, sulfonic acid, sulfate, phosphonate, and phosphate groups.

[0140] 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 ... -hexadecylammonio)-2-hydroxy-propane-1-sulfonate, 4-[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 the detergent surfactants may be straight or branched, saturated or unsaturated.

[0141] Zwitterionic surfactants suitable for use in the present compositions include betaines of the following general structure: [ka]

[0142] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH, nor do they exhibit reduced water solubility in these isoelectric ranges. Unlike "external" quaternary ammonium salts, betaines can coexist with anions. Examples of suitable betaines include coconut acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C 12 - 14 Acylamidopropyl betaine, C 8-14 Acylamidohexyl diethyl betaine, 4-C 14-16 Acylmethylamidodiethylammonio-1-carboxybutane, C 16-18 Acylamide dimethyl betaine, C 12-16 Acylamide pentane diethyl betaine, and C 12-16 Acylmethylamidodimethylbetaine is an example.

[0143] Sultaines useful in the present invention have the formula (R(R 1 ) 2 N + R 2 SO 3- wherein R is C 6 ~C 18 is a hydrocarbyl group, and each R 1 are typically independently 1 ~C 3 alkyl, e.g., methyl; R 2 is C 1 ~C 6 Hydrocarbyl groups, such as C 1 ~C 3 It is an alkylene or hydroxyalkylene group.

[0144] A representative listing of zwitterionic classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). Each of these references is incorporated herein in their entirety.

[0145] Preferred Embodiments Preferred concentrations of the components (and optional ingredients) of the low foam cleaning composition are set forth in Tables 1A-1C (all upper and lower concentration values ​​are modified by the term about as defined herein). [Table 1] [Table 2] [Table 3]

[0146] As mentioned above, low foaming cleaning compositions can be formulated as concentrated (liquid or solid) compositions and then diluted to form a use composition, or they can be formulated as a ready-to-use composition. In general, 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 low foaming cleaning composition that contacts the article to be washed can be referred to as a concentrate or a use composition (or a use solution or a ready-to-use composition) depending on the formulation employed in the method according to the present invention. It should be understood that the concentration of the quaternary ammonium compound and polycarboxylic acid and / or its salt, as well as other optional ingredients, in the low foaming cleaning composition will vary depending on whether the composition is provided as a concentrate or as a use solution.

[0147] Use solutions may be prepared from the concentrates by diluting the concentrates with water at a dilution ratio that provides a use solution having a desired concentration. 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. A typical dilution factor is approximately 1 to approximately 10,000, but will depend on factors such as water hardness, amount of soil to be removed, etc. In one embodiment, the concentrates are diluted at a ratio of concentrate to water of about 1:10 to about 1:10,000. Specifically, the concentrates are diluted at a ratio of concentrate to water of about 1:100 to about 1:5,000. More specifically, the concentrates are diluted at a ratio of concentrate to water of about 1:250 to about 1:2,000.

[0148] Preferably, the low foaming cleaning composition is low foaming or non-foaming. As used herein, non-foaming means that the composition does not form foam when diluted or forms foam that breaks in less than 10 seconds, more preferably less than 5 seconds, at a temperature of about 20°C to about 100°C. As used herein, low foaming means that the composition forms foam that breaks in less than 30 seconds, more preferably less than 20 seconds, most preferably less than 15 seconds, at a temperature of about 20°C to about 100°C.

[0149] Method for Producing a Low-Foaming Cleaning Composition The low foaming cleaning composition can be prepared as a solid or liquid composition. Suitable solid cleaning compositions include, but are not limited to, granulated and pelletized solid compositions, powders, solid block compositions, cast solid block compositions, extruded solid block compositions, pressed solid compositions, and the like.

[0150] Solid particulate cleaning compositions can be made by simply blending the dry solid components formed according to the present invention in the appropriate ratios, or by agglomerating the materials in a suitable agglomeration system. Pelletized materials can be produced by compressing solid granular or agglomerated materials in suitable pelletizing equipment to provide appropriately sized pelletized materials. Solid block and cast solid block materials can be made by introducing into a container either a block of pre-hardened material or a castable liquid that hardens into a solid block in the container. Preferred containers include disposable plastic containers or water-soluble film containers. Other suitable packaging for the compositions include flexible bags, packets, shrink wrap, and water-soluble films such as polyvinyl alcohol.

[0151] The solid low-foam cleaning composition can be formed using a batch or continuous mixing system. In an exemplary embodiment, a single or twin screw extruder is used to combine and mix one or more components with high shear to form a homogeneous mixture. In some embodiments, the processing temperature is equal to or lower than the melting temperature of the components. The processed mixture can be dispensed from the mixer by molding, casting, or other suitable means, where the cleaning composition hardens into a solid form. The structure of the matrix can be characterized according to its hardness, melting point, material distribution, crystal structure, and other similar properties by methods known in the art. In general, the solid cleaning composition processed according to the method of the present invention is substantially homogeneous throughout its mass with respect to the distribution of components and is dimensionally stable.

[0152] In the extrusion process, liquid and solid components are introduced into a final mixing system and are mixed continuously until the components form a substantially homogenous semi-solid mixture in which the components are distributed throughout its mass. The mixture is then discharged from the mixing system into or through a die or other shaping means. The product is then packaged. In an exemplary embodiment, the formed composition begins to harden into a solid form in about 1 minute to about 3 hours. Specifically, the formed composition begins to harden into a solid form in about 1 minute to about 2 hours. More specifically, the formed composition begins to harden into a solid form in about 1 minute to about 20 minutes.

[0153] In the casting process, the liquid and solid components are introduced into a final mixing system and mixed continuously until the components form a substantially homogenous liquid mixture in which the components are distributed throughout its mass. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 60 seconds. Once mixing is complete, the product is transferred to a packaging container where solidification occurs. In an exemplary embodiment, the cast composition begins to harden into a solid form in approximately 1 minute to approximately 3 hours. Specifically, the cast composition begins to harden into a solid form in approximately 1 minute to approximately 2 hours. More specifically, the cast composition begins to harden into a solid form in approximately 1 minute to approximately 20 minutes.

[0154] In the press solid process, flowable solids such as granular solids and other particulate solids may be combined under pressure. In the press solid process, the flowable solids of the composition are placed in a form (e.g., a mold or container). The method may include gently pressing the flowable solids into the form to produce a solid cleaning composition. Pressure may be applied by a block machine or a rotary plate press, or the like. Pressure may be applied at about 1 to about 3000 psi, about 5 to about 2500 psi, or about 10 psi to about 2000 psi. As used herein, the term "psi" or "pounds per square inch" refers to the actual pressure applied to the flowable solid being pressed, and not to the gauge or water pressure measured at a point in the pressing device. The method may include a curing step to produce a solid cleaning composition. As referred to herein, the uncured composition including the flowable solids is compressed to provide sufficient surface contact between the particles that make up the flowable solids that the uncured composition will solidify into a stable solid cleaning composition. A sufficient amount of particles (e.g., granules) in contact with one another provides effective particle-to-particle bonding to create a stable solid composition. Inclusion of an optional curing step can include allowing the pressed solid to solidify for a period of time, such as several hours or about a day (or more). In an additional aspect, the method can include vibrating the flowable solid in a form or mold, such as the method disclosed in U.S. Patent No. 8,889,048, which is incorporated herein by reference in its entirety.

[0155] The use of pressed solids offers many advantages over conventional solid block or tablet compositions that require high pressure in a tablet press or casting, which requires melting the composition consuming significant amounts of energy, and / or extrusion, which requires expensive equipment and advanced technical knowledge. Pressed solids overcome such various limitations of other solid formulations that are necessary for the creation of solid cleaning compositions. Furthermore, pressed solid compositions retain their shape under conditions under which the composition may be stored or handled.

[0156] By the term "solid" it is meant that the hardened composition will not flow under moderate stress or pressure or simple gravity and will substantially retain its shape. The solid can be in various forms such as powder, flakes, granules, pellets, tablets, drops, pucks, briquettes, bricks, solid blocks, unit doses, or another solid form known to those skilled in the art. The hardness of the solid cast and / or pressed solid compositions can range from that of a relatively dense and hard fused solid product, such as concrete, to that characterized as being a hardened paste. In addition, the term "solid" refers to the state of the cleaning composition under the expected conditions of storage and use of the solid cleaning composition. In general, it is expected that the cleaning composition will remain in solid form when exposed to temperatures up to approximately 100°F, specifically up to approximately 120°F.

[0157] The resulting solid foaming cleaning composition may take the form of, but is not limited to, a cast solid product, an extruded, molded, or formed solid pellet, block, tablet, powder, granule, flake, compressed solid, or the formed solid may then be ground or formed into a powder, granule, or flake. In an exemplary embodiment, the extruded pellet material formed by the solidification matrix has a weight of about 50 grams to about 250 grams, the extruded solid formed by the composition has a weight of about 100 grams or more, and the solid block detergent formed by the composition has a mass of about 1 to about 10 kilograms. The solid composition provides a stabilized source of functional materials. In some embodiments, the solid composition may be dissolved, for example, in an aqueous or other medium, to generate a concentrated solution and / or a use solution. This solution may be directed to a reservoir for subsequent use and / or dilution, or may be applied directly to the point of use.

[0158] The following patents disclose various combinations of solidifying agents, binders, and / or hardeners that may be utilized in the solid cleaning compositions of the present invention: U.S. Patents 7,153,820, 7,094,746, 7,087,569, 7,037,886, 6,831,054, 6,730,653, 6,660,707, 6,653,266, 6,583,094, 6,410,495, 6,258,765, 6,310,102 ... ,177,392, 6,156,715, 5,858,299, 5,316,688, 5,234,615, 5,198,198, 5,078,301, 4,595,520, 4,680,134, RE32,763, and RE32818 are incorporated herein by reference.

[0159] Liquid compositions can typically be made by forming the components in an aqueous liquid or aqueous liquid solvent system. Such systems are typically made by dissolving or suspending the active ingredient in water or a compatible solvent, and then diluting the product to an appropriate concentration to form either a concentrate or its use solution. Gelled compositions can similarly be made by dissolving or suspending the active ingredient in a compatible aqueous, aqueous liquid, or mixed aqueous-organic system containing a gelling agent at an appropriate concentration. All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains.

[0160] Methods of Using Low-Foam Cleaning Compositions The low-foam cleaning composition can be used in a variety of ways. It is expected that the low-foam cleaning composition is applied to the article to be cleaned by contacting the article. This contacting can be performed by pouring, spraying, mopping, wiping, or any other method of applying the composition. In a preferred embodiment, the article can be rinsed with water after application of the low-foam cleaning composition. In a preferred embodiment, the article can be rinsed before application of the low-foam cleaning composition.

[0161] The low-foaming cleaning composition can be applied to a cleaning process at a temperature in the range of about 20° C. to about 100° C. In a preferred embodiment, the low-foaming cleaning composition is applied to a low-temperature cleaning process at a temperature of about 20° C. to about 70° C., more preferably about 20° C. to about 60° C., and most preferably about 20° C. to about 50° C.

[0162] Methods of use may include, but are not limited to, dishwashing methods, laundry methods, clean-in-place methods, hard surface cleaning methods, and disinfecting methods. The low foam cleaning composition may be applied to any of these methods as a pre-treatment, washing step, rinsing step, and / or finishing step.

[0163] 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. EXAMPLES

[0164] The embodiments of the present invention are further defined in the following non-limiting examples. It should be understood that these examples, while showing specific embodiments of the present invention, are given by way of illustration only. From the above description and these examples, a person skilled in the art can ascertain the essential features of the present invention, and can make various changes and modifications of the embodiments of the present invention to adapt it to various applications and conditions without departing from the spirit and scope of the present invention. Thus, in addition to those shown and described herein, various modifications of the embodiments of the present invention will be apparent to a person skilled in the art from the foregoing description. Such modifications are also intended to be included within the scope of the appended claims. The materials used in the following examples are listed below.

[0165] The following commercially available polycarboxylic acids and their salts were employed in the examples: citrate, succinate, malate, ethylenediaminetetraacetic acid (EDTA), N,N-dicarboxymethylglutamic acid tetrasodium salt (GLDA), and methylglycine diacetic acid (MGDA).

[0166] The following commercially available quaternary ammonium compounds were employed in the examples: alkyl alkoxylated quaternary ammonium, alkyl diethanol quaternary ammonium, alkyl C10-C16 benzyl ammonium chloride (ADBAC), alkyl C10-C16 ethyl benzyl ammonium chloride (ADEBAC), and dialkyl C8-C16 dialkyl C1-C4 ammonium salts. Quaternary ammonium compounds provided under the following trade names were also employed in the examples: Bardac 205M, Bardac 2250, Carboquat, Stepan Quat, and BarQuat MB-50.

[0167] The following exemplary commercially available antifoam agents were employed in the examples: Airase® (a siloxane antifoam agent available from Evonik), Plurafac SLF-180 (an alcohol alkoxylate available from several commercial suppliers), N3 (an exemplary commercially available reverse block copolymer antifoam surfactant), and Surfynol® MD 20 (a gemini-based antifoam surfactant commercially available from Evonik).

[0168] Example 1 Foam Rating The foaming properties of the quaternary ammonium compounds were evaluated and then tested for reduced foaming when a traditional antifoam compound was included. Foam height was determined by the following procedure steps: 1. A 1200 ppm solution of the test composition was mixed in water. 2. The foam height was measured immediately after mixing. 3. The solution was stirred and the foam height was measured after 15 seconds. 4. The solution was stirred and after an additional 45 seconds of stirring (a total of 60 seconds after the solution was mixed) the solution was measured.

[0169] The temperature of the solution was 120° F. for the duration of the test. The results of these preliminary tests are provided in Figures 1A and 1B. As can be seen in Figures 1A and 1B, the various quaternary ammonium compounds tested provided significant post-mix foam height after 15 seconds of mixing. Traditional antifoam agents have different effects on the foaming properties of the quaternary ammonium compounds.

[0170] The ability of polycarboxylic acids and / or salts to control foam of different quaternary ammonium compounds was also tested. The same procedural steps outlined above were followed. The results of this testing are shown in Figures 2A and 2B. As seen in Figures 2A and 2B, most of the polycarboxylic acids and / or salts provided significant reduction in foaming. Those that did not were acetate, sodium sulfate, and sodium benzoate. Without wishing to be bound by theory, this is believed to be due in part to the monobasic nature of acetate and sodium benzoate, and the strong acid pKa of sodium sulfate (pKa of -3). Other polycarboxylic acids provided similar, and in many cases, superior, foam reduction, in contrast to the traditional antifoam agents shown in Figures 1A and 1B.

[0171] Example 2 Antimicrobial Evaluation Quaternary ammonium compounds were tested for antimicrobial efficacy against exemplary bacteria (E. coli and Staphylococcus aureus) under different pH conditions. For this evaluation, various test solutions were prepared in 500 ppm hard water at a temperature of 120° F. The microbial population was contacted with the test composition for approximately 30 seconds. The microbial population was measured before and after the contact procedure, and the difference was taken to determine the log reduction. The quaternary ammonium compounds tested, their concentrations, and the corresponding log reduction are shown in Table 2 below. [Table 4]

[0172] This test was conducted to determine the appropriate pH conditions that would maintain the antimicrobial efficacy of the quaternary ammonium compounds so that polycarboxylic acids and / or their salts could be effectively employed in the compositions. As seen in Table 2, the compositions provided significant log reductions at pHs between about 5 and 9. For example, at pH values ​​of about 5, 8, and 9, solutions of the tested quaternary ammonium compositions provided greater than about 6 log reductions after 30 seconds of contact time with the microbial population of Staphylococcus aureus.

[0173] The invention being thus described, it will be apparent that it 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 an explanation 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. Quaternary ammonium compounds and Polycarboxylic acids and / or salts thereof, A low-foaming cleaning composition comprising, The polycarboxylic acid has at least two pKa values ​​less than 7, The quaternary ammonium compound is alkyl(C8-C16)dimethylbenzylammonium chloride (ADBAC), dialkyl(C8-C16)dimethylammonium chloride (DAAC), or a mixture thereof. A low-foaming cleaning composition wherein the composition is a liquid and has a pH of 5 to 9.

2. The low-foaming cleaning composition according to Claim 1, wherein the polycarboxylic acid and / or salt thereof is one or more of citric acid, succinic acid, malic acid, or ethylenediaminetetraacetic acid (EDTA).

3. The low-foaming cleaning composition according to claim 1 or 2, wherein the polycarboxylic acid has at least two pKa values ​​less than 6.

5.

4. The low-foaming cleaning composition according to any one of claims 1 to 3, wherein the polycarboxylic acid has at least two pKa values ​​less than 6.

5. The low-foaming cleaning composition according to any one of claims 1 to 4, wherein the pKa values ​​of the polycarboxylic acid are each 2 to 6.

6. The low-foaming cleaning composition according to any one of claims 1 to 5, wherein the quaternary ammonium compound is concentrated at a concentration of 10 ppm to 40% by weight, and the polycarboxylic acid or its salt is concentrated at a concentration of 25 ppm to 50% by weight.

7. The low-foaming cleaning composition according to any one of claims 1 to 6, wherein the composition is a concentrated liquid composition, the quaternary ammonium compound is concentrated in a concentration of 1% to 40% by weight, and the polycarboxylic acid or its salt is concentrated in a concentration of 1% to 50% by weight.

8. The low-foaming cleaning composition according to any one of claims 1 to 6, wherein the composition is a ready-to-use liquid composition, the quaternary ammonium compound is concentrated at a concentration of 10 ppm to 1,000 ppm, and the polycarboxylic acid or its salt is concentrated at a concentration of 25 ppm to 10,000 ppm.

9. The low-foaming cleaning composition according to any one of claims 1 to 8, wherein the composition further comprises a carrier in a concentration of 5% to 95% by weight.

10. The low-foaming cleaning composition according to any one of claims 1 to 9, wherein the composition further comprises a dye, a deodorant, a pH adjuster, a coating agent, a surfactant, or a mixture thereof.

11. The low-foaming cleaning composition according to any one of claims 1 to 10, wherein the polycarboxylic acid and / or salt thereof is one or more citric acid and / or ethylenediaminetetraacetic acid (EDTA).

12. A method for cleaning an article, wherein the method is: A method comprising bringing the low-foaming cleaning composition according to any one of claims 1 to 11 into contact with the article.

13. The method according to claim 12, further comprising the step of dissolving and / or diluting the low-foaming cleaning composition before or during the contact step.

14. The method according to claim 12 or 13, wherein the article is tableware, fabric, or a hard surface.

15. The method according to any one of claims 12 to 14, wherein the method further comprises the step of rinsing the article.

16. The method according to any one of claims 12 to 15, wherein the method is carried out at a temperature of 20°C to 100°C.

17. The method according to any one of claims 12 to 16, wherein the method is carried out at a temperature of 20°C to 70°C, and the washing method is a disinfection method.

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