Interaction of antimicrobial quaternary compounds with anionic polymers or chelating agents
By blending the quaternary ammonium compound with anionic surfactant or polymer/chelating agent to form an enhanced antimicrobial composition, the problem of insufficient efficacy of the antimicrobial quaternary ammonium compound in the prior art under low concentrations and adverse conditions is solved. Enhanced antimicrobial and disinfecting activity at neutral to alkaline pH is achieved.
Patent Information
- Application Number
- CN202411526817.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2016-08-11
- Filing Date
- 2017-02-28
- Publication Date
- 2025-02-07
AI Technical Summary
Existing antimicrobial quaternary ammonium compounds are difficult to maintain their killing efficacy against Gram-negative microorganisms such as E. coli at low concentrations, and are low in reduced temperature and pH.
By blending the quaternary ammonium compound with anionic surfactant or anionic polymer/chelating agent, an enhanced antimicrobial composition is formed, improving its antimicrobial activity and disinfection effectiveness.
The composition provides enhanced antimicrobial and disinfectant activity at neutral to alkaline pH, overcoming the lack of efficacy of quaternary ammonium compounds at low concentrations and adverse conditions, while improving its killing of Gram-negative microorganisms ability.
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Abstract
Description
[0001] This application is a divisional application of the Chinese invention patent application with application number 201780045623.2, application date February 28, 2017, and invention name “Interaction between antimicrobial quaternary compounds and anionic surfactants”.
[0002] CROSS-REFERENCE TO RELATED APPLICATIONS
[0003] This application is a non-provisional application claiming priority to U.S. Provisional Application No. 62 / 373,772 filed on August 11, 2016, the entire contents of which are incorporated herein by reference. Technical Field
[0004] The present invention relates to antimicrobial compositions, including activated or deactivated antimicrobial compositions. In certain embodiments, antimicrobial quaternary ammonium compounds and anionic surfactants are provided in combination, providing compositions with enhanced antimicrobial properties, which may include enhanced surface activity and / or disinfection efficacy. In other aspects, a combination of antimicrobial quaternary ammonium compounds and anionic polymers or chelating agents is provided. Specifically, compared with independent anionic surfactants or quaternary ammonium compounds, this combination provides enhanced antimicrobial activity. In other embodiments, antimicrobial quaternary ammonium compounds and anionic surfactants are provided in combination, to provide compositions with deactivation antimicrobial properties. Advantageously, according to the present invention, activated or deactivated compositions are provided according to specific use applications. Background Art
[0005] Antimicrobial agents are chemical compositions used to prevent microbial contamination and degradation of products, materials, media (such as water treatment streams) and systems. Antimicrobial agents and compositions are used as, for example, bactericides or disinfectants associated with hard surface cleaning, food preparation, animal feed, cooling water, hotel services, hospitals and medical uses, pulp and paper manufacturing, cleaning textiles and water treatment. Among various types of antimicrobial agents and compositions, quaternary ammonium compounds represent one of the largest categories in use. At low concentrations, quaternary ammonium antimicrobial agents are bacteriostatic, fungistatic, algastatic, spore-inhibiting and tuberculosis-inhibiting. At moderate concentrations, they have bactericidal, fungicidal, algaecidal and virucidal effects on lipophilic viruses. It is known that quaternary ammonium compounds are difficult to maintain killing efficacy against Gram-negative microorganisms such as Escherichia coli (E. coli) below about 150ppm, and are also inefficient at reduced temperatures and pH. Therefore, it is desirable to improve the antimicrobial activity of chemical substances such as quaternary ammonium compounds. It is desirable to improve the antimicrobial activity of these chemicals for us in various applications.
[0006] It is therefore an object of the claimed invention to develop an enhanced antimicrobial quaternary ammonium compound based composition.
[0007] It is another object of the present invention to provide synergistic combinations of quaternary ammonium compounds and anionic surfactants which provide increased dynamic surface activity (as measured by reduction in dynamic surface tension).
[0008] It is another object of the present invention to provide synergistic combinations of quaternary ammonium compounds and anionic polymers or chelating agents to provide such improved and synergistic surface activity.
[0009] It is an object of the present invention to provide activated compositions with enhanced and / or synergistic surface activity having use applications including, for example, disinfecting and / or sterilizing surfaces, including high level disinfectants for medical devices, antimicrobial lubricants, laundry cleaning and disinfecting, antimicrobials with enhanced mildness and reduced irritation, enhanced combination products, third sink applications, and the like.
[0010] It is another object of the present invention to provide enhanced antimicrobial and / or disinfectant activity via blends of quaternary ammonium compounds and anionic surfactants, including overcoming conventional limitations of quaternary ammonium compounds, including conventional requirements for neutral to alkaline pH for performance efficacy, hard water performance limitations requiring increased concentrations, and the need for higher concentrations of actives for efficacy.
[0011] Another aspect of the present invention is to provide a disinfecting composition to improve upon conventional quaternary ammonium compounds that are not themselves very surface active. In one aspect, the antimicrobial and / or disinfecting activity enhanced with a blend of a quaternary ammonium compound and an anionic surfactant, including enhanced wettability in some applications, unexpectedly provides such activity at or above pH neutrality (as opposed to the acidic pH conventionally used, as tested for 500 ppm water hardness suspension). In another aspect, and as an additional benefit of the present invention, the composition provides enhanced mildness and reduced irritation while leaving less residue on the substrate surface.
[0012] It is another object of the present invention to provide blends of quaternary ammonium compounds and anionic surfactants having inactivating antimicrobial and / or disinfecting efficacy through the selection of anionic surfactants for use in the composition.
[0013] An object of the present invention is to provide a composition of neutralized quaternary ammonium compound and anionic surfactant deactivation, which has use applications including, for example, water treatment, quaternary ammonium compound titration kit, surfactant recovery, etc.
[0014] Other objects, advantages and features of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings. Summary of the invention
[0015] The compositions according to the present invention provide the ability to enhance or inactivate the antimicrobial efficacy of quaternary ammonium compounds. In one aspect, the selected anionic surfactants disclosed herein provide such a selection for providing an antimicrobial composition or an inactivated antimicrobial composition. According to one embodiment, anionic surfactants with strong ionic bonds are used to inactivate the antimicrobial efficacy of quaternary ammonium compounds, while anionic surfactants with weaker ionic bonds provide enhanced or "activated" antimicrobial efficacy of quaternary ammonium compounds.
[0016] The composition of the present invention provides a quaternary ammonium compound combined with anionic surfactants. In certain embodiments, the quaternary ammonium with a carbon chain less than 20 is included in the composition of the present invention. Examples of quaternary ammonium compounds suitable for the present invention include but are not limited to alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride and didecyl dimethyl ammonium chloride etc. Single quaternary ammonium or a combination of more than one quaternary ammonium may be included in the composition of the present invention. Other examples of quaternary ammonium compounds suitable for the present invention include but are not limited to benzethonium chloride, ethyl benzethonium chloride, myristyl trimethyl ammonium chloride, methyl benzethonium chloride, cethamonium chloride, cetrimonium bromide (CTAB), carnitine, dofadumium chloride, tetraethyl ammonium bromide (TEAB), domiphene, benzododecyl bromide, benzozonium chloride, choline, cocamidopropyl betaine (CAPB) and denatonium.
[0017] Compositions of the present invention further include anionic surfactants, which are selected to have the desired antimicrobial or inactivated antimicrobial effect on the quaternary ammonium compound. As described in accordance with the present invention, it has been found that the combination of quaternary ammonium compound and anionic surfactant can enhance the antimicrobial efficacy or inactivate the antimicrobial efficacy, which can be selected according to its surface activity. That is, if the combination has high surface activity (low surface tension) compared to another combination, the combination with the highest surface activity can enhance the antimicrobial efficacy of the quaternary ammonium. On the contrary, if the combination has lower surface activity (higher surface tension) compared to another combination, the combination with low surface activity neutralizes the antimicrobial efficacy of the quaternary ammonium or inactivates the antimicrobial efficacy of the quaternary ammonium.
[0018] In certain preferred aspects, the combination of at least one quaternary ammonium compound and an anionic surfactant based on a carboxylate provides improved antimicrobial activity compared to any component used alone. In preferred aspects, the synergistic combination increases the activity of the quaternary ammonium compound to the microbial load, wherein the anionic surfactant and the quaternary ammonium compound are not effective alone. Therefore, the composition has advantages over existing antimicrobial treatment agents and provides improved results. The combination of the antimicrobial agent disclosed herein and the anionic surfactant provides better results than when any single component is used alone. Examples of preferred carboxylate anionic surfactants for enhancing the surface activity and antimicrobial efficacy of quaternary ammonium compounds include carboxylates with C6-C10 carbon chains. Examples of anionic carboxylate surfactants include organic acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid and decanoic acid. Examples of branched organic acids include ethylhexyl carboxylate, isononanoic acid and tridecyl carboxylate. Examples of commercially available surfactants include Marlowet4539 (C9-alcohol polyglycol ether carboxylic acid purchased from Sasol). In other embodiments, phosphates are used to enhance the antimicrobial activity of quaternary ammonium compounds.
[0019] Composition of the present invention further comprises anionic polymer or chelating agent.In one aspect, composition is silane-free quaternary ammonium compound, and it has less than C20 chain length and is combined with anionic polymer and / or chelating agent.In some respects, anionic polymer and / or chelating agent used in combination with quaternary ammonium compound is polyacrylate, acrylamide, carboxylate, phosphinic acid or phosphonate, or its mixture.In one aspect, the pH of composition is 3 or lower.On the other hand, composition is substantially free of oxidant.In other embodiments, the quaternary ammonium compound used for the present composition is composed of a mixture of dialkyl quaternary ammonium and alkyl benzyl quaternary ammonium, and anionic polymer is polyacrylate, acrylamide, carboxylate, phosphinic acid or phosphonate, or its mixture.
[0020] In a preferred embodiment, the quaternary ammonium compound used in the antimicrobial composition of the present invention consists of a mixture of dialkyl quaternary ammonium and alkyl benzyl quaternary ammonium, and the anionic surfactant is caprylic acid, nonanoic acid or capric acid or a mixture thereof.
[0021] In other preferred aspects, the combination of at least one quaternary ammonium compound and an anionic surfactant based on sulfate or sulfonate provides an inactivated antimicrobial or surface activity of the quaternary ammonium compound. In certain preferred aspects, the combination of at least one quaternary ammonium compound and anionic surfactant having a relatively strong ionic bond inactivates the antimicrobial efficacy of the quaternary ammonium compound. Examples of commercially available sulfate or sulfonated anionic surfactants include X-AES (available from Huntsman Chemical), C-AES (available from Huntsman Chemical), and C-AES (available from Huntsman Chemical). 12-14 -(PO) 16-(EO)2-sulfate), SLS (sodium lauryl sulfate) and SLES (sodium lauryl ether sulfate).
[0022] Methods of using the compositions are also included in embodiments of the invention.
[0023] Although multiple embodiments are disclosed, other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the present invention. Therefore, the drawings and specific embodiments are to be regarded as illustrative rather than restrictive in nature. These and other features, objects and advantages of the present invention will become apparent from the following detailed description of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 is a graph showing the dynamic surface tension of a composition prepared with a 9:1 mass ratio of quaternary ammonium compound:anionic surfactant evaluated according to an embodiment of the present invention.
[0025] Figure 2 is a graph showing the dynamic surface tension of compositions prepared with a mole:mole ratio of quaternary ammonium compound:anionic sulfate surfactant.
[0026] Figure 3A The following is a diagram showing the use of the user evaluation according to the embodiment of the present invention.
[0027] Plot of dynamic surface tension of compositions prepared with mole:mole ratios of Bardac 205M quaternary ammonium compound:anionic carboxylate surfactant.
[0028] Figure 3B is a graphical representation of the dynamic surface tension of Bardac 205M and various concentrations of decanoic acid as described in Example 3.
[0029] Figures 4A-4C Depicted are dynamic surface tension graphs comparing compositions prepared using quaternary ammonium compounds interacting with various sulfate-based anionic surfactants to compositions prepared using quaternary ammonium compounds with carboxylate anionic surfactants. Figure 4A The evaluation results using SLS are shown. Figure 4B Evaluation results using NAS-FAL are shown. Figure 4C The evaluation results using EH-S are shown.
[0030] Figure 5A is a graph showing the pH of compositions prepared with quaternary ammonium compounds and carboxylate-based anionic surfactants based on molar ratios evaluated according to examples of the present invention.
[0031] Figure 5Bis a graph showing the pH of compositions prepared with quaternary ammonium compounds and carboxylate-based anionic surfactants based on molar ratios evaluated according to examples of the present invention.
[0032] Fig. 6A is a graph illustrating the antimicrobial efficacy of the compositions of the present invention at different molar ratios against Escherichia coli and Staphylococcus aureus evaluated according to examples of the present invention.
[0033] Figure 6B is a graph illustrating the antimicrobial efficacy of compositions of the present invention prepared with a quaternary ammonium:anionic surfactant mass ratio of 7.5:1 at 300 ppm, 150 ppm and 75 ppm Bardac 205M evaluated in accordance with examples of the present invention.
[0034] Figure 7 is a graph showing the antimicrobial efficacy of different anionic surfactants in combination with the quaternary ammonium Bardac 205M evaluated according to an example of the present invention.
[0035] Figure 8 is a graph illustrating the antimicrobial efficacy of the composition of the present invention against Staphylococcus.
[0036] Fig.9A is a graph illustrating the antimicrobial efficacy of the compositions of the present invention against Staphylococcus at pH 4.0 or pH 8.0.
[0037] Fig. 9B Graphs show the antimicrobial efficacy of the composition of the present invention against Escherichia coli at pH 4.0 or pH 8.0.
[0038] Fig.10 Shown is a graphical representation of the average dynamic surface tension of Bardac LF80 and anionic polymer as described in Example 16.
[0039] Fig.11 A graphical representation showing the average dynamic surface tension of Bardac LF80 and different concentrations of polymer at pH 7.0 as described in Example 16.
[0040] Fig.12 Shown is a graph of the average dynamic surface tension at pH 11 for Bardac LF80 and different concentrations of polymer as described in Example 16.
[0041] Fig.13 is a graphical representation of the average dynamic surface tension of Bardac 2250 and anionic polymers as described in Example 17.
[0042] Fig.14 is a graphical representation of the average dynamic surface tension of Bardac 2250 and different concentrations of polymer at pH 7.0 as described in Example 17.
[0043] Fig.15 is a graph showing the average dynamic surface tension of Bardac 2250 and different concentrations of polymer as described in Example 17 at pH 11 and pH 7.0.
[0044] Fig.16 A graphical representation showing the average dynamic surface tension of Bardac 205M and anionic polymers as described in Example 17.
[0045] Fig.17 A graphical representation of the average dynamic surface tension of Uniquat QAC50 and anionic polymers as described in Example 17 is shown.
[0046] Fig.18 is a graphical representation of the average dynamic surface tension of Bardac LF80 and the anionic chelator HEDP at different concentrations as described in Example 18.
[0047] Fig.19 is a graphical representation of the average dynamic surface tension of Bardac 2250 and anionic chelating agent pairs as described in Example 18.
[0048] Fig. 20 is a graph showing the average dynamic surface tension of Uniquat QAC50 and anionic chelating agent pairs as described in Example 18.
[0049] Fig.21 A graphical representation showing the variation in average dynamic surface tension as a function of pH for Bardac LF80 and the anion chelator Trilon M evaluated according to an example of the present invention.
[0050] Fig. 22 Representative images of mineral deposit removal and chelating agent activation from polypropylene surfaces evaluated according to embodiments of the present invention are shown.
[0051] Fig.23 Representative images of mineral deposit removal and polymer activation from polypropylene surfaces evaluated according to embodiments of the present invention are shown.
[0052] Various embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein the same reference numerals in several drawings represent the same components. Reference to various embodiments does not limit the scope of the present invention. The drawings shown herein are not limitations of the various embodiments according to the present invention, but are intended to provide exemplary illustrations of the present invention. DETAILED DESCRIPTION
[0053] Embodiments of the present invention are not limited to specific compositions for hard surface cleaning (including antimicrobial and / or disinfection applications of activated compositions and alternative cleaning and use of inactivated compositions), methods for preparing the compositions and / or methods of use, which may vary and are understood by the skilled person. In order to more easily understand the present invention, certain terms are first defined. It should also be understood that all terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limited in any manner or scope. For example, as used in this specification and the appended claims, unless the content clearly indicates otherwise, the singular forms "a or an", "a or an" and "the" may include plural objects. In addition, all units, prefixes and symbols may be expressed in their SI accepted forms.
[0054] The numerical ranges listed in the specification include the numbers that define the ranges, and include each integer within the defined range. Throughout the present disclosure, various aspects of the present invention are presented in range form. It should be understood that the description in range form is only for convenience and brevity, and should not be interpreted as a rigid limitation on the scope of the present invention. Therefore, it should be considered that the description of the range has all possible sub-ranges that are clearly disclosed and the individual numerical values within the range. For example, it should be considered that the description of a range such as 1 to 6 has clearly disclosed sub-ranges, such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and the individual numbers within the range, for example, 1, 2, 3, 4, 5 and 6. This applies regardless of the breadth of the range.
[0055] In order to more easily understand the present invention, first define some terms. Unless otherwise limited, all technical and scientific terms used herein have the same meaning as those of ordinary skill in the art to which the embodiments of the present invention belong. Many methods and materials similar to, modified or equivalent to the methods and materials described herein can be used to practice embodiments of the present invention without excessive experimentation, and preferred materials and methods are described herein. When describing and claiming embodiments of the present invention, the following terms will be used according to the definition given below.
[0056] As used herein, the term "about" refers to variations in quantity that may occur, for example, through typical measurements and liquid handling procedures used in real life to prepare concentrates or use solutions; through inadvertent errors in these procedures; through differences in the manufacture, source, or purity of ingredients used to prepare the composition or perform the method; and the like. The term "about" also encompasses differences in quantity due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether or not modified by the term "about," the claims include equivalents to the quantities.
[0057] The terms "active" or "active percent" or "active weight percent" or "active concentration" are used interchangeably herein and refer to the concentration of those ingredients that participate in cleaning, expressed as a percentage after deducting inert ingredients such as water or salt.
[0058] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, including 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 "carbocyclyl") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched 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).
[0059] Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl." As used herein, the term "substituted alkyl" refers to alkyl groups in which substituents replace one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halide, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxy, phosphate, phosphonate, phosphinate, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), amide (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl or aromatic (including heteroaromatic) groups.
[0060] As used herein, the term "cleaning" refers to a method for promoting or assisting decontamination, bleaching, reduction of microbial populations, and any combination thereof. As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colony) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, prions, mimiviruses, viruses, bacteriophages, and some algae. As used herein, the term "microorganism (microbe)" is synonymous with microorganism (microorganism).
[0061] For the 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 by water washing. Greater microbial population reduction provides a higher level of protection.
[0062] As used herein, the term "sterilizer" refers to an agent that kills all vegetative cells of pathogenic microorganisms including most of the identified ones, and is used in the procedures described in "AOAC Use Dilution Methods", the official analytical method of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, the 15th edition, 1990 (EPA Guide 91-2). As used herein, the term "high-level sterilization" or "high-level sterilizer" refers to a compound or composition that kills substantially all organisms except high-level bacterial spores and is achieved by a chemical sterilizer that is clearly sold as a sterilant by the Food and Drug Administration. As used herein, the term "intermediate level sterilization" or "intermediate level sterilizer" refers to a compound or composition that kills mycobacteria, most viruses and bacteria with a chemical sterilizer registered as a tuberculosis-killing agent by the Environmental Protection Agency (EPA). As used herein, the term "low-level germicidal" or "low-level germicide" refers to a compound or composition that kills some viruses and bacteria with a chemical germicide registered by the EPA as a hospital disinfectant.
[0063] As used herein, the phrase "food processing surface" refers to the surface of a tool, machine, equipment, structure, building, etc., that is used as part of a food processing, preparation, or storage activity. Examples of food processing surfaces include surfaces of food processing or preparation equipment (e.g., slicing, canning, or transport equipment, including sinks), food processing utensils (e.g., utensils, cutlery, washing utensils, and bar glasses), and floors, walls, or fixtures of structures where food processing is performed. Food processing surfaces are found and employed in food anti-spoilage air circulation systems, aseptic packaging sanitizers, food refrigeration and cooler cleaners and sanitizers, warewashing sanitizers, blancher cleaning and sanitizers, food packaging materials, cutting board additives, third sink sanitizers, beverage coolers and warmers, meat cooling or blanching water, buffet tray sanitizers, sanitizing gels, cooling towers, food processing antimicrobial clothing sprays, and non-aqueous to low-aqueous food preparation lubricants, oils, and rinse additives.
[0064] As used herein, the phrase "food" includes any food substance that may need to be treated with an antimicrobial agent or composition and can be eaten with or without further preparation. Food includes meat (e.g., red meat and pork), seafood, poultry, agricultural products (e.g., fruits and vegetables), eggs, live eggs, egg products, ready-to-eat foods, wheat, seeds, roots, tubers, leaves, stems, grains, flowers, sprouts, seasonings, or combinations thereof. The term "agricultural products" refers to foods, such as fruits and vegetables, and plants or plant-derived materials that are usually sold in an uncooked manner, and are usually not packaged, and can sometimes be eaten raw.
[0065] As used herein, the phrase "health care surface" refers to the surface of an instrument, device, cart, cover, furniture, structure, building, etc. used as part of a health care activity. Examples of health care surfaces include medical or dental instruments, medical or dental devices, electronic devices for monitoring patient health, and surfaces of floors, walls, or structural fixtures in which health care is performed. Health care surfaces are found in hospitals, surgeries, illnesses, delivery, morgues, and clinical diagnostic rooms. These surfaces can be those having the following characteristics: "hard surfaces" (such as walls, floors, bed boards, etc.); or fabric surfaces, such as woven, woven, and nonwoven surfaces (such as surgical gowns, drapes, bedding, bandages, etc.); or patient care equipment (such as respirators, diagnostic equipment, shunts, human specula, wheelchairs, beds, etc.); or surgical and diagnostic equipment. Health care surfaces include articles and surfaces used for animal health care.
[0066] As used herein, the term "instrument" refers to various medical or dental instruments or devices that may benefit from cleaning with a composition according to the present invention.
[0067] As used herein, the phrases "medical instrument," "dental instrument," "medical device," "dental device," "medical equipment," "dental equipment" refer to instruments, devices, tools, appliances, implements, and equipment used in medicine or dentistry. Such instruments, devices, and equipment may be cold sterilized, immersed or washed and then heat sterilized, or otherwise benefit from cleaning in the compositions of the present invention. These various instruments, devices and equipment include, but are not limited to, diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g., bone saws and their blades), hemostats, knives, chisels, bone forceps, folders, pliers, drills, drill bits, rasps, burrs, applicators, crushers, elevators, clamps, needle holders, racks, clips, hooks, chisels, curettes, retractors, levelers, punches, extractors, spoons, keratomes, scrapers, presses, trocars, dilators, covers, glassware, tubes, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes and arthroscopes) and related equipment, the like, or any combination thereof.
[0068] As used herein, the term "microbe" is synonymous with microorganism. For the purpose of this patent application, successful microbial reduction is achieved when the microbial population is reduced by at least about 50% or significantly reduced more than by water washing. More microbial population reduction provides a higher level of protection. The distinction between the "killing" or "inhibiting" activity of antimicrobial, the definition describing the degree of efficacy, and the official laboratory protocol for measuring the efficacy are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can achieve two categories of microbial cell damage. The first is a fatal, irreversible effect that produces complete microbial cell destruction or incapacity. The second type of cell damage is reversible, so that if the organism does not contain an agent, it can reproduce again. The former is called bactericidal, and the latter is called antibacterial. According to definition, disinfectants and bactericides are agents that provide antimicrobial or microbicidal activity. In contrast, preservatives are generally described as inhibitors or antibacterial compositions.
[0069] As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colonies) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, prions, mimiviruses, viruses, bacteriophages, and some algae.
[0070] As used herein, the term "disinfectant" refers to an agent that reduces the number of bacterial contaminants to a safe level judged according to public health requirements. In one embodiment, the disinfectant used in the present invention will provide at least 99.999% reduction (5-log magnitude reduction). These reductions can be evaluated using the procedures described in "Bactericidal and Laundering Disinfection of Disinfectants", Official Analytical Methods of the Official Analytical Chemists Association, paragraph 960.09 and applicable chapters, 15th edition, 1990 (EPA Guide 91-2). According to this reference, the disinfectant should provide a 99.999% reduction (5-log magnitude reduction) in 30 seconds for several test organisms at room temperature 25±2°C. According to an embodiment of the present invention, the disinfectant rinse provides a 99.999% reduction (5-log magnitude reduction) in the desired organisms (including bacterial contaminants) at the use temperature. The distinction between the "killing" or "inhibiting" activity of antimicrobial agents, the definition describing the degree of efficacy, and the official laboratory protocol for measuring the efficacy are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can achieve two categories of microbial cell damage. The first is a lethal, irreversible effect that produces complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, such that the organism can reproduce again if it is free of the agent. The former is called bactericidal and the latter is called bacteriostatic. By definition, disinfectants and bactericides are agents that provide antimicrobial or microbicidal activity. In contrast, antiseptics are often described as inhibitory or bacteriostatic compositions.
[0071] As used herein, the term "substantially free" refers to a composition that is completely lacking the component or has such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or as a 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.
[0072] As used herein, the term "surfactant" is a compound containing a lipophilic segment and a hydrophilic segment, which, when added to water or a solvent, reduces the surface tension of the system.
[0073] As used herein, the term "ware" refers to items such as dining and cooking utensils, dishes and other hard surfaces, such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles and floors. As used herein, the term "warewashing" refers to washing, cleaning or rinsing utensils. Utensils also refer to items made of plastic. The types of plastics that can be cleaned according to the composition of the present invention include, but are not limited to, those plastics including 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).
[0074] As used herein, the term "water" includes food processing or transport water. Food processing or transport water includes production transport water (e.g., as found in aqueducts, pipe transport, cutters, slicers, blanchers, distillation systems, washers, etc.), belt sprays for food transport lines, drip trays for shoe and hand washing, third sink rinse water, etc. Water also includes domestic and recreational water, such as swimming pools, spas, leisure flumes and water slides, fountains, etc.
[0075] As used herein, the terms "weight percent," "wt-%," "percent by weight," "% by weight," and variations thereof refer to the concentration of a substance divided by the total weight of the composition and multiplied by 100. It should be understood that "percent," "%," and the like, as used herein, are intended to be synonymous with "weight percent," "weight %," and the like.
[0076] As used herein, the term "water-soluble" refers to a composition or component if it is at least 90% soluble in water, at least 95% soluble in water, at least 98% soluble in water, at least 99% soluble in water, or at least 99.9% soluble in water.
[0077] The methods and compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention and other ingredients described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or ingredients, but only if the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
[0078] Activated antimicrobial composition
[0079] According to the present invention, the antimicrobial composition of at least one quaternary ammonium compound and at least one anionic surfactant provides an improved antimicrobial activity than any component used alone. In some respects, the antimicrobial composition according to the present invention beneficially provides a synergistic surface activity (reduced dynamic surface tension) and is cost effective. It has been further found that the combination of synergistic antimicrobial and / or disinfecting efficacy is also used to reduce the unpleasant odor of some anionic surfactants (e.g., C6-C10 carboxylated surfactants) (e.g., fatty acids), thereby providing the additional benefits of the present composition.
[0080] In one aspect, the antimicrobial composition according to the present invention comprises, consists of and / or consists essentially of a quaternary ammonium compound and an anionic surfactant and / or an anionic acid. In another aspect, the antimicrobial composition according to the present invention comprises, consists of and / or consists essentially of a quaternary ammonium compound with a C20 or less chain length per R group, and an anionic surfactant with a C10 or less chain length for a straight or branched carboxylate. In one aspect, the carboxylate may be alkoxylated or unalkoxylated. In another aspect, the antimicrobial composition according to the present invention comprises, consists of and / or consists essentially of a quaternary ammonium compound with a C20 or less chain length per R group, and an anionic surfactant with a C13 or less chain length for an alkoxylated anionic straight or branched carboxylate.
[0081] Antimicrobial compositions according to the present invention overcome the insufficient surface activity of quaternary ammonium compounds, while providing effective antimicrobial and / or disinfecting capabilities. The composition of quaternary ammonium compounds and anionic surfactants has greater surface activity and effectiveness under synergy, which advantageously provides improved performance under stress conditions. In some respects, antimicrobial compositions are effective at neutral and / or alkaline pH (contrary to the lower pH range of about 1-5 required for the EPA standard used in the water hardness suspension test). Advantageously, due to the synergy of the composition and the improved wettability, the selection of anionic surfactants and quaternary ammonium compounds activates (i.e. causes synergy) quaternary ammonium compounds to provide required surface activity, including antimicrobial and / or disinfecting activity. In one aspect, and not limited to specific mechanism of action, anionic surfactants with C10 or less chain length provide activation suitable for providing antimicrobial compositions according to the present invention. This combination of quaternary ammonium compounds and anionic surfactants with required anionic head groups and chain lengths is a non-oxidative method for enhancing the surface activity and antimicrobial efficacy of quaternary ammonium compound complexes in an unexpected manner. Additionally, the provided antimicrobial compositions have enhanced mildness and reduced irritation due to neutralization or partial neutralization, and result in reduced residue on substrate surfaces.
[0082] According to some embodiments, the antimicrobial composition according to the present invention provides the surface activation and synergistic effect of the quaternary ammonium compound of molar ratio dependence. In one aspect, the composition includes about one mole: molar ratio of quaternary ammonium compound and anionic surfactant. In other aspects, the composition includes at most about 10 to about 1 molar ratio of quaternary ammonium compound and anionic surfactant. In other aspects, the composition includes at most about 1 to about 10 molar ratios of quaternary ammonium compound and anionic surfactant, or any combination thereof. In another embodiment, the molar ratio of the anionic surfactant of the antimicrobial composition to the quaternary ammonium is about 1 mole of anionic surfactant to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of the anionic surfactant of the antimicrobial composition to the quaternary ammonium compound is about 1.5 moles of anionic surfactant to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of the anionic surfactant of the antimicrobial composition to the quaternary ammonium compound is about 1 mole of anionic surfactant to about 10 moles of quaternary ammonium compound. In another embodiment, the molar ratio of the anionic surfactant of the antimicrobial composition to the quaternary ammonium compound is about 2 moles of anionic surfactant to about 1 mole of quaternary ammonium compound.
[0083] Inactivation of antimicrobial compositions (inactivation of antimicrobial QACs)
[0084] It is further found that the antimicrobial compositions described herein can be modified to preferentially select at least one quaternary ammonium compound and at least one anionic surfactant to provide an inactivated composition. According to the present invention, some anionic surfactants help reduce the antimicrobial activity of quaternary ammonium compounds. In one aspect, sulfated and sulfonated anionic surfactants inactivate the antimicrobial activity of quaternary ammonium compounds. It is believed that anionic surfactants with stronger ionic charges are used to inactivate the antimicrobial efficacy of quaternary ammonium compounds, while anionic surfactants with weaker ionic charges are used to enhance or activate the antimicrobial efficacy of quaternary ammonium compounds.
[0085] In one aspect, the inactivated antimicrobial composition according to the invention comprises, consists of and / or consists essentially of: a quaternary ammonium compound and an anionic surfactant. In another aspect, the inactivated antimicrobial composition according to the invention comprises, consists of and / or consists essentially of: a quaternary ammonium compound having a chain length of C20 or less for each R group, and a sulfate or sulfonate anionic surfactant having an alkyl chain greater than C10 for linear or branched chains.
[0086] The antimicrobial composition of deactivation according to the present invention is expected to provide reduced surface activity of quaternary ammonium compounds for specific use applications. Without being bound by theory, the present invention proves that the complex or ion pair between the quaternary ammonium salt and the anionic surfactant effectively reduces the hydrophilic cross-sectional area of the two surfactants due to charge neutralization, making the accumulation in the interface very favorable. The formation of the complex is so favorable that it can overcome the cohesive force between the fatty acid molecules. According to one aspect of the present invention, the stronger ionic charge with some anionic surfactants (such as sulfate or sulfonate anionic surfactants) effectively neutralizes (or partially neutralizes the quaternary ammonium ion charge) or deactivates the antimicrobial quaternary ammonium compound.
[0087] According to some embodiments, the inactivated antimicrobial composition according to the present invention provides a surface activation of a quaternary ammonium compound with a reduced molar ratio dependency. In one aspect, the composition includes about one mole: molar ratio of a quaternary ammonium compound and an anionic surfactant. In other aspects, the composition includes a quaternary ammonium compound and an anionic surfactant at a molar ratio of up to about 10 to about 1. In other aspects, the composition includes a quaternary ammonium compound and an anionic surfactant at a molar ratio of up to about 1 to about 10. In another embodiment, the molar ratio of the anionic surfactant to the quaternary ammonium of the inactivated antimicrobial composition is about 1 mole of anionic surfactant to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of the anionic surfactant to the quaternary ammonium of the inactivated antimicrobial composition is about 1.5 moles of anionic surfactant to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of the anionic surfactant to the quaternary ammonium compound of the inactivated antimicrobial composition is about 1 mole of anionic surfactant to about 10 moles of quaternary ammonium compound. In another embodiment, the molar ratio of the anionic surfactant to the quaternary ammonium compound of the inactivated antimicrobial composition is about 2 moles of anionic surfactant to about 1 mole of quaternary ammonium compound.
[0088] Exemplary Embodiments
[0089] Exemplary ranges of activated or inactivated antimicrobial compositions according to the present invention in the concentrated liquid compositions are each shown in Table 1 in weight percent.
[0090] Table 1
[0091]
[0092] According to the present invention, the concentrated antimicrobial compositions and / or inactivated antimicrobial compositions listed in Table 1 have any suitable pH for use applications, including from about 1 to about 12. However, according to aspects of the present invention, the diluted use solutions may have an acidic or neutral to alkaline pH, depending on their specific use applications, including from about 1 to about 12.
[0093] In some aspects, applications such as use solutions of antimicrobial compositions and / or inactivated antimicrobial compositions may have a pH of about 1 to about 12. In other aspects, the compositions of the present invention have a pH between about 1 and about 7. In other aspects, the compositions of the present invention have a pH between about 1 and about 5.5. In other aspects, the compositions of the present invention have a pH between about 1 and about 4. In another embodiment, the pH of the composition is between about 2 and about 7, between about 3 and about 7, between about 4 and about 7, between about 5 and about 7, between about 6 and about 7. In another embodiment, the pH of the composition is between about 1 and about 6, between about 1 and about 5, between about 1 and about 4, between about 1 and about 3, between about 1 and about 2. In other embodiments, the pH of the composition is between about 2 and about 6, between about 3 and about 6, between about 4 and about 6, between about 5 and about 6. In other embodiments, the pH of the composition is between about 1 and about 5, between about 2 and about 5, between about 3 and about 5, between about 4 and about 5. In other embodiments, the pH of the composition is between about 1 and about 4, between about 2 and about 4, between about 3 and about 4. Without limiting the scope of the invention, numerical ranges are inclusive of the numbers defining the range and include each integer within the defined range.
[0094] Quaternary ammonium compounds
[0095] The antimicrobial compositions and inactivated antimicrobial compositions according to the present invention include at least one quaternary ammonium compound. It is known that certain quaternary ammonium compounds have antimicrobial activity. Therefore, various quaternary ammonium compounds with antimicrobial activity can be used in the compositions of the present invention. In one aspect, the quaternary ammonium compound is an antimicrobial "quaternary ammonium salt". The term "quaternary ammonium compound" or "quaternary ammonium salt" generally refers to any composition having the formula:
[0096]
[0097] Wherein R1-R4 is substituted or unsubstituted, saturated or unsaturated, branched or unbranched and cyclic or acyclic alkyl which may be the same or different, and may contain ether, ester or amide bonds; they may be aromatic or substituted aromatic groups. In one aspect, the groups R1, R2, R3 and R4 each have a chain length of less than C20. X- is an anionic counterion. The term "anionic counterion" includes any ion that can form a salt with a quaternary ammonium. Examples of suitable counterions include halides such as chloride and bromide, propionate, methylsulfate, sugar acid, ethylsulfate, hydroxide, acetate, phosphate, carbonate (such as commercially available from Lonza as Carboquat H) and nitrate. Preferably, the anionic counterion is chloride.
[0098] The composition of the present invention provides a quaternary ammonium compound combined with anionic surfactants. In certain embodiments, the quaternary ammonium with a carbon chain less than 20 is included in the composition of the present invention. Examples of quaternary ammonium compounds suitable for the present invention include but are not limited to alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride and didecyl dimethyl ammonium chloride etc. Single quaternary ammonium or a combination of more than one quaternary ammonium may be included in the composition of the present invention. Other examples of quaternary ammonium compounds suitable for the present invention include but are not limited to benzethonium chloride, ethyl benzethonium chloride, myristyl trimethyl ammonium chloride, methyl benzethonium chloride, cethamonium chloride, cetrimonium bromide (CTAB), carnitine, dofadumium chloride, tetraethyl ammonium bromide (TEAB), domiphene, benzododecyl bromide, benzozonium chloride, choline, cocamidopropyl betaine (CAPB) and denatonium.
[0099] In certain embodiments, the quaternary ammonium with a carbon chain less than 20 or C2-C20 is included in the composition of the present invention. In other embodiments, the quaternary ammonium with C6-C18, C12-C18, C12-C16 and C6-C10 carbon chains is included in the composition of the present invention. Examples of quaternary ammonium compounds suitable for the present invention include but are not limited to alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride and didecyl dimethyl ammonium chloride, etc. Single quaternary ammonium or a combination of more than one quaternary ammonium may be included in the composition of the present invention. Other examples of quaternary ammonium compounds suitable for the present invention include but are not limited to benzethonium chloride, ethyl benzyl ammonium chloride, myristyl trimethyl ammonium chloride, methyl benzethonium chloride, cethamonium chloride, cetrimonium bromide (CTAB), carnitine, dofamonium chloride, tetraethyl ammonium bromide (TEAB), domiphene, benzododecyl bromide, benzozonium chloride, choline, cocamidopropyl betaine (CAPB), denatonium and mixtures thereof. In one aspect, combinations of quaternary ammonium compounds are particularly preferred for use in the compositions of the present invention, for example the commercially available product Bardac 205 / 208M.
[0100] 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; diquaternary ammonium salts; and polymeric quaternary ammonium salts. Each category will be discussed herein.
[0101] 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 hexadecyltrimethylammonium bromide, commercially available under the trade names Rhodaquat M242C / 29 and Dehyquart A; alkyltrimethylammonium chloride, commercially available under Arquad 16; alkylaryltrimethylammonium chloride; and hexadecyldimethylethylammonium bromide, commercially available under Ammonyx DME.
[0102] Monoalkyldimethylbenzylammonium salts contain one R group as a long chain alkyl group, a second R group as a benzyl group, and the remaining two R groups are short chain alkyl groups, such as methyl or ethyl. Monoalkyldimethylbenzylammonium salts are generally compatible with nonionic surfactants, detergent builders, fragrances, and other ingredients. Some non-limiting examples of monoalkyldimethylbenzylammonium salts include alkyldimethylbenzylammonium chloride, commercially available from Lonza as Barquat; and benzethonium chloride, commercially available from Lonza as Lonzagard. In addition, monoalkyldimethylbenzylammonium salts may be substituted. Non-limiting examples of such salts include dodecyldimethyl-3,4-dichlorobenzylammonium chloride. Finally, there is a mixture of alkyldimethylbenzyl and alkyldimethyl-substituted benzyl (ethylbenzyl) ammonium chloride, commercially available from Stepan Company as BTC2125M, and commercially available from Lonza as Barquat 4250.
[0103] Dialkyldimethylammonium salts contain two R groups that are long chain alkyl groups, and the remaining R groups are short chain alkyl groups, such as methyl groups. Some non-limiting examples of dialkyldimethylammonium salts include didecyldimethylammonium halide, commercially available from Lonza as Bardac 22; didecyldimethylammonium chloride, commercially available from Lonza as Bardac 2250; dioctyldimethylammonium chloride, commercially available from Lonza as Bardac LF and Bardac LF-80); and octyldecyldimethylammonium chloride, sold as a mixture with didecyl and dioctyldimethylammonium chloride, commercially available from Lonza as Bardac 2050 and 2080.
[0104] Heteroaromatic ammonium salts contain one R group that is a long chain alkyl group, with the remaining R groups provided by some aromatic system. Thus, the quaternary nitrogen to which the R group is attached is part of an aromatic system, such as pyridine, quinoline, or isoquinoline. Some non-limiting examples of heteroaromatic ammonium salts include hexadecylpyridinium halides, commercially available from Zeeland Chemical Inc. as Sumquat 6060 / CPC; 1-[3-chloroalkyl]-3,5,7-triaza-1-azaadamantane, commercially available from Dow Chemical Company as Dowicil 200; and alkylisoquinoline bromides.
[0105] Polysubstituted quaternary ammonium salts are monoalkyl trimethyl ammonium salts, monoalkyl dimethyl benzyl ammonium salts, dialkyl dimethyl ammonium salts or heteroaromatic ammonium salts, wherein the anion portion of the molecule is a large high molecular weight (MW) organic ion. Some non-limiting examples of polysubstituted quaternary ammonium salts include alkyl dimethyl benzyl ammonium sulphonate and dimethyl ethyl benzyl cyclohexyl ammonium sulfamate.
[0106] The diquaternary ammonium salt contains two symmetrical quaternary ammonium parts and has the following general formula:
[0107]
[0108] Wherein the R group can be a long chain or short chain alkyl, benzyl or provided by an aromatic system. Z is a carbon-hydrogen chain connected to each quaternary nitrogen. Some non-limiting examples of diquaternary ammonium salts include 1,10-bis(2-methyl-4-aminoquinoline chloride)-decane; and 1,6-bis[1-methyl-3-(2,2,6-trimethylcyclohexyl)-propyldimethylammonium chloride]hexane or tropiquatium chloride.
[0109] In one aspect, the quaternary ammonium compound is a medium to long chain alkyl R group, such as 8 carbons to about 20 carbons, 8 carbons to about 18 carbons, about 10 to about 18 carbons, and about 12 to about 16 carbons, and provides solubility and good antimicrobial agents.
[0110] In one aspect, the quaternary ammonium compound is a short dialkyl chain quaternary ammonium compound having R groups such as 2 carbons to about 12 carbons, 3 carbons to about 12 carbons, or 6 carbons to about 12 carbons.
[0111] In a preferred aspect, the quaternary ammonium compound is an alkylbenzyl ammonium chloride, a dialkylbenzyl ammonium chloride, a blend of an alkylbenzyl ammonium chloride and a dialkylbenzyl ammonium chloride, a didecyldimethylammonium chloride, a dioctyldimethylammonium chloride, a blend of didecyldimethylammonium chloride and dioctyldimethylammonium chloride, or a mixture thereof. In a preferred embodiment, the quaternary ammonium compound used in the antimicrobial composition of the present invention is composed of a mixture of dialkyl quaternary ammonium and alkylbenzyl quaternary ammonium.
[0112] In some embodiments, the quaternary ammonium compound is silane-free. In a preferred embodiment, an antimicrobial composition is provided that includes a silane-free quaternary ammonium compound having a chain length of less than C-20.
[0113] In a preferred embodiment, the quaternary ammonium compound can be selected based on its consideration or classification as a food additive. For example, the quaternary ammonium compound can include benzalkonium chloride and is therefore suitable for use in a sanitizing rinse for contact with food.
[0114] According to the embodiment of the present invention that antimicrobial composition is provided, the combination of quaternary ammonium compound and anionic surfactant of effective amount is provided, to provide the synergistic antimicrobial efficacy for wide spectrum microorganism (comprising Gram-negative microorganism, such as Escherichia coli).In this use solution, the suitable concentration of quaternary ammonium compound comprises at least about 10ppm, at least about 50ppm, or at least about 100ppm, or at least about 150ppm, or at least about 200ppm, or at least about 250ppm, or at least about 300ppm, or about 100-500ppm, or about 100-300ppm, or any scope therein.In some respects, for any antimicrobial efficacy under the concentration lower than about 150ppm or lower than about 100ppm, according to the synergistic effect of anionic surfactant and / or acid combination, the quaternary ammonium compound more than 150ppm is usually required according to the activated microbial composition of the present invention for Gram-negative effectiveness.Advantageously, the low activity of quaternary ammonium compound is the result of the beneficial synergistic effect with anionic surfactant.Not limited by the present invention, all enumerated scopes include the numeral limiting the scope and include each integer in the defined range.
[0115] According to embodiments of the present invention providing an inactivated antimicrobial composition, an effective amount of a quaternary ammonium compound in combination with an anionic surfactant is provided to provide an inactivated quaternary ammonium composition, such as one that may not wish to affect the antimicrobial efficacy of the treated system. Suitable concentrations of the quaternary ammonium compound in such a use solution include at least about 0.0001 ppm, at least about 0.001 ppm, or at least about 0.01 ppm, or any range therein, or any suitable molar concentration of the inactivating anion and the quaternary ammonium compound for a particular use application. Without limitation of the present invention, all recited ranges include the numbers defining the ranges and include each integer within the defined range.
[0116] For antimicrobial compositions and inactivated antimicrobial compositions, other suitable concentrations of quaternary ammonium compounds in use solutions include between about 1 ppm and about 10,000 ppm, between about 1 ppm and about 1,000 ppm, between 5 ppm and about 400 ppm, between 10 ppm and about 400 ppm, between 20 ppm and about 400 ppm, between 25 ppm and about 400 ppm, between 50 ppm and about 400 ppm, between 75 ppm and about 400 ppm, or between 100 ppm and about 400 ppm. Without limitation of the present invention, all recited ranges include the numbers defining the ranges and include each integer within the defined ranges.
[0117] According to an embodiment of the present invention, the quaternary ammonium compound can be provided in the concentrated composition in an amount between: about 0.001 wt %-75 wt %, about 0.1 wt %-75 wt %, about 0.01 wt %-75 wt %, about 1 wt %-75 wt %, about 1 wt %-50 wt %, about 1 wt %-30 wt %, about 5 wt %-30 wt %. In addition, without limitation of the present invention, all recited ranges include the numbers defining the ranges and include each integer within the defined ranges.
[0118] Anionic surfactants
[0119] The antimicrobial composition according to the present invention and / or the inactivated antimicrobial composition comprises at least one anionic surfactant. In other aspects, the antimicrobial composition according to the present invention and / or the inactivated antimicrobial composition comprises at least two anionic surfactants. Anionic surfactants are classified as: anionic surfactants, because the charge of the hydrophobe is negative; or the hydrophobic part of the molecule is uncharged unless the pH is raised to pKa or neutral or higher surfactants (e.g., carboxylic acids). Carboxylate, sulfonate, sulfate and phosphate are polar (hydrophilic) solubilizing groups found in anionic surfactants.
[0120] In one aspect, the anionic surfactant is straight or branched. In one aspect, the straight or branched anionic surfactant is a medium chain surfactant with 6-20 carbon chain length, or 6-18 carbon chain length, preferably 6-12 carbon chain length, and more preferably 6-10 carbon length. In one aspect, the straight or branched medium chain anionic surfactant is alkoxylated. In one aspect, the straight or branched anionic surfactant is an alkoxylated medium chain surfactant with 6-18 carbon chain length, preferably 6-13 carbon chain length, and more preferably 6-10 carbon. In one aspect, the anionic surfactant is a carboxylate. In an alternative aspect, the anionic surfactant is a weak acid anionic surfactant, such as a phosphate. In another alternative aspect, the anionic surfactant is a sulfonate and / or sulfate. In another aspect, the anionic surfactant used in combination with a quaternary ammonium is alkoxylated or unalkoxylated, and can be a primary straight or branched carboxylate.
[0121] In one aspect, anionic surfactants suitable for use in the present composition to activate the synergistic effect of quaternary ammonium compounds and enhanced surface activity include carboxylates. Anionic carboxylate surfactants suitable for use in the present composition include carboxylic acids (and salts) such as alkanoic acid (and alkanoate), carboxylates (e.g., alkyl succinate), carboxylic acid ethers, sulfonated fatty acids, such as sulfonated oleic acid and other suitable carboxylic acids include, for example, capric acid, octanoic acid, nonanoic acid, ethylhexyl acid and isononanoic acid. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylates surfactants and soaps (e.g., alkyl carboxylates). Secondary carboxylates suitable for use in the present composition include those containing carboxyl units connected to secondary carbons. Secondary carbons may be in a ring structure, such as in p-octylbenzoic acid, or in alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants generally do not contain ether bonds, do not contain ester bonds and do not contain hydroxyl groups. In addition, they generally do not have nitrogen atoms in the head group (amphiphilic part). Suitable secondary soap surfactants typically contain a total of 11-13 carbon atoms, but more carbon atoms may be present (e.g., up to 16). Suitable carboxylates also include acylamino acids (and salts), such as acyl glutamates, acyl peptides, sarcosinates (e.g., N-acyl sarcosinates), tartrates (e.g., N-acyl tartrates and fatty acid amides of methyltaurine), and the like.
[0122] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: RO-(CH2CH2O) n (CH2) m -CO2X, wherein R is a C8-C22 alkyl group or
[0123]
[0124] Wherein R1 is C4-C16 alkyl; 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 C8-C16 alkyl. In some embodiments, R is C12-C14 alkyl, n is 4, and m is 1.
[0125] Such alkyl and alkaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are usually purchased as the acid form which can be readily converted to the anion or salt form.
[0126] In one aspect, carboxylate-based anionic surfactants provide improved antimicrobial activity over any component used alone. Examples of preferred activated anionic surfactants include carboxylates with C6-C10 carbon chains. Examples of anionic carboxylate surfactants include organic acids such as caproic acid, heptanoic acid, caprylic acid, nonanoic acid and capric acid. Examples of branched organic acids include ethylhexyl carboxylate and tridecyl carboxylate. Examples of commercially available surfactants include Marlowet 4539 (C9-alcohol polyglycol ether carboxylic acid purchased from Sasol), Emulsogen CNO (C8-alcohol 8 mole polyglycol ether carboxylic acid purchased from Clariant) and Emulsogen DTC (C13-alcohol 7 mole polyglycol ether carboxylic acid purchased from Clariant) etc.
[0127] In one aspect, anionic surfactants suitable for use in the compositions of the present invention to activate the microbial synergy and enhanced surface activity (as measured by reduction in dynamic surface tension) of the quaternary ammonium compounds further comprise phosphate esters.
[0128] In one aspect, anionic surfactants suitable for use in the compositions of the present invention to inactivate or reduce the surface activity of quaternary ammonium compounds include sulfonates and / or sulfates. In one aspect, anionic surfactants suitable for use in the compositions of the present invention include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C5-C17 acyl-N--(C1-C4 alkyl) and--N--(C1-C2 hydroxyalkyl) reduced glucosamine sulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides, etc. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 ethylene oxide groups per molecule). Anionic sulfonate surfactants suitable for use in the compositions of the present invention also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates and aromatic sulfonates which may or may not have substitution groups.
[0129] In one aspect, sulfated and sulfonated anionic surfactants provide reduced or inactivated surface activity of quaternary ammonium compounds. Sulfated and sulfonated anionic surfactants have stronger ionic bonds for inactivating the antimicrobial efficacy of quaternary ammonium compounds, while anionic surfactants with weaker ionic bonds are used to enhance or activate the antimicrobial efficacy of quaternary ammonium compounds. Examples of commercially available sulfated or sulfonated anionic surfactants include X-AES (available from Huntsman's C 12-14 -(PO) 16 -(EO)2-sulfate), SLS (sodium lauryl sulfate), SLES (sodium lauryl ether sulfate), LAS (linear alkyl benzyl sulfonate) and AOS (alpha-olefin sulfonate).
[0130] As described herein according to the present invention, the ability of a combination of a quaternary ammonium compound and an anionic surfactant to enhance or inactivate antimicrobial efficacy can be predicted based on their surface activity. That is, if the combination has a high surface activity compared to another combination (which indicates that the quaternary ammonium compound is water-soluble and therefore can be used for surface activity and antimicrobial action), the combination with the highest surface activity enhances the antimicrobial efficacy of the quaternary ammonium. Conversely, if the combination has a lower surface activity compared to another combination, the combination with a low surface activity neutralizes or inactivates the antimicrobial efficacy of the quaternary ammonium.
[0131] In one aspect of the invention, the antimicrobial efficacy of the composition can be dialed up or down, depending on the anionic surfactant used.According to the present invention, a method of modulating the antimicrobial activity of a quaternary ammonium compound is provided.
[0132] According to embodiments of the present invention providing antimicrobial compositions, an effective amount of anionic surfactants and quaternary ammonium compounds are provided to provide synergistic antimicrobial efficacy. Suitable concentrations of anionic surfactants in use solutions are included between about 1ppm and about 5,000ppm, between about 15ppm and about 2,500ppm, between about 1ppm and about 1,000ppm, between about 1ppm and about 100ppm, between about 1ppm and about 50ppm, or between about 1ppm and about 5ppm. Without limitation of the present invention, all enumerated ranges include the numerals limiting the range and include each integer in the defined range.
[0133] According to other embodiments of the present invention providing an inactivated antimicrobial composition, an effective amount of anionic surfactant is provided in combination with a quaternary ammonium compound to inactivate or reduce the antimicrobial efficacy of the quaternary ammonium compound. Suitable concentrations of anionic surfactants in the use solution include between about 1 ppm and about 5,000 ppm, between about 15 ppm and about 2,500 ppm, between about 1 ppm and about 1,000 ppm, between about 1 ppm and about 100 ppm, between about 1 ppm and about 50 ppm, or between about 1 ppm and about 25 ppm.
[0134] According to embodiments of the present invention, anionic surfactant can be provided in the concentrated composition in an amount between: about 0.0001 wt %-50 wt %, about 0.001 wt %-50 wt %, about 0.01 wt %-50 wt %, about 0.1 wt %-50 wt %, about 0.1 wt %-30 wt %, about 1 wt %-30 wt %, about 0.1 wt %-20 wt %, or about 1 wt %-20 wt %. In addition, without limitation of the present invention, all enumerated ranges include the numerals defining the ranges and include each integer within the defined ranges. As those skilled in the art will determine from the disclosure of the present invention, the concentration of anionic surfactant and / or acid combined with quaternary ammonium compound will vary according to the type of anionic surfactant (e.g., selected for activation and deactivation), quaternary ammonium compound concentration (molar ratio) and additional components in the composition solution.
[0135] Anionic polymers and / or chelating agents
[0136] In some embodiments, the composition according to the present invention includes at least one anionic polymer or chelating agent in combination with a quaternary ammonium compound to provide a surface-active complex. In other aspects, the composition according to the present invention includes at least two anionic polymers, or anionic polymers and anionic surfactants. In other aspects, the composition according to the present invention includes at least two anionic chelating agents, or anionic polymers and anionic chelating agents, or anionic chelating agents and anionic surfactants. Anionic polymers and chelating agents are classified as: anionic surfactants, because the charge of the hydrophobic substance is negative; or surfactants (such as carboxylic acids) in which the hydrophobic part of the molecule is uncharged unless the pH is raised to neutral or higher. Carboxylates, sulfonates, sulfates, and phosphates are polar (hydrophilic) solubilizing groups found in anionic compounds. Sodium, lithium, and potassium in the cations (counterions) associated with these polar groups give water solubility; ammonium and substituted ammonium ions provide water and oil solubility; and calcium, barium, and magnesium promote oil solubility.
[0137] It has further been found according to the present invention that phosphate esters serve to enhance the surface activity and antimicrobial activity of quaternary ammonium compounds and are therefore suitable for use in activated compositions. In one aspect, phosphosuccinate adducts / oligomers (PSOs) are particularly suitable for activated compositions according to the present invention.
[0138] In one aspect, the anionic polymer or chelating agent is straight or branched. In one aspect, the straight or branched anionic surfactant is a medium chain compound having a carbon chain length of 6-18, preferably 6-10, and more preferably 6-9 carbon chain length. In one aspect, the straight or branched medium chain anionic surfactant is alkoxylated or unalkoxylated. In one aspect, the anionic polymer or chelating agent is a carboxylate. In another alternative aspect, the anionic polymer or chelating agent is a sulfonate and / or sulfate.
[0139] In one aspect, anionic polymers or chelating agents suitable for use in the compositions of the present invention include carboxylates. Anionic carboxylates suitable for use in the compositions of the present invention include carboxylates (and salts) such as alkanoic acid (and alkanoates), carboxylates (e.g., alkyl succinates), carboxylic acid ethers, sulfonated fatty acids, such as sulfonated oleic acid, etc. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, and alkyl polyethoxy polycarboxylates. Secondary carboxylates suitable for use in the compositions of the present invention include those containing carboxyl units connected to secondary carbons. Secondary carbons may be in a ring structure, such as in p-octylbenzoic acid, or in alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants generally do not contain ether bonds, ester bonds, and hydroxyls. In addition, they generally do not have nitrogen atoms in the head group (amphiphilic part). Suitable secondary soap surfactants generally contain a total of 11-13 carbon atoms, but may have more carbon atoms (e.g., up to 16). Suitable carboxylates also include acylamino acids (and salts), such as acylglutamates, acyl peptides, sarcosinates (eg, N-acyl sarcosinates), tartrates (eg, N-acyl tartrates and fatty acid amides of methyltaurine), and the like.
[0140] In one aspect, anionic polymers or chelating agents suitable for use in the compositions of the present invention include polycarboxylates. Particularly suitable polycarboxylates include, for example, polyacrylates and acrylamides. Suitable polycarboxylates in addition include, for example, polyacrylic acid, maleic acid / olefin copolymers, acrylic acid / maleic acid copolymers, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymaleic acid, polyfumaric acid, copolymers of acrylic acid and itaconic acid, phosphino polycarboxylates, their acid or salt forms, their mixtures, etc. Suitable commercially available maleic acid homopolymers are Aquatreat AR-801 (maleic acid homopolymers neutralized by low molecular weight parts). In another aspect, hydrolysis or water-soluble salts or partial salts of these polymers or copolymers, such as their respective alkali metals (e.g., sodium or potassium) or ammonium salts, may also be used. The weight average molecular weight of the polymer is from about 4000 to about 12,000. A suitable commercially available polyacrylic acid polymer is Acusol 445N, available from Rohm & Haas LLC. Preferred polymers include polyacrylic acid, partial sodium salts of polyacrylic acid or sodium polyacrylate, having an average molecular weight in the range of 4,000 to 8,000.
[0141] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: RO-(CH2CH2O) n (CH2) m -CO2X, wherein R is a C8-C22 alkyl group or
[0142]
[0143] Where R 1 In some embodiments, R is a C4-C16 alkyl group; n is an integer from 1 to 20; m is an integer from 1 to 3; and X is a counterion such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10 and m is 1. In some embodiments, R is a C8-C16 alkyl group. In some embodiments, R is a C12-C14 alkyl group, n is 4, and m is 1.
[0144] Such alkyl and alkaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are usually purchased as the acid form which can be readily converted to the anion or salt form.
[0145] In one aspect, anionic polymers or chelating agents suitable for use in the compositions of the present invention include sulfonates and / or sulfates. In one aspect, anionic surfactants suitable for use in the compositions of the present invention include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5-C17 acyl-N--(C1-C4 alkyl) and--N--(C1-C2 hydroxyalkyl) reduced glucosamine sulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides, etc. Also included are alkyl sulfates, alkyl poly(ethylene oxide) ether sulfates and aromatic poly(ethylene oxide) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (usually with 1 to 6 ethylene oxide groups per molecule). Anionic sulfonates suitable for use in the compositions of the present invention also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates and aromatic sulfonates with or without substituents.
[0146] In some embodiments, the composition of the present invention includes a combination of one or more anionic chelating agents and quaternary ammonium compounds to provide a surface active complex. Chelating agents include, for example, chelating agents or screening agents. Suitable screening agents preferably include, but are not limited to, metal ions in the screening solution, particularly organic chelating compounds of transition metal ions. Such screening agents include organic amino polyphosphonic acid or organic hydroxy polyphosphonic acid complexing agents (in acid form or in soluble salt form), carboxylic acids (e.g., polymeric polycarboxylates), hydroxycarboxylic acids, aminocarboxylic acids, or heterocyclic carboxylic acids, such as pyridine-2,6-dicarboxylic acids (pyridine dicarboxylic acids).
[0147] Chelating agents may include masking agents such as phosphonic acids or phosphonates. Suitable phosphonic acids and phosphonates include HEDP; ethylenediamine tetrakis methylenephosphonic acid (EDTMP); diethylenetriamine pentakis methylenephosphonic acid (DTPMP); cyclohexane-1,2-tetramethylenephosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylenediamine[tetramethylene-phosphonic acid)]; 2-phosphonobutane-1,2,4-tricarboxylic acid; or salts thereof, such as alkali metal salts, ammonium salts, or alkanoylamine salts, such as monoethanolamine, diethanolamine or tetraethanolamine salts; picolinic acid, dipicolinic acid, or mixtures thereof. In some embodiments, organic phosphonates such as HEDP are included in the compositions of the present invention. Commercially available food additive chelating agents include those sold under the trade names Phosphonates are commercially available, including, for example, 1-hydroxyethylidene-1,1-diphosphonic acid, 2010 from Monsanto Industrial Chemicals Co., St. Louis, Mo.; amino(tri(methylenephosphonic acid)), (N[CH2PO3H2]3), 2000 purchased from Monsanto; ethylenediamine [tetrakis(methylenephosphonic acid)], 2041 was purchased from Monsanto; and 2-phosphonobutane-1,2,4-tricarboxylic acid was purchased as Bayhibit AM from Mobay Chemical Corporation, Inorganic Chemicals Division, Pittsburgh, PA.
[0148] The chelating agent may further be of aminocarboxylic acid type or aminocarboxylic acid salt or derivative. Suitable aminocarboxylic acid type masking agents include acids or alkali metal salts thereof, such as aminoacetates and salts thereof. Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid; hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid (EDTA); N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA); diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diacetic acid, etc.; and mixtures thereof. Various biodegradable aminocarboxylates or their derivatives are suitable for use as chelating agents, including, for example, Trilon Methyl glycine diacetic acid (MGDA) was purchased from BASF.
[0149] An effective amount of anionic polymer or chelating agent is provided in combination with a quaternary ammonium compound to provide synergistic antimicrobial and disinfecting efficacy. Suitable concentrations of anionic polymer or chelating agent in the formulation composition include about 0.01 to about 50 weight %, or about 0.1 to about 50 weight %. Without limitation of the present invention, all enumerated ranges include the numbers defining the ranges and include each integer within the defined range. In certain embodiments of the present invention, anionic polymer or chelating agent may be an acidic compound, and therefore may be suitable for use as an acidulant and polymer or chelating agent of the present invention, such as GLDA and HEDP.
[0150] Suitable concentrations of anionic polymers or chelating agents in the use solution include between about 1 ppm and about 500 ppm, between 5 ppm and about 250 ppm, between 10 ppm and about 100 ppm, between 20 ppm and about 100 ppm, between 25 ppm and about 100 ppm, between 10 ppm and about 50 ppm, between 20 ppm and about 50 ppm, between 25 ppm and about 50 ppm, or between about 50 ppm and about 100 ppm. Without limiting the invention, all recited ranges include the numbers defining the ranges and include each integer within the defined ranges.
[0151] According to an embodiment of the present invention, anionic polymers or chelating agents can be provided in the concentrated composition in an amount between about 0.0001 wt %-50 wt %, about 0.001 wt %-50 wt %, about 0.01 wt %-50 wt %, about 0.1 wt %-50 wt %, about 0.1 wt %-30 wt %, about 1 wt %-30 wt %, about 0.1 wt %-20 wt %, or about 1 wt %-20 wt %. In addition, without limitation of the present invention, all recited ranges include the numbers defining the ranges and include each integer within the defined ranges.
[0152] Additional optional components
[0153] The components of the composition can be further combined with various functional components. In certain embodiments, the composition comprising quaternary ammonium compounds and anionic surfactants constitutes a large amount of the gross weight of the composition, or even substantially all. For example, in some embodiments, few additional functional ingredients are added therein or no additional functional ingredients are added. In other embodiments, additional functional ingredients may be included in the composition. Functional ingredients provide required characteristics and functions to the composition. For the purpose of this application, the term "functional ingredient" is included in the material that provides beneficial properties in a specific application when being dispersed or dissolved in an aqueous use solution. Some specific examples of functional materials are discussed in more detail below, although the specific materials discussed are only given by way of example, other functional ingredients of a wide range can also be used.
[0154] In some embodiments, the composition may include additional functional ingredients, including, for example, additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, stabilizers, such as chelating agents or sequestering agents, corrosion inhibitors, sequestering agents and / or chelating agents, solidifying agents, tableting, pH adjusting components, including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, scents, or fragrances), other cleaning agents, hydrotropes or coupling agents, buffers, etc. In addition, the composition may be used in combination with one or more conventional cleaning agents, such as alkaline detergents.
[0155] According to embodiments of the present invention, various additional functional ingredients can be provided in the composition, and its amount is: about 0 wt %-90 wt %, about 0 wt %-75 wt %, about 0 wt %-50 wt %, about 0.01 wt %-50 wt %, about 0.1 wt %-50 wt %, about 1 wt %-50 wt %, about 1 wt %-30 wt %, about 1 wt %-25 wt %, or about 1 wt %-20 wt %.In addition, not limited by the present invention, all enumerated scopes include the numeral that limits the scope and include each integer in the limited scope.In some preferred embodiments, composition of the present invention does not include some additional functional ingredients.In one aspect, composition does not include halides.In one aspect, composition does not include oxidants.
[0156] Sources of alkalinity and / or acidity
[0157] In some embodiments, the compositions of the present invention include a source of alkalinity and / or an acidulant. In preferred embodiments, the compositions of the present invention include an acidulant. The acidulant is effective to form a concentrate composition or a use solution having a desired acidic to neutral pH. The acidulant is effective to form a use composition having a pH of about 7, about 6 or less, about 5 or less, about 4, about 4 or less, about 3, about 3 or less, about 2, about 2 or less, etc. In some embodiments, an acidulant is included in the composition depending on the anionic surfactant used in the composition. In one embodiment, the acidulant is used in combination with a linear short chain carboxylate (e.g., pH 3-5) and / or in combination with a branched / alkoxylated carboxylate having a wider pH.
[0158] In one embodiment, the acidulant comprises an inorganic acid. Suitable inorganic acids include, but are not limited to, sulfuric acid, sodium bisulfate, phosphoric acid, nitric acid and hydrochloric acid. In certain embodiments, the acidulant comprises an organic acid. Suitable organic acids include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, xylenesulfonic acid, benzenesulfonic acid, formic acid, acetic acid, monocarboxylic acids, dicarboxylic acids or tricarboxylic acids (succinic acid, citric acid), picolinic acid, dipicolinic acid and mixtures thereof. In certain embodiments, the composition of the present invention does not contain or is substantially free of phosphorus-based acids. In certain embodiments, the selected acidulant can also be used as a stabilizer. Therefore, the composition of the present invention can be substantially free of additional acidulants.
[0159] In certain embodiments, the compositions of the present invention include about 0 to about 80% by weight of an acidulant, about 0.5% to about 80% by weight of an acidulant, about 0.1 to about 50% by weight, about 1 to about 50% by weight, or about 5 to about 30% by weight of an acidulant. It should be understood that the compositions of the present invention encompass all values and ranges between these values and ranges.
[0160] Stabilizer
[0161] In some embodiments, the composition of the present invention includes one or more stabilizers. In some embodiments, an acidic stabilizer can be used. Therefore, in some embodiments, the composition of the present invention can be substantially free of additional acidifiers. Suitable stabilizers include, for example, chelating agents or masking agents. Suitable masking agents preferably include, but are not limited to, metal ions in the masking solution, particularly organic chelating compounds of transition metal ions. Such masking agents include organic amino polyphosphonic acid or organic hydroxy polyphosphonic acid complexing agents (in acid form or in soluble salt form), carboxylic acids (e.g., polymeric polycarboxylates), hydroxycarboxylic acids, aminocarboxylic acids, or heterocyclic carboxylic acids, such as pyridine-2,6-dicarboxylic acids (pyridine dicarboxylic acids).
[0162] In some embodiments, the compositions of the present invention include dipicolinic acid as a stabilizer. Compositions including dipicolinic acid can be formulated to be free of or substantially free of phosphorus. It has also been observed that including dipicolinic acid in the compositions of the present invention helps achieve phase stability of the composition compared to other conventional stabilizers, such as 1-hydroxyethylidene-1,1-diphosphonic acid (CH3C(PO3H2)2OH) (HEDP).
[0163] In other embodiments, the masking agent can be or include a phosphonic acid or a phosphonate. Suitable phosphonic acids and phosphonates include HEDP; ethylenediaminetetramethylenephosphonic acid (EDTMP); diethylenetriaminepentamethylenephosphonic acid (DTPMP); cyclohexane-1,2-tetramethylenephosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylenediamine[tetramethylene-phosphonic acid)]; 2-phosphonobutane-1,2,4-tricarboxylic acid; or a salt thereof, such as an alkali metal salt, an ammonium salt, or an alkanoylamine salt, such as a monoethanolamine, diethanolamine or tetraethanolamine salt; picolinic acid, dipicolinic acid, or a mixture thereof. In some embodiments, organic phosphonates, such as HEDP, are included in the compositions of the present invention. Commercially available food additive chelating agents include those sold under the trade names Phosphonates are commercially available, including, for example, 1-hydroxyethylidene-1,1-diphosphonic acid, 2010 from Monsanto Industrial Chemicals, St. Louis, MO; amino(tris(methylenephosphonic acid)), (N[CH2PO3H2]3), 2000 purchased from Monsanto; ethylenediamine [tetrakis(methylenephosphonic acid)], 2041 was purchased from Monsanto; and 2-phosphonobutane-1,2,4-tricarboxylic acid was purchased as Bayhibit AM from Mobay Chemical Company, Inorganic Chemicals Division, Pittsburgh, Pennsylvania.
[0164] The masking agent may be or include an aminocarboxylic acid type masking agent. Suitable aminocarboxylic acid type masking agents include acids or alkali metal salts thereof, such as aminoacetates and salts thereof. Suitable aminocarboxylates include N-hydroxyethylaminodiacetic acid; hydroxyethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid (EDTA); N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA); diethylenetriaminepentaacetic acid (DTPA); and
[0165] Alanine-N,N-diacetic acid, etc.; and mixtures thereof.
[0166] The chelating agent can be or include a polycarboxylate. Suitable polycarboxylates include, for example, polyacrylic acid, maleic acid / olefin copolymers, acrylic acid / maleic acid copolymers, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymaleic acid, polyfumaric acid, copolymers of acrylic acid and itaconic acid, phosphino polycarboxylates, their acid or salt forms, mixtures thereof, and the like.
[0167] In certain embodiments, the present composition may contain about 0 to about 10% by weight of a stabilizer, about 0.01 to about 10% by weight of a stabilizer, about 0.4 to about 4% by weight of a stabilizer, about 0.6 to about 3% by weight of a stabilizer, about 1 to about 2% by weight of a stabilizer. It should be understood that the present invention encompasses all values and ranges within these values and ranges.
[0168] Wetting agent or defoamer
[0169] In addition, suitable for use in the composition of the present invention are wetting agents and defoamers. Wetting agents are used to improve the surface contact or penetration activity of the antimicrobial composition of the present invention. Wetting agents that can be used in the composition of the present invention include any of those components known in the art to promote the surface activity of the composition of the present invention. In aspects of the present invention, various quaternary ammonium compounds are suitable for rinse aid and disinfection rinse aid applications, without the need to use additional defoamers in the formulation. In other embodiments using commercially available quaternary ammonium compounds, defoamers are preferred in the composition or in combination with the composition, for example using the composition of Bardac 2250, Bardac MB50 and Bardac 205M.
[0170] Generally, defoamers that can be used according to the present invention preferably include alcohol alkoxylates and EO / PO block copolymers. In some embodiments, the compositions of the present invention may include anti-foaming agents or defoamers of food grade quality considering the application of the method of the present invention. For this purpose, one of the more effective anti-foaming agents includes silicones. Silicones (such as dimethyl silicones), glycol polysiloxanes, methylphenol polysiloxanes, trialkyl or tetraalkyl silanes, hydrophobic silica defoamers and mixtures thereof can all be used in defoaming applications. Commonly available commercial defoamers include silicones, such as those from Armour Industrial Chemical Company. It is a silicone bonded in an organic emulsion; available from Krusable Chemical Company as Foam or These are silicone and non-silicone type defoamers and silicone esters; and Anti-Foam and DC-200, both of which are food grade silicones, etc. These defoamers may be present in a concentration range of about 0.01 wt % to 20 wt %, 0.01 wt % to 20 wt %, about 0.01 wt % to 5 wt %, or about 0.01 wt % to about 1 wt %.
[0171] Thickener or gelling agent
[0172] The composition of the present invention may include any of various known thickeners. Suitable thickeners include natural gums, such as xanthan gum, guar gum or other gums from plant mucus; polysaccharide thickeners, such as alginates, starches and cellulose polymers (such as carboxymethyl cellulose); polyacrylate thickeners; and hydrocolloid thickeners, such as pectin. In one embodiment, the thickener does not leave contaminating residues on the surface of the object. For example, the thickener or gelling agent can be compatible with food or other sensitive products in the contact area. Typically, the thickener concentration used in the composition or method of the present invention depends on the viscosity required in the final composition. However, as a general guideline, the range of the viscosity enhancer or thickener in the composition of the present invention is from about 0.1% by weight to about 5% by weight, from about 0.1% by weight to about 1.0% by weight, or from about 0.1% by weight to about 0.5% by weight.
[0173] Additional surfactant
[0174] Antimicrobial compositions according to the present invention and / or the antimicrobial compositions of deactivation may include additional surfactants. In a particular aspect, nonionic surfactants are particularly useful in applications requiring additional defoaming. In some respects, it may be desirable that nonionic surfactants and compositions of the present invention are combined (such as included in the detergent formulations used in combination therewith). For example, in certain embodiments, such as food soil defoaming applications, it may be desirable that nonionic surfactants preferably include alcohol alkoxylates and EO / PO block copolymers.
[0175] Suitable nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are usually produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic basic oxide moiety which is conventionally ethylene oxide or its polyhydrated product polyethylene glycol. Virtually any hydrophobic compound having a hydroxyl, carboxyl, amino or amide group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydrated adducts or mixtures thereof with alkylene oxides such as propylene oxide to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be readily adjusted to produce a water dispersible or water soluble compound having the desired degree of balance between hydrophilicity and hydrophobicity. Suitable nonionic surfactants include:
[0176] Block polyoxypropylene-polyoxyethylene polymeric compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compounds. Examples of polymeric compounds made by sequential propoxylation and ethoxylation of initiators can be found under the trade name and (manufactured by BASF) is commercially available. The compound is a difunctional (two reactive hydrogen) compound formed by the condensation of 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 weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlling the length to constitute from about 10% to about 80% by weight of the final molecule. The compound is a tetrafunctional block copolymer obtained by sequentially adding propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype is in the range of about 500 to about 7,000; and the hydrophilic ethylene oxide is added to constitute about 10% to about 80% by weight of the molecule.
[0177] The condensation products of one mole of alkylphenol with about 3 to about 50 moles of ethylene oxide, in which the alkyl chain contains about 8 to about 18 carbon atoms, either in a straight or branched configuration or in a single or double alkyl group. The alkyl group may be represented, for example, by diisobutylene, dipentyl, polymerized propylene, isooctyl, nonyl and dinonyl. These surfactants may be polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols. Examples of commercial compounds of this chemical nature are marketed under the trade names (Made by Rhodiaand) (manufactured by The Dow Chemical Company).
[0178] The condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alcohol portion can consist of a mixture of alcohols within the carbon ranges depicted above, or it can consist of alcohols having a specific number of carbon atoms within this range. Examples of similar commercial surfactants are available under the trade names (manufactured by Shell Chemical Co.) and (manufactured by Sasol North America Inc.)
[0179] The condensation products 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 it may consist of an acid having a specific number of carbon atoms within this range.
[0180] In addition to the ethoxylated carboxylic acids commonly referred to as polyethylene glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerol and polyhydroxy (sugar or sorbitan / sorbitol) alcohols also have applications in the present invention for certain embodiments, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecules that can be further acylated or ethylene oxide (alkoxide) added to control the hydrophilicity of these materials. When adding these fatty esters or acylated carbohydrates to the compositions of the present invention containing amylases and / or lipases, special care must be taken due to potential incompatibility.
[0181] Examples of nonionic low foaming surfactants include:
[0182] Compounds from (1) modified, essentially inversely, by adding ethylene oxide to ethylene glycol to provide a hydrophile of a 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 weighs from about 1,000 to about 3,100, with the intermediate hydrophile constituting from 10% to about 80% by weight of the final molecule. These inversely It is produced by BASF under the trade name R surfactant manufacturing. Similarly, R surfactants are produced by BASF by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of the molecule weighs from about 2,100 to about 6,700, with the intermediate hydrophile constituting 10 to 80 weight percent of the final molecule.
[0183] Compounds from Group (1), Group (2), Group (3) and Group (4) which have been modified by "capping" or "end blocking" one or more terminal hydroxyl groups (of the multifunctional moiety) to reduce foaming by reaction with small hydrophobic 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 which convert terminal hydroxyl groups to chloride groups. Such modification of terminal hydroxyl groups can produce full block, segmented, segmented or fully hybrid nonionic surfactants.
[0184] Additional examples of effective low foaming nonionic surfactants include:
[0185] Alkylphenoxypolyethoxyalkanols are described in U.S. Pat. No. 2,903,486, issued to Brown et al. on Sept. 8, 1959, and are represented by the formula:
[0186]
[0187] wherein R is an alkyl group having 8 to 9 carbon atoms, A is an alkylene chain having 3 to 4 carbon atoms, n is an integer from 7 to 16, and m is an integer from 1 to 10.
[0188] U.S. Pat. No. 3,048,548, issued to Martin et al. on Aug. 7, 1962, discloses a polyalkylene glycol condensate 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 hydrophilic linking units each constitute approximately one third of the condensate.
[0189] The defoaming nonionic surfactant disclosed in U.S. Pat. No. 3,382,178 issued May 7, 1968 to Lissant et al. has the general formula Z[(OR) n OH]z , wherein Z is an alkoxylatable material, R is a group derived from a basic oxide, which may be ethylene and propylene, and n is an integer such as 10 to 2,000 or more, and z is an integer determined by the number of reactive alkoxylatable groups.
[0190] The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,677,700 issued May 4, 1954 to Jackson et al. correspond to the formula Y(C3H6O) n (C2H4O) m 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 weight percent to about 90 weight percent of the molecule.
[0191] The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,674,619 issued to Lundsted et al. on April 6, 1954, have the formula Y[(C3H6O n (C2H4O) m H] x , wherein Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein x has 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 defined range for Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylenediamine, and the like. The oxypropylene chain optionally but advantageously contains a small amount of ethylene oxide, and the oxyethylene chain also optionally but advantageously contains a small amount of propylene oxide.
[0192] The additional conjugated polyoxyalkylene surfactant advantageously used in the composition of the present invention corresponds to the formula: P[(C3H6O) n (C2H4O) m H] x , wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene moiety is at least about 44 and m has a value such that the oxyethylene content of the molecule is from about 10% to about 90% by weight. In either case, the oxypropylene chain may optionally but advantageously contain small amounts of oxyethylene, and the oxyethylene chain may also optionally but advantageously contain small amounts of propylene oxide.
[0193] Polyhydroxy fatty acid amide surfactants suitable for use in the compositions of the present invention include those having the formula R2CON R1Z, wherein: R1 is H, C1-C4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof; R2 is C5-C 31 A hydrocarbon group, which may be a straight chain; and Z is a polyhydroxy hydrocarbon group having a linear hydrocarbon chain with at least 3 hydroxyl groups directly attached to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z may be derived from a reducing sugar in a reductive amination reaction; such as a glycidyl moiety.
[0194] The alkyl ethoxylation condensation products of fatty alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the compositions of the present invention. The alkyl chain of the fatty alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
[0195] Ethoxylated C6-C 18 Fatty alcohols and C6-C 18 Mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the compositions of the present invention, especially those which are water soluble. Suitable ethoxylated fatty alcohols include C6-C 18 Ethoxylated fatty alcohols.
[0196] Suitable nonionic alkyl polysaccharide surfactants particularly suitable for use in the compositions of the present invention include those disclosed in U.S. Pat. No. 4,565,647, issued to Llenado on January 21, 1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms; and a polysaccharide, such as a polysaccharide glycoside hydrophilic group containing from about 1.3 to about 10 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be substituted for the glucosyl moiety. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions, thereby obtaining glucose or galactose as opposed to glucoside or galactoside.) The intersugar linkage can be, for example, between one position of the additional sugar unit and the 2-, 3-, 4- and / or 6-position on the preceding sugar unit.
[0197] Fatty acid amide surfactants suitable for use in the compositions of the present invention include those having the formula R6CON(R7)2, wherein R6 is an alkyl group containing from 7 to 21 carbon atoms and each R7 is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl or --(C2H4O) X H, where x is in the range of 1 to 3.
[0198] Suitable classes of nonionic surfactants include those defined as alkoxylated amine or most particularly alcohol alkoxylated / aminated / alkoxylated surfactants. These nonionic surfactants may be represented at least in part by the general formula: R 20 --(PO)S N--(EO) t H.R 20 --(PO) S N--(EO) t H(EO) t H and R 20 --N(EO) t H; where R 20 R is an alkyl, alkenyl or other aliphatic group or alkyl-aryl group having 8 to 20, preferably 12 to 14 carbon atoms, EO is ethylene oxide, PO is propylene oxide, 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 of the range of these compounds can be represented by the alternative formula: R 20 --(PO) V --N[(EO) w H][(EO) z H], where R 20 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. Commercially, these compounds are represented by a series of products sold by Huntsman Chemical as nonionic surfactants. Preferred chemicals of this category include PEA25 amine alkoxylate. Preferred nonionic surfactants for use in the compositions of the present invention include alcohol alkoxylates, EO / PO block copolymers, alkylphenol alkoxylates, and the like.
[0199] The monograph "Nonionic Surfactants", (by Schick, MJ, ed., Vol. 1, Surfactant Science Series, Marcel Dekker, Inc., New York, 1983) is an excellent reference for a wide variety of nonionic compounds commonly used in the practice of the present invention. A typical list of nonionic classes and materials of these surfactants is given in U.S. Patent No. 3,929,678, granted to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch).
[0200] Semi-polar nonionic surfactant
[0201] Semi-polar type nonionic surfactants are another class of nonionic surfactants suitable for use in the compositions of the present invention. Generally speaking, semi-polar nonionic surfactants are advanced foaming agents and foam stabilizers, which limits their use in CIP systems. However, within the compositional embodiments of the present invention designed for high foam cleaning methods, semi-polar nonionic surfactants will have direct utility. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides, and alkoxylated derivatives thereof.
[0202] Amine oxides are tertiary amine oxides corresponding to the following general formula:
[0203]
[0204] where the arrow is a conventional representation of a semipolar bond; and, R 1 , R 2 and R 3 It can be an aliphatic group, an aromatic group, a heterocyclic group, an alicyclic group or a combination thereof. Generally speaking, for the amine oxide of the relevant detergent, R 1 is an alkyl group of about 8 to about 24 carbon atoms; R 2 and R 3 is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a mixture thereof; R 2 and R 3 may be linked to each other, for example, via an oxygen atom or a nitrogen atom to form a ring structure; R 4 is a base or hydroxyalkylene group containing 2 to 3 carbon atoms; and n is in the range of 0 to about 20.
[0205] Suitable water-soluble amine oxide surfactants are selected from coconut or animal fat alkyl di-(lower alkyl) amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-tri(octadecyl)dimethylamine oxide and 3-dodecyloxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.
[0206] Suitable semi-polar nonionic surfactants also include water-soluble phosphine oxides having the following structure:
[0207]
[0208] where the arrow is a conventional representation of a semipolar bond; and, R 1 is an alkyl, alkenyl or hydroxyalkyl moiety having a chain length ranging from 10 to about 24 carbon atoms; and R 2 and R 3 Each is an alkyl moiety independently selected from an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.
[0209] Examples of suitable phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide and bis(hydroxymethyl)tetradecylphosphine oxide.
[0210] Semi-polar nonionic surfactants suitable for use herein also include water-soluble sulfoxide compounds having the following structure:
[0211]
[0212] where the arrow is a conventional representation of a semipolar bond; and, R 1 is an alkyl or hydroxyalkyl moiety having from about 8 to about 28 carbon atoms, 0 to about 5 ether linkages, and 0 to about 2 hydroxyl substituents; and R 2 It is an alkyl moiety composed of an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group.
[0213] Suitable examples of such sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecyl methyl sulfoxide; and 3-hydroxy-4-dodecyloxybutyl methyl sulfoxide.
[0214] Semi-polar nonionic surfactants for use in the composition of the present invention include dimethyl amine oxides, such as lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinations thereof, etc. Suitable 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 dimethyl amine oxide, nonyl dimethyl amine oxide, decyl dimethyl amine oxide, undecyl dimethyl amine oxide, dodecyl dimethyl amine oxide, isododecyl dimethyl amine oxide, tridecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, pentadecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, heptadecyl dimethyl amine oxide. 1-hydroxypropylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-tri(octadecyl)dimethylamine oxide and 3-dodecyloxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.
[0215] Suitable nonionic surfactants for use with the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, blocked EO / PO copolymers, alcohol alkoxylates, blocked alcohol alkoxylates, mixtures thereof, and the like. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers, such as and inverting Surfactants; alcohol alkoxylates, such as LS-54(R-(EO)5(PO)4) and LS-36(R-(EO)3(PO)6); and capped alcohol alkoxylates, such as LF221 and EC11; mixtures thereof, etc.
[0216] Masking Agent
[0217] The composition may contain an organic or inorganic masking agent or a mixture of masking agents. Organic masking agents such as sodium citrate, alkali metal salts of nitrilotriacetic acid (NTA), dicarboxymethylglutamic acid tetrasodium salt (GLDA), EDTA, alkali metal gluconates, polyelectrolytes (such as polyacrylic acid), etc. may be used herein. Due to the compatibility of the masking agent with the formulation base, the most preferred masking agent is an organic masking agent such as sodium gluconate.
[0218] The present invention can also add masking agents to include materials such as complex phosphate masking agents, including sodium tripolyphosphate, sodium hexametaphosphate, etc. and mixtures thereof. Phosphates, sodium condensed phosphate hardness masking agent components are used as water softeners, cleaning agents and detergent builders. Alkali metal (M) linear and cyclic condensed phosphates generally have a molar ratio of M2O:P2O5 of about 1:1 to 2:1 and higher. Typical polyphosphates of this type are preferred sodium tripolyphosphate, sodium hexametaphosphate, sodium metaphosphate and the corresponding potassium salts of these phosphates and mixtures thereof. The particle size of the phosphate is not important, and any finely divided or granular commercially available product can be used.
[0219] Curing agent or hardener
[0220] If it is desired that the composition of the present invention is prepared as a solid, a curing agent may be included in the composition. In certain embodiments, a curing agent may be used as a solid rinse aid composition to form and / or maintain the composition. In other embodiments, a curing agent may solidify the composition without unacceptably impairing the final release of the active ingredient. Curing agents may include, for example, organic or inorganic solid compounds with neutral inert characteristics or functional, stable or decontamination contributions to the composition of the present invention. Suitable curing agents include solid polyethylene glycol (PEG), solid polypropylene glycol, solid EO / PO block copolymers, amides, ureas (also referred to as urea), nonionic surfactants (which may be used together with coupling agents), anionic surfactants, starches (e.g., by acid or alkaline treatment processes) that have been water-soluble, celluloses that have been water-soluble, inorganic agents, poly(maleic anhydride / methyl vinyl ether), polymethacrylic acid, other commonly used functional or inert materials with high melting points, mixtures thereof, etc.
[0221] Suitable diol curing agents include solid polyethylene glycol or solid polypropylene glycol, which may, for example, have a molecular weight of about 1,400 to about 30,000. In certain embodiments, the curing agent includes or is solid PEG, such as PEG 1500 to PEG 20,000. In certain embodiments, PEG includes PEG 1450, PEG 3350, PEG 4500, PEG 8000, PEG 20,000, etc. Suitable solid polyethylene glycols are commercially available from Union Carbide under the trade name CARBOWAX.
[0222] Suitable amide curing agents include stearic acid monoethanolamide, lauric acid diethanolamide, stearic acid diethanolamide, stearic acid monoethanolamide, cocoic acid diethyleneamide, alkylamides, mixtures thereof, etc. In one embodiment, the composition of the present invention may include a glycol (eg, PEG) and an amide.
[0223] Suitable inorganic curing agents include phosphates (e.g., alkali metal phosphates), sulfates (e.g., magnesium sulfate, sodium sulfate, or sodium bisulfate), acetates (e.g., anhydrous sodium acetate), borates (e.g., sodium borate), silicates (e.g., in precipitated or fumed form) (e.g., Sipernat available from Degussa), ), carbonates (such as calcium carbonate or carbonate hydrates), other known hydratable compounds, mixtures thereof, etc. In one embodiment, the inorganic curing agent may include an organic phosphonate compound and a carbonate, such as an E-type composition.
[0224] In some embodiments, the compositions of the present invention may include any agent or combination of agents that provide the necessary degree of solidification, and water solubility may be included in the compositions of the present invention. In other embodiments, increasing the concentration of the solidifying agent in the compositions of the present invention may tend to increase the hardness of the composition. In other embodiments, decreasing the concentration of the solidifying agent may tend to loosen or soften the concentrate composition.
[0225] In some embodiments, the curing agent may include any organic or inorganic compound that imparts solubility characteristics to the compositions of the present invention and / or controls the solubility characteristics of the compositions of the present invention, for example, when placed in an aqueous environment. For example, if the curing agent has greater water solubility than the other ingredients in the composition, the curing agent can provide controlled distribution. Urea can be one such curing agent. As a further example, for systems that can benefit from lower water solubility or slower dissolution rates, organic nonionic or amide hardeners may be suitable.
[0226] In some embodiments, the composition of the present invention may include a curing agent that provides convenient processing or manufacturing of the composition of the present invention. For example, the curing agent can be selected to form a composition that can harden into a solid form at an ambient temperature of about 30 to about 50° C. within about 1 minute to about 3 hours, or about 2 minutes to about 2 hours, or about 5 minutes to about 1 hour after mixing is stopped and the mixture is dispensed from the mixing system.
[0227] In one exemplary aspect, the solid rinse aid may include an effective amount of a curing agent or hardener, such as urea, which changes the solubility of the composition in an aqueous medium during use so that the rinse aid and / or other active ingredients can be dispensed from the solid composition over an extended period of time. The composition may include a hardener in an amount ranging from about 50% by weight to about 50% by weight. In other embodiments, the hardener may be present in an amount ranging from about 20% by weight to about 40% by weight, or in an amount ranging from about 5 to about 15% by weight.
[0228] The composition of the present invention may include any effective amount of curing agent. The amount of the curing agent included in the composition of the present invention will vary according to the following: the type of composition, the composition of the composition, the intended use of the composition, the amount of the distribution solution applied to the solid composition over time during use, the temperature of the distribution solution, the hardness of the distribution solution, the physical size of the solid composition, the concentration of other ingredients, the concentration of the cleaning agent in the composition and other similar factors. Suitable amount may include about 1 to about 99% by weight, about 1.5 to about 85% by weight, about 2 to about 80% by weight, about 10 to about 45% by weight, about 15 to about 40% by weight, about 20% to about 30% by weight, about 30% to about 70%, about 40% to about 60%, about 50% by weight at most, about 40% to about 50%.
[0229] Additional Exemplary Embodiments
[0230] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %, and an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %.
[0231] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001% to about 75% by weight; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001% to about 50% by weight; and at least one additional functional ingredient selected from the group consisting of an acidulant in an amount of about 0.1% to about 50% by weight, a stabilizer in an amount of about 0.01% to about 10% by weight, a defoamer in an amount of about 0.01% to about 20% by weight, a viscosity enhancer or thickener in an amount of about 0.1% to about 5% by weight, an additional surfactant in an amount of about 0.01% to about 50% by weight, a sequestering agent in an amount of about 0.01% to about 50% by weight, and a curing agent in an amount of about 0.01% to about 50% by weight.
[0232] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least two additional functional ingredients selected from the group consisting of an acidulant in an amount of about 0.1 wt % to about 50 wt %, a stabilizer in an amount of about 0.01 wt % to about 10 wt %, a defoamer in an amount of about 0.01 wt % to about 20 wt %, a viscosity enhancer or thickener in an amount of about 0.1 wt % to about 5 wt %, an additional surfactant in an amount of about 0.01 wt % to about 50 wt %, a sequestering agent in an amount of about 0.01 wt % to about 50 wt %, and a curing agent in an amount of about 0.01 wt % to about 50 wt %.
[0233] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least three additional functional ingredients selected from the group consisting of an acidulant in an amount of about 0.1 wt % to about 50 wt %, a stabilizer in an amount of about 0.01 wt % to about 10 wt %, a defoamer in an amount of about 0.01 wt % to about 20 wt %, a viscosity enhancer or thickener in an amount of about 0.1 wt % to about 5 wt %, an additional surfactant in an amount of about 0.01 wt % to about 50 wt %, a sequestering agent in an amount of about 0.01 wt % to about 50 wt %, and a curing agent in an amount of about 0.01 wt % to about 50 wt %.
[0234] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least four additional functional ingredients selected from the group consisting of: an acidulant in an amount of about 0.1 wt % to about 50 wt %, a stabilizer in an amount of about 0.01 wt % to about 10 wt %, a defoamer in an amount of about 0.01 wt % to about 20 wt %, a viscosity enhancer or thickener in an amount of about 0.1 wt % to about 5 wt %, an additional surfactant in an amount of about 0.01 wt % to about 50 wt %, a sequestering agent in an amount of about 0.01 wt % to about 50 wt %, and a curing agent in an amount of about 0.01 wt % to about 50 wt %.
[0235] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least five additional functional ingredients selected from the group consisting of an acidulant in an amount of about 0.1 wt % to about 50 wt %, a stabilizer in an amount of about 0.01 wt % to about 10 wt %, a defoamer in an amount of about 0.01 wt % to about 20 wt %, a viscosity enhancer or thickener in an amount of about 0.1 wt % to about 5 wt %, an additional surfactant in an amount of about 0.01 wt % to about 50 wt %, a sequestering agent in an amount of about 0.01 wt % to about 50 wt %, and a curing agent in an amount of about 0.01 wt % to about 50 wt %.
[0236] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least six additional functional ingredients selected from the group consisting of: an acidulant in an amount of about 0.1 wt % to about 50 wt %, a stabilizer in an amount of about 0.01 wt % to about 10 wt %, a defoamer in an amount of about 0.01 wt % to about 20 wt %, a viscosity enhancer or thickener in an amount of about 0.1 wt % to about 5 wt %, an additional surfactant in an amount of about 0.01 wt % to about 50 wt %, a sequestering agent in an amount of about 0.01 wt % to about 50 wt %, and a curing agent in an amount of about 0.01 wt % to about 50 wt %.
[0237] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of, and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001% to about 75% by weight; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001% to about 50% by weight; an acidulant in an amount of about 0.1% to about 50% by weight; a stabilizer in an amount of about 0.01% to about 10% by weight; a defoaming agent in an amount of about 0.01% to about 20% by weight; a viscosity enhancer or thickener in an amount of about 0.1% to about 5% by weight; an additional surfactant in an amount of about 0.01% to about 50% by weight, a sequestering agent in an amount of about 0.01% to about 50% by weight, and a curing agent in an amount of about 0.01% to about 50% by weight.
[0238] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001% to about 75% by weight; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001% to about 50% by weight; and at least one additional functional ingredient selected from the group consisting of: additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, corrosion inhibitors, sequestering agents and / or chelating agents, curing agents, tableting agents, pH adjusting components, including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, odorants or fragrances), other cleaning agents, hydrotropes or coupling agents, buffers, etc., in an amount of about 0.01% to about 50% by weight.
[0239] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least two additional functional ingredients selected from the group consisting of: additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, corrosion inhibitors, sequestering agents and / or chelating agents, curing agents, tableting agents, pH adjusting components, including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, odorants or fragrances), other cleaning agents, hydrotropes or coupling agents, buffers, etc., in an amount of about 0.01 wt % to about 50 wt %.
[0240] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001% to about 75% by weight; an anionic surfactant or an anionic polymer / chelating agent in an amount of about 0.0001% to about 50% by weight; and at least three additional functional ingredients selected from the group consisting of: additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, corrosion inhibitors, sequestering agents and / or chelating agents, curing agents, tableting agents, pH adjusting components, including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, odorants or fragrances), other cleaning agents, hydrotropes or coupling agents, buffers, etc., in an amount of about 0.01% to about 50% by weight.
[0241] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001% to about 75% by weight; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001% to about 50% by weight; and at least four additional functional ingredients selected from the group consisting of: additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, corrosion inhibitors, sequestering agents and / or chelating agents, curing agents, tableting agents, pH adjusting components, including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, odorants or fragrances), other cleaning agents, hydrotropes or coupling agents, buffers, etc., in an amount of about 0.01% to about 50% by weight.
[0242] In some aspects, the antimicrobial composition or inactivated antimicrobial composition according to the present invention may comprise, consist of and / or consist essentially of: a quaternary ammonium compound in an amount of about 0.001 wt % to about 75 wt %; an anionic surfactant or anionic polymer / chelating agent in an amount of about 0.0001 wt % to about 50 wt %; and at least five additional functional ingredients selected from the group consisting of: additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, corrosion inhibitors, sequestering agents and / or chelating agents, curing agents, tableting agents, pH adjusting components, including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, odorants or fragrances), other cleaning agents, hydrotropes or coupling agents, buffers, etc., in an amount of about 0.01 wt % to about 50 wt %.
[0243] Solubilized fatty acids
[0244] A method comprising solubilizing fatty acids. In exemplary applications, solubilizing fatty acids are particularly suitable for solubilizing and thus removing fatty acid dirt (cohesive energy). The method comprises providing a carboxylic fatty acid and solubilizing it with a quaternary ammonium. Such methods produce compositions with enhanced antimicrobial activity. In one embodiment, a fatty acid and a quaternary ammonium compound are solubilized using a mole: molar ratio. In another embodiment, the solubilization of fatty acids comprises approximately a mole: molar ratio of quaternary ammonium compounds and fatty acids. In other aspects, the composition comprises a quaternary ammonium compound and a fatty acid at most about 10 to about 1 molar ratio. In other aspects, the composition comprises a quaternary ammonium compound and a fatty acid at most about 1 to about 10 molar ratios, or any combination thereof. In another embodiment, the molar ratio of the fatty acid of the composition to the quaternary ammonium is about 1 mole of fatty acid to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of the fatty acid of the composition to the quaternary ammonium compound is about 1.5 moles of fatty acid to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of the fatty acid of the composition to the quaternary ammonium compound is about 1 mole of fatty acid to about 10 moles of quaternary ammonium compound. In another embodiment, the composition has a molar ratio of fatty acid to quaternary ammonium compound of about 2 moles of fatty acid to about 1 mole of quaternary ammonium compound.
[0245] Without being limited to a particular mechanism of action, when fatty acids are said to be solubilized, it is meant that the combination comprising the fatty acids is soluble in water. A composition is said to be "water soluble" if it is at least 90% soluble in water, at least 95% soluble in water, at least 98% soluble in water, at least 99% soluble in water, and at least 99.9% soluble in water.
[0246] Use Composition
[0247] The activated antimicrobial composition of the present invention and the composition of deactivation may include a concentrate composition and a use composition, or may be diluted to form a use composition. For example, the concentrate composition may be diluted, for example, with water to form a use composition. In general, a concentrate refers to a composition intended to be diluted with water to provide a use solution, which is contacted with a surface and / or product that needs to be treated to provide the required surface activity. Depending on the formulation adopted in the method according to the present invention, the antimicrobial composition or the deactivated antimicrobial composition that contacts the surface and / or product that needs to be treated may be referred to as a concentrate or a use composition (or a use solution). It should be understood that the concentration of the quaternary ammonium compound and the anionic surfactant in the composition will vary depending on whether the composition is provided as a concentrate or as a use solution. In one embodiment, the concentrate composition may be diluted to a use solution before being applied to an object. The concentrate may be sold on the market, and the end user may dilute the concentrate to a use solution with water or an aqueous diluent.
[0248] Compositions of the present invention can be prepared and sold for use as is, or used as solvent concentrates. If desired, this type of concentrate can be used as an antimicrobial agent at full strength. However, concentrates will usually be diluted with a fluid (e.g., water) or a working solution that forms a dilute phase subsequently. Preferably, concentrates form a single phase before such dilution, and remain so when stored in a container to be sold. When combined with water or other required dilution fluids with an appropriate dilution level and gently stirred (e.g., by stirring or pumping compositions), some compositions of the present invention will form pseudo-stable dispersions, and other compositions of the present invention will form a clear or quasi-stable solution or dispersion. If a pseudo-stable composition is formed, the composition is preferably maintained at a pseudo-stable sufficiently long time so that the composition can be applied to the surface before phase separation begins. When adopting appropriate rapid application technology such as spraying, or when stirring during application, pseudo-stable only needs to last for a few seconds. After mixing and when the composition is stored in a suitable container, pseudo-stable is expected to last at least one minute or longer, and preferably lasts five minutes or longer after mixing. Typically, normal refilling or replenishing of the applicator (eg, by dipping the applicator into the composition) will provide sufficient agitation to maintain a pseudo-steady state of the composition during application.
[0249] A use solution can be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having the desired disinfecting and / or other antimicrobial properties. The water used to dilute the concentrate to form the use composition can be referred to as dilution water or diluent, and can vary from site to site. Typical dilution factors are between about 1 and about 10,000, but will depend on factors including water hardness, the amount of soil to be removed, and the like. In one embodiment, the concentrate is diluted at a concentrate:water ratio between about 1:10 and about 1:10,000. Specifically, the concentrate is diluted at a concentrate:water ratio between about 1:100 and about 1:5,000. More specifically, the concentrate is diluted at a concentrate:water ratio between about 1:250 and about 1:2,000.
[0250] In a preferred embodiment, the present invention includes a concentrate composition and a use composition. In one embodiment, the concentrate composition can be diluted into a use solution before being applied to an object. The concentrate can be sold on the market, and the end user can dilute the concentrate into a use solution with water or an aqueous diluent. The content of the active component in the concentrate composition depends on the expected dilution factor and the desired activity of the antimicrobial composition. Typically, for the aqueous composition of the present invention, a dilution of about 1 fluid ounce to about 10 gallons of water to about 10 fluid ounces to about 1 gallon of water is used. In some embodiments, if an elevated use temperature (greater than 25°C) or an extended exposure time (greater than 30 seconds) can be used, a higher use dilution can be used. In a typical use site, the concentrate is diluted with a large proportion of water using commonly available tap water or service water with a dilution ratio of about 3 to about 40 ounces of concentrate per 100 gallons of water.
[0251] In some embodiments, the concentrate composition can be diluted at a dilution ratio of about 0.1 g / L to about 100 g / L concentrate to diluent, about 0.5 g / L to about 10.0 g / L concentrate to diluent, about 1.0 g / L to about 4.0 g / L concentrate to diluent, or about 1.0 g / L to about 2.0 g / L concentrate to diluent.
[0252] In other embodiments, the use composition can include about 0.01 to about 10 weight percent of the concentrate composition and about 90 to about 99.99 weight percent of the diluent; or about 0.1 to about 1 weight percent of the concentrate composition and about 99 to about 99.9 weight percent of the diluent.
[0253] The amount of ingredient in use composition can be calculated from the amount of the concentrate composition listed above and these dilution factors. In certain embodiments, dilute concentrate composition of the present invention so that the quaternary ammonium component exists with about 10ppm to about 100ppm, or about 50ppm to about 400ppm. In other embodiments, dilute concentrate composition of the present invention so that the quaternary ammonium component exists with about 20ppm or higher, about 40ppm or higher, about 60ppm or higher, about 80ppm or higher, about 100ppm or higher, about 500ppm, about 1000ppm or about 10,000 to about 20,000ppm. It should be understood that all values and scopes between these values and scopes are encompassed by the present invention.
[0254] A variety of fluids can be used as diluent solvents, including water in liquid form; steam; condensed gases and other supercritical fluids (such as CO2); perchloroethylene; oils, such as silicone oils (e.g., siloxanes), gear oils, variable speed drive oils, mineral oils, or vegetable oils; and carboxylates, such as methyl soy ester. If desired, a mixture of diluent solvents can be used. Preferably, the diluent solvent consists essentially of or consists of water in liquid form. The remainder of this specification will primarily discuss the use of water in liquid form as the diluent solvent, with the understanding that other suitable fluids can be added to or substituted for water in liquid form if desired.
[0255] In one embodiment of the present invention, the concentrate compositions and use compositions maintain their disinfecting efficacy while tolerating water conditions, or are independent of water conditions such as water hardness. According to embodiments of the present invention, the compositions tolerate water conditions of about 0 parts per million (ppm) to about 500 ppm (about 0 to about 30 grains per gallon) of water hardness without affecting the disinfecting efficacy according to embodiments of the present invention. As referred to herein, water hardness ppm refers to the ppm of calcium, magnesium, and other metals that can be found in water and contribute to the hardness level.
[0256] Manufacturing method
[0257] The composition of the present invention is prepared by adding anionic surfactants to the quaternary ammonium. The quaternary ammonium compound readily couples the more hydrophobic organic acid into solution with minimal or no agitation.
[0258] In one aspect, the addition of the material is provided in a molar ratio of quaternary ammonium to anionic surfactant of up to about 10: about 1. In one embodiment, the ratio of quaternary ammonium to anionic surfactant is about 1:1 molar ratio.
[0259] In some aspects, the compositions according to the present invention can be prepared by combining the components in an aqueous diluent using commonly available containers and blending devices. Advantageously, no special manufacturing equipment is required to prepare the compositions using quaternary ammonium compounds and anionic surfactants. A preferred method of making the cleaning compositions of the present invention comprises introducing the components into a stirred production vessel.
[0260] Antimicrobial compositions according to the present invention and / or the antimicrobial compositions of deactivation can be provided with single use or multiple use compositions. In preferred aspects, compositions are concentrated liquid or solid compositions. Various solids can be used according to the present invention, but do not limit the scope of the invention. It should be understood that compositions and methods embodying the present invention are suitable for preparing a variety of solid compositions, such as solid pellets, blocks, sheets, etc., cast, extruded, compressed, molded or shaped. In certain embodiments, solid compositions can be shaped to have a weight of 50 grams or less, and in other embodiments, solid compositions can be shaped to have a weight of 50 grams or more, 500 grams or more, or 1 kilogram or more.
[0261] Methods of using the antimicrobial compositions of the present invention
[0262] The present invention includes methods of using the antimicrobial compositions of the present invention for various applications. The present invention includes methods of reducing microbial populations, methods of reducing microbial populations on the skin, and methods of treating skin diseases. These methods can be operated on articles, on surfaces, in vivo, or in water streams or gases, etc., by contacting articles, surfaces, the body, or streams with the compositions of the present invention. Contact can include any of the various methods for applying the compositions of the present invention, such as spraying the compositions, immersing the articles in the compositions, treating the articles with compound or composition foams or gels, or combinations thereof.
[0263] In some embodiments, the compositions of the present invention include killing one or more pathogenic bacteria associated with health care surfaces and environments, including but not limited to Salmonella typhimurium, Staphylococcus aureus, methicillin resistant Staphylococcus aureus, Salmonella choleraesurus, Pseudomonas aeruginosa, Escherichia coli, mycobacteria, yeast and mold. The compositions of the present invention have activity against a variety of microorganisms, such as Gram-positive bacteria (e.g., Listeria monocytogenes or Staphylococcus aureus) and Gram-negative bacteria (e.g., Escherichia coli or Pseudomonas aeruginosa), yeast, mold, bacterial spores, viruses, etc. As described above, the compounds and compositions of the present invention have activity against a variety of human pathogens. The compounds and compositions of the invention can kill a wide variety of microorganisms on food processing surfaces, on food surfaces, in water used to wash or process food, on health care surfaces, or in health care environments.
[0264] The inventive method can be used to achieve any suitable reduction of the microbial population in and / or on the target or treated target composition. In certain embodiments, the inventive method can be used to reduce the microbial population in and / or on the target or treated target composition by at least one log10. In other embodiments, the inventive method can be used to reduce the microbial population in and / or on the target or treated target composition by at least two log10. In still other embodiments, the inventive method can be used to reduce the microbial population in and / or on the target or treated target composition by at least three log10. In still other embodiments, the inventive method can be used to reduce the microbial population in and / or on the target or treated target composition by at least five log10. Without limiting the scope of the present invention, the numerical range includes the numbers defining the range and includes each integer within the defined range.
[0265] The compositions of the present invention can be used in various household or industrial applications, for example, to reduce microbial or viral populations on surfaces or objects or in bodies or in water streams. The compounds can be applied to a variety of fields, including kitchens, bathrooms, factories, hospitals, dental clinics and food factories, and can be applied to a variety of hard or soft surfaces with smooth, irregular or porous morphologies. Suitable hard surfaces include, for example, building surfaces (e.g., floors, walls, windows, sinks, tables, counters and signs); dining utensils; hard surface medical or surgical instruments and devices; and hard surface packaging. Such hard surfaces can be made of a variety of materials, including, for example, ceramics, metals, glass, wood or hard plastics. Suitable soft surfaces include, for example, paper; filter media; hospital and surgical sheets and clothing; soft surface medical or surgical instruments and devices; and soft surface packaging. Such soft surfaces can be made of a variety of materials, including, for example, paper, fibers, woven or nonwoven fabrics, soft plastics and elastomers. The compositions of the present invention can also be applied to soft surfaces, such as food and skin (e.g., hands). The compounds of the present invention can be used as foaming or non-foaming environmental disinfectants or sterilants.
[0266] The compositions of the present invention can be included in products such as disinfectants, sanitizers, germicides, preservatives, deodorants, antibacterials, fungicides, bactericides, sporicides, virucides, detergents, bleaches, hard surface cleaners, hand soaps, waterless hand soaps, lubricants, rinse aids; 2-in-1 and / or 3-in-1 products such as insecticide / cleaner / disinfectant, 3 sink applications, and pre- or post-operative scrubs.
[0267] The compositions can also be used in veterinary products such as mammalian skin treatments, or in products for disinfecting or sterilizing animal pens, enclosures, watering stations, and veterinary treatment areas such as examination tables and operating rooms. The compositions of the present invention can be used in antimicrobial foot baths for livestock or humans.
[0268] In some aspects, the composition of the present invention can be used to reduce the colony of pathogenic microorganisms, such as pathogens of humans, animals, etc. The compound shows activity against pathogens, including fungi, molds, bacteria, spores and viruses, such as Staphylococcus aureus, Escherichia coli, Streptococcus, Legionella (Legionella), Pseudomonas aeruginosa, Mycobacterium, tuberculosis, bacteriophages, etc. These pathogens can cause a variety of diseases and conditions, including mastitis or other mammal milking diseases, tuberculosis, etc. The composition of the present invention can reduce the microbial population on animal skin or other external or mucosal surfaces. In addition, the compounds of the present invention can kill pathogenic microorganisms that are transferred and spread by water, air or surface substrates. The composition only needs to be applied to the skin, other external or mucosal surfaces of animal water, air or surface.
[0269] Antimicrobial compositions can also be used on food and plant species to reduce surface microbial populations; for treating manufacturing or processing sites of such food and plant species; or for treating process water around such sites. For example, compounds can be used in food transportation lines (e.g., as belt sprayers); boots and hand-washing dip pans; food storage facilities; antiseptic air circulation systems; refrigeration and cooling equipment; beverage coolers and heaters, blanchers, cutting boards, third sink areas, and meat coolers or scalding devices. The compositions of the present invention can be used to treat agricultural product transportation water, such as those found in water diversion troughs, pipeline transportation, cutters, slicers, blanchers, distillation systems, washing machines, etc. Specific foods that can be treated with the compounds of the present invention include eggs, meat, seeds, leaves, fruits, and vegetables. Specific plant surfaces include harvested and growing leaves, roots, seeds, skins or shells, stems, rods, tubers, bulbs, fruits, etc.
[0270] In some aspects, the composition of the present invention is suitable for cleaning or disinfecting containers, processing facilities or equipment in the food service or food processing industry. The composition is particularly suitable for food packaging materials and equipment, especially cold or hot aseptic packaging. Examples of processing facilities that can use the compounds of the present invention include dairy line dairy products, continuous brewing systems, food processing production lines such as pumpable food systems and beverage production lines, etc. Food service dishes can be sterilized with the compounds of the present invention. For example, the compound can also be used in dishwashing machines, low-temperature dishwashing machines, tableware, bottle washing machines, bottle coolers, heaters, third sink washers, cutting areas (e.g., water knives, slicers, cutters and saws) and egg washers on or in. Specific treatable surfaces include packaging such as cartons, bottles, films and resins; tableware such as glasses, plates, utensils, pots and pans; dishwashing machines and low-temperature dishwashing machines; exposed food preparation area surfaces such as sinks, counters, tables, floors and walls; processing equipment such as tanks, barrels, pipelines, pumps and hoses (e.g., dairy processing equipment for processing milk, cheese, ice cream and other dairy products); and transportation vehicles. Containers include glass bottles, PVC or polyolefin film bags, cans, polyester, PEN or PET bottles of various capacities (100 ml to 2 liters, etc.), one-gallon milk containers, cardboard juice or milk containers, etc.
[0271] The compositions of the present invention may also be applied by immersing food processing equipment in the use solution, soaking the equipment for a time sufficient to sanitize the equipment, and wiping or draining excess solution from the equipment. The compositions may be further applied by spraying or wiping food processing surfaces with the use solution, keeping the surfaces wet for a time sufficient to sanitize the surfaces, and removing excess solution by wiping, draining, vacuuming, etc.
[0272] The compositions of the present invention may also be used in methods of disinfecting hard surfaces such as institutional-type equipment, utensils, cutlery, healthcare or tools, instruments, and other hard surfaces.
[0273] Antimicrobial compositions can be applied to microorganisms or soiled or cleaned surfaces using a variety of methods. These methods can operate on objects, on surfaces, in vivo, or in water streams or gases, etc., by contacting an object, surface, body, or stream with a compound of the invention. Contact can include any of a variety of methods for applying the compound, such as spraying the compound, immersing the object in the compound, treating the object with a compound foam or gel, or a combination thereof.
[0274] The concentrate or use concentration of the compounds of the invention can be applied to or contacted with an object by any conventional method or apparatus for applying antimicrobial or cleaning compounds to an object. For example, an object can be wiped, sprayed, foamed on, and / or immersed in a compound or a use solution made from the composition. The composition can be sprayed, foamed, or wiped onto a surface; the composition can be flowed over a surface, or the surface can be immersed in the composition. Contacting can be done manually or by machine. Food processing surfaces, food, food processing or transport water, and the like can be treated with liquid, foam, gel, aerosol, gas, wax, solid, or powder stabilizing compounds according to the invention or solutions containing these compounds.
[0275] Various treatment methods according to the present invention may include the use of any suitable level of quaternary ammonium compounds and anionic surfactants. In certain embodiments, when diluted for use, the treated target composition comprises a quaternary ammonium compound of about 1ppm to about 1000ppm. In other embodiments, when diluted for use, the treated target composition comprises a quaternary ammonium compound of about 1ppm and about 500ppm, 5ppm and about 400ppm, 10ppm and about 100ppm, 20ppm and about 100ppm, 25ppm and about 100ppm, 10ppm and about 75ppm, 20ppm and about 75ppm, 25ppm and about 75ppm, or about 50ppm. In certain embodiments, the treated target composition comprises an anionic surfactant of about 1ppm to about 1000ppm in the use solution. In other embodiments, when diluted for use, the treated target composition comprises between about 1 ppm and about 500 ppm, 5 ppm and about 250 ppm, 10 ppm and about 100 ppm, 20 ppm and about 100 ppm, 25 ppm and about 100 ppm, 10 ppm and about 50 ppm, 20 ppm and about 50 ppm, 25 ppm and about 50 ppm, or about 50 ppm and about 100 ppm of anionic surfactant.
[0276] In one aspect, the method of the present invention comprises producing a use solution from a concentrated solid or liquid composition of the present invention. The use solution can be prepared from a concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having the desired disinfecting and / or other antimicrobial properties. The water used to dilute the concentrate to form the use composition can be referred to as dilution water or diluent, and can vary from location to location. Typical dilution factors are between about 1 and about 10,000. In one embodiment, the concentrate is diluted with a concentrate:water ratio between about 1:10 and about 1:10,000. Specifically, the concentrate is diluted with a concentrate:water ratio between about 1:100 and about 1:5,000. More specifically, the concentrate is diluted with a concentrate:water ratio between about 1:250 and about 1:2,000.
[0277] In one aspect, the concentrated antimicrobial composition is diluted to a use solution having a concentration of about 0.001% (wt / vol.) to about 10% (wt / vol.), or about 0.001% (wt / vol.) to about 5% (wt / vol.), or about 0.001% (wt / vol.) to about 2% (wt / vol.), or about 0.01% (wt / vol.) to about 1% (wt / vol.). Without limiting the scope of the invention, numerical ranges include the numbers defining the range and include each integer within the defined range.
[0278] Compositions of the present invention can be prepared and sold for use as is, or used as solvents or solid concentrates. If desired, such concentrates can be used as disinfecting rinse compositions at full strength. However, concentrates are usually diluted with fluids (e.g., water) or use solutions that subsequently form a dilute phase. Preferably, concentrates form a single phase before such dilution, and remain so when stored in containers to be sold. When combined with water or other required dilution fluids with appropriate dilution levels and gently stirred (e.g., by stirring or pumping compositions), some compositions of the present invention will form pseudo-stable dispersions, and other compositions of the present invention will form clear or quasi-stable solutions or dispersions. If pseudo-stable compositions are formed, compositions are preferably maintained at pseudo-stable sufficiently long times so that compositions can be applied to surfaces before phase separation begins. When appropriate rapid application techniques such as spraying are adopted, or when stirring during application, pseudo-stable states only need to last for a few seconds. After mixing and when compositions are stored in suitable containers, pseudo-stable states are expected to last at least one minute or longer, and preferably last five minutes or longer after mixing. Typically, normal refilling or replenishing of the applicator (eg, by dipping the applicator into the composition) will provide sufficient agitation to maintain a pseudo-steady state of the composition during application.
[0279] Various use applications described herein provide quaternary ammonium compounds and anionic surfactant compositions to surfaces and / or water sources. Advantageously, the compositions of the present invention are quick-acting. However, for sufficient antimicrobial action to occur, the inventive method requires a certain minimum contact time between the composition and the surface or product to be treated. The contact time can vary with the concentration of the composition, the method of applying the composition, the temperature of the composition, the pH of the composition, the amount of the surface or product to be treated, the amount of dirt or substrate on / in the surface or product to be treated, etc. The contact or exposure time can be about 15 seconds, at least about 15 seconds, about 30 seconds or greater than 30 seconds. In certain embodiments, the exposure time is about 1 to 5 minutes. In other embodiments, the exposure time is a few minutes to a few hours. In other embodiments, the exposure time is a few hours to a few days. The contact time will further vary according to the use concentration of the active substance of the composition according to the present invention.
[0280] Descaling / Demineralization
[0281] The activated quaternary ammonium compound and anionic surfactant (or polymer / chelating agent) composition of the present invention is further suitable for use in various applications and methods where scaling needs to be treated or prevented, including hard water / mineral scale control on surfaces. In preferred embodiments, the anionic polymer or chelating agent provides a surfactant material suitable for concentrating at the interface to provide beneficial scale mineral removal. In addition, the method of the present invention is very suitable for controlling water hardness accumulation on multiple surfaces. The method of the present invention prevents moderate to severe accumulation of hardness and / or redeposition of dirt on the treated substrate surface, which advantageously improves the aesthetic appearance of the surface. In certain embodiments, the surface that needs to prevent hard water scale accumulation includes, for example, plastic, metal and / or glass surfaces.
[0282] In one beneficial aspect of the present invention, the method of the present invention reduces the formation, precipitation and / or deposition of hard scale, such as calcium carbonate, on hard surfaces contacted by the activated composition. In one embodiment, the activated composition is used to prevent the formation, precipitation and / or deposition of hard scale on articles such as glass, plates, silverware, etc. In various applications, such as warewashing applications using various water sources (including hard water), the activated composition effectively removes hard scale and / or prevents hard scale accumulation and / or prevents soil redeposition. In addition, the activated composition is suitable for use in temperature ranges commonly used in industrial warewashing applications, including, for example, from about 150°F to about 165°F during the washing step, and from about 170°F to about 185°F during the rinsing step.
[0283] Additionally, the method of use of the activated composition according to the present invention is also suitable for CIP and / or COP methods to replace the use of block detergents that leave hard water residues on the treated surface. The method of use is desirable in additional applications where industry standards focus on the quality of the treated surface, so that the prevention of hard water scale accumulation provided by the activated composition of the present invention is also desirable. Such applications may include, but are not limited to, vehicle care, industrial, hospital and textile care.
[0284] Additional examples of use applications for the activated compositions include, for example, alkaline detergents effective as grill and oven cleaners, dishwashing detergents, laundry detergents, laundry prepregs, drain cleaners, hard surface cleaners, surgical instrument cleaners, transportation vehicle cleaning, vehicle cleaners, dishwashing prepregs, dishwashing detergents, beverage machine cleaners, concrete cleaners, building exterior cleaners, metal cleaners, floor polishes, degreasers, and burnt-on soil removers. In a variety of these applications, cleaning compositions with very high alkalinity are most desirable and effective; however, the damage caused by hard water scale accumulation is undesirable.
[0285] Generally, various use applications can be applied by dipping, spraying, immersing or otherwise contacting the surface with the use solution for a sufficient time, including from a few seconds to several minutes or longer. The method can further include wiping or draining excess solution from the surface.
[0286] Decolorization
[0287] The activated quaternary ammonium compound and anionic surfactant (or polymer / chelating agent) composition of the present invention is further suitable for use in various applications and methods requiring decolorization. Generally speaking, the composition can be used for decolorization by dipping, spraying, immersing or otherwise contacting the surface with the use solution for a sufficient time (including a few seconds to a few minutes or longer) and wiping or draining the excess solution away from the equipment. The composition of the present invention can be further used by spraying or wiping the food processing surface with the use solution, keeping the surface wet for a time sufficient to disinfect the surface, and removing the excess solution by wiping, vertical draining, vacuuming, etc.
[0288] The activating compositions obtained according to the present invention can also be used in methods for decolorizing various hard surfaces, such as institutional type equipment, utensils, tableware, health care equipment or tools, and other hard surfaces.
[0289] Laundry Application
[0290] In some aspects, the compounds and compositions can also be used to disinfect contaminated articles, such as textiles. In other aspects, the compounds and compositions can also be used to clean and sterilize articles such as textiles. The articles are contacted with the compounds of the present invention for a period of time at a use temperature of about 4°C to 80°C to effectively disinfect, sterilize and / or sterilize the articles. In some embodiments, the compositions of the present invention can be used to disinfect articles at a temperature of about 30°C to about 50°C or about 40°C. For example, in some embodiments, the compositions of the present invention can be injected into the washing water or rinse water of a washing machine and contacted with the contaminated fabric for a sufficient time to disinfect the fabric. In some embodiments, the contaminated fabric is contacted with the compounds and compositions of the present invention for about 5 to about 30 minutes. The excess solution can then be removed by rinsing or centrifuging the fabric.
[0291] The composition of the present invention can be used alone to treat articles, such as textiles, or can be used in combination with conventional detergents suitable for articles to be treated. The composition of the present invention can be used together with conventional detergents in a variety of ways, for example, the composition of the present invention can be formulated with conventional detergents. In other embodiments, the composition of the present invention can be used to treat articles as an additive separated from conventional detergents. When used as a separate additive, the compounds and compositions of the present invention can contact the articles to be treated at any time. For example, the composition of the present invention can contact the articles before, after or substantially simultaneously with the selected detergent.
[0292] In some embodiments, when used as a disinfectant / sterilizer for laundry applications, the compounds of the present invention will be present in the composition at a concentration of about 5 ppm to about 1000 ppm. In other embodiments, when used as a disinfectant / sterilizer for laundry applications, the compounds of the present invention or mixtures of compounds will be present in the composition at about 25 ppm to about 100 ppm. In other embodiments, when used as a disinfectant / sterilizer in laundry applications, the compounds of the present invention or mixtures thereof will be present at about 20, about 40, about 60, or about 80 ppm.
[0293] Methods of using the inactivated antimicrobial compositions of the present invention
[0294] Water treatment applications
[0295] The inactivated compositions can be used for a variety of purposes, including, for example, treating water sources and water treatment applications. In various applications, water sources and waste sources contain residual antimicrobial agents, including quaternary ammonium compounds.
[0296] In one embodiment, the inactivated composition can be used in a water treatment method connected to a water pipe of a house or business. The inactivated composition can be used in a pipeline before a hot water heater or after a hot water heater. In other aspects, the present invention provides an inactivated composition for a cleaning process.
[0297] In other embodiments, once water is treated, treated water is provided to an automatic washing machine, such as an automatic dishwashing machine or dishwasher, a vehicle washing system, an instrument washer, a cleaning system in situ, a food processing cleaning system, a bottle washer, and an automatic washing machine from the treated water delivery line of the equipment. Alternatively, treated water can be used in a manual washing system. Any automatic or manual washing machine that will benefit from using the water treated according to the method of the invention can be used. The treated water is then combined with the detergent composition in the washing machine to provide a use composition. Any detergent composition can be used in the system of the present invention, such as a cleaning composition, a rinse agent composition, or a drying agent composition. The article to be cleaned is then contacted with the use solution in the automatic washing machine to clean them.
[0298] The water treatment method and system of the present invention can be used in a variety of industrial and domestic applications. The water treatment method and system can be used in a residential environment or a commercial environment, for example, in a restaurant, a hotel, a hospital. For example, the water treatment methods, systems or apparatus of the present invention can be used in the following: warewashing applications, such as washing dining and cooking utensils and other hard surfaces, such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors and floors; laundry applications, such as for treating water used in automatic textile washing machines during the pretreatment, washing, acidification, softening and / or rinsing stages; vehicle care applications, such as for treating water used for pre-rinsing (e.g., alkaline prepregs and / or low pH prepregs), washing, polishing and rinsing vehicles; industrial applications, such as cooling towers, boilers, industrial equipment including heat exchangers; food service applications, such as for treating water pipes for coffee and tea brewers, espresso machines, ice machines, pasta cookers, water heaters, steamers and / or proofing machines; health care equipment care applications, such as soaking, cleaning and / or rinsing surgical instruments, treating the feed water of autoclaves; and feed water for various applications, such as humidifiers, hot tubs and swimming pools
[0299] In certain embodiments, the water treatment method can be applied when used. That is, the water treatment method, system or equipment can be applied to the upstream water source of the application such as the washing system. In certain embodiments, the water treatment will be applied before the desired water source end use. For example, the equipment of the present invention can be used to connect to the water pipe of household or restaurant electrical appliances such as coffee machine, espresso machine, ice machine. The equipment adopting the inventive method can be located in the washing system. For example, it can also be included as a part of the electrical appliance using the water source, for example, a water treatment system, coffee machine, ice machine or any other system that can benefit from the use of treated water in an automatic or manual washing system.
[0300] In various applications, the anionic surfactants disclosed in accordance with the present invention can be added directly to a water source or waste source containing residual quaternary ammonium compounds. The application of anionic surfactants in accordance with the present invention can be used to inactivate quaternary ammonium compounds in a water source or waste stream that might otherwise negatively interfere with or destroy bacteria or other compounds therein. Therefore, it may be desirable to inactivate quaternary ammonium compounds in a water source or waste stream by means of an in situ inactivation antimicrobial composition.
[0301] Kits for use in applications
[0302] According to various applications of the composition according to the present invention, a test kit for dosing the composition according to the present invention (including the quaternary ammonium composition of inactivation or activation) can be provided. In specific applications, the inactivated composition can be provided by using a test kit according to an embodiment of the present invention. The test kit for dosing and / or providing the deactivated quaternary ammonium composition according to the present invention may comprise the following, be composed of the following and / or be essentially composed of the following: a quaternary ammonium compound and an anionic surfactant (and / or a chelating agent and / or a polymer). Alternatively, the test kit may comprise the following, be composed of the following and / or be essentially composed of the following: anionic surfactant (and / or a chelating agent and / or a polymer), for dosing with the quaternary ammonium compound in the use application. The test kit may further comprise a measuring device and / or a dosing device.
[0303] In one aspect, a kit is used to dose an appropriate amount of anionic surfactant (and / or chelating agent and / or polymer) to inactivate the quaternary ammonium compound. In one aspect, it may be desirable to dose or provide a surface and / or antimicrobial inactivating amount of anionic surfactant (and / or chelating agent and / or polymer). In an embodiment, it is desirable to reduce the surface activity (higher surface tension) compared to another combination of anionic surfactant (and / or chelating agent and / or polymer) and quaternary ammonium compound, such that the low surface activity neutralizes or inactivates the antimicrobial efficacy of the quaternary ammonium compound.
[0304] According to some embodiments of using the kit, the composition and / or system with quaternary ammonium compound is quantitatively dosed with anionic surfactant (and / or chelating agent and / or polymer) in a molar ratio-dependent amount. In one aspect, the composition includes about one mole: molar ratio of quaternary ammonium compound and anionic surfactant. In other aspects, the composition includes quaternary ammonium compound and anionic surfactant at most about 10 to about 1 molar ratio. In other aspects, the composition includes quaternary ammonium compound and anionic surfactant at most about 1 to about 10 molar ratios, or any combination thereof. In another embodiment, the molar ratio of anionic surfactant to quaternary ammonium of the antimicrobial composition is about 1 mole of anionic surfactant to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of anionic surfactant to quaternary ammonium compound of the antimicrobial composition is about 1.5 moles of anionic surfactant to about 1 mole of quaternary ammonium compound. In another embodiment, the molar ratio of anionic surfactant to quaternary ammonium compound of the antimicrobial composition is about 1 mole of anionic surfactant to about 10 moles of quaternary ammonium compound. In another embodiment, the molar ratio of anionic surfactant to quaternary ammonium compound of the antimicrobial composition is about 2 moles of anionic surfactant to about 1 mole of quaternary ammonium compound. In each example, the kit provides molar ratios for inactivating quaternary ammonium compounds.
[0305] The kit may further comprise additional elements. For example, the kit may further comprise instructions for using the inactivated composition. The instructions included in the kit may be attached to the packaging material or may be included as a packaging insert. Although the instructions are typically written or printed materials, they are not limited thereto. The present disclosure contemplates any medium capable of storing such instructions and transmitting them to an end user. Such media include, but are not limited to, electronic storage media (e.g., disks, tapes, cassettes, chips), optical media (e.g., CDs, DVDs), etc. As used herein, the term "instructions" may include the address of an Internet site providing the instructions. The various components of the kit are optionally provided in suitable containers, such as bottles, jars, or vials, as needed.
[0306] Examples
[0307] Embodiments of the present invention are further defined in the following non-limiting examples. It should be understood that although these examples indicate certain embodiments of the present invention, they are only given by way of illustration. From the above discussion and these examples, those skilled in the art can determine the basic characteristics of the present invention, and can make various changes and modifications to the embodiments of the present invention without departing from its spirit and scope, so that it is suitable for various purposes and conditions. Therefore, in addition to those shown and described herein, various modifications of the embodiments of the present invention will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to also fall within the scope of the appended claims.
[0308] BARDAC 2250R and 2280R as used in the examples herein are purchased from Lonza and are each double chain dimethyl ammonium chloride. Bardac 2250R includes 50% by weight didecyl dimethyl ammonium chloride, 10% by weight ethanol and 40% by weight water. Bardac 2280R includes 80% by weight didecyl dimethyl ammonium chloride, 10% by weight ethanol and 10% by weight water. The structures of various other commercially available quaternary ammonium compounds and raw materials are listed in Table 2.
[0309] Table 2
[0310]
[0311] Example 1
[0312] Dynamic surface tension of Bardac 205M and anionic surfactants
[0313] The SITA Scientific Series T60 measures the dynamic surface tension of liquids up to the semi-static range. Bubbles are generated from a capillary of known radius. The bubble pressure is measured as a function of the bubble lifetime, which can be related to the surface tension according to the Young-Laplace equation. Dynamic surface tension gives an understanding of the dynamic behavior of surfactants and other surface-active compounds under dynamic conditions, i.e. how quickly the surfactant reaches the surface. The dynamic surface tension behavior of surfactants is particularly important in applications where a fast-responding surfactant is required, for example, in the short rinse cycle of automatic dishwashing.
[0314] Equipment and Materials
[0315] 1.SITA T60 (Sita Messtechnik, Germany)
[0316] 2. Oil bath with stirring bar
[0317] 3. Heat and stir the plate
[0318] 4. Glass beaker
[0319] 5. Glass vial (20mL)
[0320] The SITA Scientific Series T60 was calibrated with deionized water. The clean water sample after calibration should have a surface tension of 72.0 ± 1.0 mN / m (depending on mass and temperature). After calibration, the SITA was programmed to take readings at the desired time intervals (i.e., 0.3, 1.6, 3.0, 9.1 seconds). To determine the effect of a 9:1 mass ratio of quaternary ammonium compound to anionic surfactant on surface activity, the following composition was prepared.
[0321] Bardac 205M is a commercially available quaternary ammonium compound from Lonza having 20 wt% active alkyl dimethyl benzyl ammonium chloride, 15 wt% octyl decyl dimethyl ammonium chloride, 6 wt% dioctyl dimethyl ammonium chloride and 9 wt% dodecyl dimethyl ammonium chloride. The Bardac 205M quaternary ammonium compound blend further includes inert ingredients of 10 wt% ethanol and 40 wt% water. The samples of this example were prepared using 100 ppm Bardac 205M. Bardac 205M was mixed with Plurafac SL-42 (comparative nonionic surfactant - ethoxylated, propoxylated C6 to C10 extended chain surfactant, anionic surfactant purchased from BASF), Surfonic PEA (amine surfactant - neutral or cationic depending on pH - comparative ethoxylated etheramine, purchased from Huntsman Chemical), X-AES (anionic surfactant C 12-14 -(PO) 16 -(EO)2-sulfate, purchased from Huntsman Chemical), SLES (anionic surfactant - sodium lauryl ether sulfate) and Marlowet 4539 (C9 alcohol polyethylene glycol ether carboxylic acid purchased from Sasol).
[0322] Transfer 10-15mL to a 20mL vial and immerse in an oil bath heated to 72°C (160°F) ± 2°C. Allow the samples to equilibrate for 10-15 minutes. Remove the samples from the oil bath individually and test them in the SITA. After testing each sample, perform the SITA cleaning procedure and then check the surface tension of the deionized water to ensure that the SITA is adequately clean. If the deionized water measurement is not within the range of 72.0 ± 1.0 mN / m, perform the cleaning procedure again. Record the surface tension (mN / m) and bubble life at 160°F and the experimental data is provided at Figure 1 middle.
[0323] Figure 1The results shown provide for most of the quaternary ammonium-anionic surfactant blends tested, and an increase in dynamic surface activity is observed. As mentioned in the entire example, the increase in dynamic surface activity is shown by the reduction of surface tension in the bubble life time process depicted in the figure. Specifically, compared with independent Bardac 205M, Bardac 205M+Marlowet4539 and Bardac 205M+Colatrope INC demonstrate a significant increase in surface activity. Interestingly, quaternary ammonium salt-nonionic surfactant blends, Bardac 205M+Plurafac SL-42 and Bardac205M+Surfonic PEA, only demonstrate slight synergy. However, Bardac 205M and X-AES or SLES (both are longer alkyl alkoxylated sulfates) do not demonstrate the synergistic enhancement of surface activity observed in the case of other quaternary ammonium salt-anionic surfactant blends.
[0324] Example 2
[0325] Dynamic surface tension of blends of BBardac 205M and anionic sulfate surfactants
[0326] To further examine the surface activity of quaternary ammonium compounds with different mole: mole ratios of anionic sulfate surfactants, the procedure described in Example 1 was followed. Bardac 205M as described above was mixed with SLS (sodium lauryl sulfate), SLES (sodium lauryl ether sulfate), X-AES (C 12-14 (PO) 16 -(EO)2-sulfate, available from Huntsman Chemical) and Stepanol EH-S (sodium 2-ethylhexyl sulfate, available from Stepan). The results are provided in Figure 2 middle.
[0327] Figure 2 The results shown show that the combinations exhibit chain length dependent surface activity compared to the quaternary ammonium compound (Bardac 205M) alone (at this molar ratio). For example, Bardac 205M in combination with EH-S or X-AES or NAS-FAL all show a rapid increase in surface activity. However, Bardac 205M, SLS or SLES blends result in an overall increase in surface activity compared to Bardac 205M alone, but show slower kinetics compared to the other blends tested, suggesting an inactivation of antimicrobial activity.
[0328] It is known that quaternary ammonium compounds themselves have excellent micro-efficacy, however, they are not very surface-active materials. When quaternary ammonium compounds are paired with suitable anionic surfactants, the combination is more surface-active than two individual components. The synergistic effect of antimicrobial efficacy activation is very relevant to the dynamic surface tension synergy. Without being bound by theory, we believe that the complex or ion pair between quaternary ammonium salts and anionic surfactants has a very similar effective cross-sectional area for both hydrophilic and hydrophobic substances due to charge neutralization, making the stacking in the interface very favorable unless they are no longer soluble. The formation of the complex is so favorable that it can overcome the cohesive force between the fatty acid molecules.
[0329] Example 3
[0330] Dynamic surface tension of Bardac 205M and anionic carboxylate surfactants by mole-to-mole ratio
[0331] The dynamic surface tension of quaternary ammonium compounds and different anionic carboxylate surfactants in mole: mole ratios were tested according to the procedure of Example 1. The following solutions were prepared: Bardac 205M at a concentration of 100 ppm as described above was combined with 48 ppm ethylhexanoic acid, 52 ppm Colatrope INC (sodium alkanoate, purchased from Colonial Chemical Inc.), 48 ppm caprylic acid, 116 ppm Marolwet 4539 SLS (C9-alcohol polyglycol ether carboxylic acid purchased from Sasol), 56 ppm capric acid and 65 ppm lauric acid in a mole: mole ratio, respectively. These data are provided in Figure 3.
[0332] Figure 3A The results shown indicate that the combination of a carboxylated anionic surfactant and a quaternary ammonium compound has reduced surface activity compared to the quaternary ammonium compound alone (Bardac 205M). The combination of Bardac 205M and capric acid appears to be particularly suitable for increasing dynamic surface activity compared to Bardac 205M alone. Figure 3A It can be seen that ethylhexanoic acid, Colatrope INC, caprylic acid, Marolwet 4539 SLS, capric acid, lauric acid and oleic acid are all able to increase the surface activity to varying degrees compared to Bardac 205M alone.
[0333] Further dynamic surface tension analysis was performed using the above procedure. The following solutions were prepared: Bardac 205M at a concentration of 100 ppm as described above was combined with varying concentrations of capric acid (10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm and 70 ppm) or 100 ppm of the caprate salt alone. The results are provided in Figure 3B middle.
[0334] As can be seen from these results, the caprate salt alone and Bardac 205M alone exhibit limited surface activity. However, when each is combined, a significant increase in surface activity is observed. Furthermore, the observed increase in surface activity of the quaternary ammonium salt-capric acid blend occurs in a dose-dependent manner. That is, the observed synergistic trend occurs as a function of anionic surfactant concentration.
[0335] Advantageously, the medium-chain long carboxylated anionic surfactants show a particularly unusual interaction with quaternary ammonium salts. In a preferred aspect of the present invention, capric acid is used in an antimicrobial composition. Capric acid is a solid material at room temperature with extremely low solubility, but is freely soluble in (slightly acidic) quaternary ammonium salts without adding any alkalinity. Moreover, under a wide range of pH, the complex formed has a very similar strong surface activity, thereby providing unexpected results. As shown in the figure, the surface activity is independent of pH.
[0336] Example 4
[0337] Dynamic surface tension of Bardac 205M and anionic sulfate surfactant combinations
[0338] The surface tension of quaternary ammonium compounds with different sulfate-based anionic surfactants at mole: mole ratios was examined following the procedure outlined in Example 1. The following solutions were prepared. Bardac 205M at a concentration of 100 ppm as described above was combined with 84 ppm of SLS (sodium lauryl sulfate), NAS-FAL (sodium n-octane sulfonate), and Stepanol EH-S (sodium 2-ethylhexyl sulfate, available from Stepan) each at a mole: mole ratio. These data are provided at Figure 4A , 4B and 4C.
[0339] Figure 4A The results shown indicate that the mole:mole combination of sodium lauryl sulfate and the quaternary ammonium Bardac 205M exhibits reduced dynamic surface tension compared to either the quaternary ammonium compound or the anionic surfactant alone. Figure 4B and Figure 4C When observing the results from the experiment, the blend of Bardac 205M + SLS showed a slower decrease in surface tension during the first half of the bubble life and then a rapid decrease in surface tension during the second half of the experiment.
[0340] Figure 4B The results shown are similar to Figure 4AThe results are consistent with those of the present invention. And it is shown that the mole: mole combination of sodium n-octane sulfonate and quaternary ammonium Bardac 205M shows a synergistic trend in reducing surface tension compared with the quaternary ammonium compound or anionic surfactant alone. Figure 4A In contrast to the results, a rapid decrease in surface tension was observed.
[0341] Figure 4C The results shown are similar to Figure 4A and Figure 4B This is consistent with the observations seen in Figure 4C It can be seen that the mole: mole combination of sodium 2-ethylhexyl sulfate and quaternary ammonium Bardac 205M also shows a synergistic reduction in surface tension compared to the quaternary ammonium compound or anionic surfactant alone. Figure 4C The kinetic decrease in surface tension observed in Figure 4B The dynamics shown.
[0342] Example 5
[0343] Study on pH of quaternary ammonium-anionic surfactant compounds
[0344] To determine the effect of pH on the observed synergistic enhancement of surface activity between the mole: mole ratio of quaternary ammonium compounds and carboxylate-based anionic surfactants, the procedure outlined in Example 1 was used, except that solutions were prepared at various pHs. Bardac 205M quaternary ammonium was combined with Marlowet 4539 (C9-alcohol polyglycol ether carboxylic acid purchased from Sasol) on a mole: mole basis. The pH of the combination was adjusted using HCl and the surface tension of the combination at pH 4.0, 6.0, 9.0 and 9.5 was plotted for comparison with 100 ppm Bardac 205M and 116 ppm Marlowet 4539. The results are provided in Figure 5A middle.
[0345] The data indicate that the synergy observed between Bardac 205M and Marlowet 4539 is maintained at a variety of pHs. The surface tension of solutions of Bardac 205M combined with Marlowet 4539 decreases at comparable rates regardless of pH. Although pH does appear to affect the surface tension of Marlowet 4539 solutions alone, solutions at pH 4.5 are more surface active than solutions at pH 10.0.
[0346] A further study examined the effect of pH on the dynamic surface tension of a combination of 100 ppm Bardac 205M quaternary ammonium compound and 56 ppm capric acid in a mole: mole ratio as described above. The pH of the combination was adjusted and the dynamic surface tension of the combination was observed at pH 3.6, 4.94, 6, 7, 7.75, 9 and 10.2. The results are provided in Figure 5B It is shown that the dynamic surface tension of the mole: mole combination of quaternary ammonium and capric acid is independent of pH. Therefore, even if the pH changes, the dynamic surface tension does not change. Figure 5A The data shown in are consistent.
[0347] Example 6
[0348] Antimicrobial efficacy of quaternary anionic surfactant compositions
[0349] Using the antimicrobial suspension test, the antimicrobial efficacy of quaternary ammonium compounds combined with anionic surfactants was shown in Fig. 6A The combination includes 7.5 to 1 mass ratio of 300 ppm active Bardac 205M to each of SLS, SLES, X-AES, NAS-FAL, ethylhexyl sulfate (EH-S), Colatrope INC and M4539. The same anionic surfactant is combined with 300 ppm of Bardac 205M in a mole: mole ratio. Bardac 205M is commercially available from Lonza and has 20 wt% active alkyl dimethyl benzyl ammonium chloride, 15 wt% octyl decyl dimethyl ammonium chloride, 6 wt% dioctyl dimethyl ammonium chloride and 9 wt% dodecyl dimethyl ammonium chloride. The Bardac 205M quaternary ammonium compound blend further includes an inert component of 10 wt% ethanol and 40 wt% water.
[0350] Fig. 6AThe results shown indicate that a 7.5 / 1 mass ratio of Bardac 205M with SLS, SLES, X-AES, EH-S and M4539 provided the highest bacterial log reduction against E. coli. The combination of Bardac 205M with SLS, SLES and X-AES also provided good antimicrobial efficacy against Staphylococcus. Additionally, data analyzing the mole: mole ratios of Bardac 205M provided that the combination of Cola INC and M4539 showed the highest log reduction against E. coli. The combination of Bardac 205M with NAS-FAL, EH-S, Colatrope INC and M4539 also provided good antimicrobial efficacy against Staphylococcus. While quaternary ammonium compositions alone are known to be very good antimicrobial agents, quaternary ammonium compounds are not very surface active compositions, limiting their use as surfactants such as disinfectants. These results indicate that antimicrobial efficacy is maintained in quaternary ammonium-anionic surfactant compositions, while the surface activity of the combination is greatly enhanced compared to the quaternary ammonium compounds alone (see Figure 1-4C ).
[0351] A further study of the antimicrobial efficacy of quaternary ammonium compounds in combination with anionic surfactants was conducted at pH 8.0 as described above. Combinations included 300 ppm, 150 ppm and 75 ppm active Bardac 205M in a 7.5 to 1 mass ratio with each of SLS, SLES, X-AES, NAS-FAL, ethylhexyl sulfate (EH-S), 2-ethylhexanoate, Colatrope INC, caprylate, Marlowet 4539 and caprate. Bardac 205M is commercially available from Lonza and its composition is described above. The results are provided in Figure 6B middle.
[0352] The results showed that Bardac 205M with SLS, SLES, X-AES, NAS-FAL, ethylhexyl sulfate, 2-ethylhexanoate, Colatrope INC, octanoate, Marlowet 4539 and decanoate in a 7.5 / 1 mass ratio provided the highest bacterial log reduction at 300 ppm of quaternary ammonium compounds. Bardac 205M with SLES and X-AES, 2-ethylhexanoate, Colatrope INC, octanoate, Marlowet 4539 and decanoate also provided good antimicrobial efficacy at 150 ppm of quaternary ammonium compounds.
[0353] Example 7
[0354] Antimicrobial efficacy of quaternary anionic surfactant compositions
[0355] The antimicrobial efficacy of the composition of the present invention against Escherichia coli is shown in Figure 7 Compositions were tested with 300 ppm of Bardac quaternary ammonium compounds combined with each of SLS, SLES, X-AES, NAS-FAL, ethylhexyl sulfate (EH-S), 2-ethylhexanoate, Colatrope INC, caprylate, Marlowet 4539, and caprate in a mole: mole ratio. The pH of all tested compositions was 8.
[0356] Figure 8 The results shown indicate that the highest bacterial log reduction occurred with the combination of Bardac 205M with 2-ethylhexanoate, Colatrope INC, and Octanoate. The combination of Bardac 205M quaternary ammonium and Marlowet 4539 exhibited less bacterial kill than the other combinations.
[0357] The results further indicate that rather than enhancing antimicrobial efficacy, some interactions contribute to reducing the antimicrobial efficacy of the quaternary ammonium. Specifically, the quaternary ammonium combined with each of SLS, SLES, X-AES, NSA-FAL, ethylhexyl sulfate, and decanoate all served to reduce the antimicrobial activity of the quaternary ammonium compound with respect to killing E. coli. The interactions between these anionic surfactants and quaternary ammonium compounds are believed to be destructive or exhibit an 'inactivation' effect.
[0358] Without being bound by theory, the present invention proves that the complex or ion pair between the quaternary ammonium salt and the anionic surfactant has very similar effective cross-sectional area to both hydrophilic and hydrophobic substances due to charge neutralization, making the accumulation in the interface very favorable, unless they are no longer soluble. The formation of the complex is so favorable that it can overcome the cohesive force between the fatty acid molecules. This test proves that the stronger ionic bonding found in sulfate or sulfonate anionic surfactant plays the effect of neutralization, reducing solubility and / or deactivating the antimicrobial quaternary ammonium compound. It is believed in addition that, due to weaker ionic bonding, the carboxylated anionic surfactant seems to strengthen or activate the antimicrobial quaternary ammonium compound. Other weakly acidic anionic surfactants such as phosphate esters also may play the effect of activating antimicrobial activity.
[0359] Example 8
[0360] Antimicrobial efficacy of quaternary anionic surfactant compositions
[0361] The antimicrobial efficacy of quaternary ammonium compounds combined with anionic surfactants against Staphylococcus aureus at pH 8 is shown in Figure 8The combinations included 300 ppm, 150 ppm and 75 ppm active Bardac 205M in a 7.5 to 1 mass ratio with each of X-AES, ethylhexyl sulfate (EH-S), 2-ethylhexanoate, Colatrope INC, caprylate, Marlowet 4539 and caprate.
[0362] Figure 8 The results shown indicate that at pH 8, a 7.5:1 mass ratio of Bardac 205M to X-AES, ethylhexyl sulfate (EH-S), 2-ethylhexanoate, Colatrope INC, octanoate, Marlowet 4539, and decanoate all exhibited excellent killing properties against Staphylococci, regardless of the concentration of the quaternary ammonium compound. As noted above, disinfecting quaternary ammonium compounds are not very surface active by themselves. The exemplary compositions of the present invention demonstrate that quaternary ammonium salt-anionic surfactant complexes become more surface active while maintaining antimicrobial efficacy.
[0363] Example 9
[0364] Solubility of quaternary ammonium-anionic surfactant combinations
[0365] The compositions of the present invention were prepared using a 1 wt% Bardac 205M solution and a sulfate-based anionic surfactant or a carboxylate-based anionic surfactant at a mole: mole ratio according to the table below, and the appearance behavior (e.g., precipitation) in the sample cup was observed. Each resulting combination was observed to determine whether a single phase was produced, whether the composition was clear or turbid, and whether precipitation occurred. The results are provided in Table 3.
[0366] Table 3
[0367]
[0368] Example 10
[0369] Antimicrobial efficacy - suspension test
[0370] The antimicrobial efficacy of Bardac 205M-decanoic acid blends against Staphylococcus aureus was evaluated using the Food Contact Disinfectant Test Method at pH 4.0 or pH 8.0 and under the conditions outlined in Tables 4A-4B. The following solutions were examined: 50 ppm Bardac 205M, 50 ppm Bardac 205M + 28 ppm decanoic acid, 75 ppm Bardac 205M, and 75 ppm Bardac 205M + 42 ppm decanoic acid. The results are provided in Tables 4C and Fig.9A middle.
[0371] Table 4A
[0372]
[0373] Table 4B
[0374] Test system: Pseudomonas aeruginosa ATCC 15442 (0.206A@620nm) Test substance diluent: EN synthetic hard water (approximately 375 ppm hardness), pH 6.95 Interfering substances: EN Clean Dirt Conditions Exposure time: 5 minutes Neutralizer: 8mL Chambers fermentation broth + 1mL sterile water Test temperature: 20℃ Plate medium: EN TSA Incubation: 35℃, 48 hours
[0375]
[0376] Another test was conducted using the above procedure to determine the antimicrobial efficacy of Bardac 205M-decanoic acid blend against E. coli. The following solutions were examined: 50 ppm Bardac 205M, 50 ppm Bardac 205M + 28 ppm decanoic acid, 75 ppm Bardac 205M, and 75 ppm Bardac 205M + 42 ppm decanoic acid. The results are provided in Fig. 9B middle.
[0377] It is known that quats have reduced efficacy in hard water compared to low water hardness conditions (DI, 5 gpg, 17 gpg). The quat / anionic surfactant synergy reduces the quat concentration requirement for full EPA efficacy and in slightly acidic media (pH of about 5 and lower). Without water hardness, the quat / anionic surfactant synergy works at common pH and low concentrations of quat (less than 50 ppm).
[0378] Example 11
[0379] Antimicrobial efficacy - hard water
[0380] The antimicrobial efficacy of quaternary ammonium compounds and anionic surfactants against Staphylococcus aureus and Escherichia coli was evaluated as shown in Table 5 A. The water control, 1% Bardac quat control, and 1% Formulation #1 provided in Table 5B were examined at pH 7.0.
[0381] Table 5A
[0382]
[0383] Table 5B
[0384] Formulation #1 weight% Bardac quaternary ammonium salt 13.75 Decanoic acid 2.5 Citric Acid 30 water 53.75
[0385] The results are provided in Tables 6-7 below.
[0386] Table 6
[0387]
[0388] Table 7
[0389]
[0390] The results shown in Tables 6-7 above indicate that quaternary ammonium salts or quaternary ammonium salt / anionic surfactant blends have difficulty killing microorganisms, especially E. coli, when they are suspended in hard water and neutral pH conditions.
[0391] Additional tests were performed using the above procedure, except that the pH of the solutions were prepared at either pH 7.0 or pH 4.5. The results are provided in Tables 8-9.
[0392] Table 8
[0393]
[0394] Table 9
[0395]
[0396]
[0397] The results shown in Tables 8-9 show that the water hardness problem is overcome by making the pH slightly acidic (pH about 4.5) in the suspension test. The lower pH helps the quat / capric acid more than the quat alone. Even at 500 ppm water hardness, the efficacy of the quat / capric acid is radically improved at pH 4.5 compared to pH 7.0, indicating that the synergistic quat / capric acid provides complete kill at 75 ppm quat level, while providing less than 5 log kill (no disinfection) for 100 ppm quat alone.
[0398] Example 12
[0399] Third Sink Disinfectant
[0400] The antimicrobial efficacy of quaternary ammonium compounds and anionic surfactants as third sink disinfectants was evaluated as shown in Table 10.
[0401] Table 10
[0402]
[0403] The results are provided in Table 11 below.
[0404]
[0405]
[0406] These results demonstrate that at 500 ppm water hardness, decanoate (anionic form at neutral pH) "inactivates" quaternary ammonium salts, while decanoic acid (protonated form at pH 4.5) "synergizes" with quaternary ammonium salts. However, alcohol ethoxycarboxylates (Emulsogen CNO) do not inactivate quaternary ammonium salts at neutral pH. Without being bound by theory, we believe that at neutral pH, the carboxyl groups on the outer wall of microorganisms such as E. coli are the primary attraction points for quaternary ammonium salts (opposite charge attraction). However, water hardness cations (Ca ++ and Mg ++ ) more attractive to them, effectively "blocking" the quaternary ammonium compounds. The quaternary ammonium salt / carboxylic acid combination according to the present invention provides further inactivation because the decanoate can be attached to the Ca2+ of the microbial outer wall. ++ and Mg ++ Attracting, making them more hydrophobic (e.g. similar to soap scum). In one aspect, this further demonstrates why alcohol ethoxy carboxylates are better than decanoates, as they are less likely to form lime soaps. However, when the pH is lowered to about 4.5, some of the carboxyl groups on the microbial exosomes are protonated, opening them up to quaternary ammonium salts, and even more to the more fundamentally surface-active quaternary ammonium / decanoic acid.
[0407] Example 13
[0408] Food Contact Disinfection - Hard Water pH Study
[0409] Additional testing was performed to analyze the antimicrobial efficacy of the quaternary ammonium salt-anionic surfactant blends under various pH conditions. Compositions according to the present invention (and controls without quaternary ammonium compounds and anionic surfactants) and the results are provided in Tables 12-13.
[0410] Table 12
[0411]
[0412] These data indicate a pH cut-off at approximately pH 5.
[0413] Table 13
[0414]
[0415] These data clearly show that the quaternary ammonium salt / capric acid synergistic effect at acidic pH at lower quaternary ammonium salt levels.
[0416] Example 14
[0417] Hard Surface Disinfection - Hard Water pH Study
[0418] Additional testing was performed to analyze the antimicrobial efficacy of the quaternary ammonium salt-anionic surfactant mixtures with hard water at various pH conditions. The compositions (and controls without quaternary ammonium compounds and anionic surfactants), evaluation conditions, and results are provided in Tables 14-18.
[0419] Table 14
[0420] Inoculum number (CFU / mL) Plate 1 Plate 2 average value Escherichia coli ATCC 11229 125e6 168e6 1.50E+08
[0421] Table 15
[0422]
[0423] Table 16
[0424]
[0425] Table 17
[0426]
[0427]
[0428] Table 18
[0429]
[0430] As shown in Tables 17-18, the unexpected results show that even in very hard water conditions (15 grains / gallon, or 2565 ppm water hardness), the combination of quaternary ammonium salt / anionic surfactant composition, as shown by quaternary ammonium salt / decanoic acid, provides a 5 log kill of the more challenging E. coli at levels as low as 50 ppm dioctyl quaternary ammonium salt. This confirms that quaternary ammonium salt / anionic surfactant is very effective against microorganisms deposited on hard surfaces even in very hard water conditions and at pH neutral or higher. Sampling from the oil sump confirmed that the microorganisms were killed, not just removed from the surface.
[0431] Example 15
[0432] High Foaming Non-Molar Ratio Research
[0433] Additional tests were performed to analyze non-molar ratios of the compositions of the present invention. The compositions, conditions, and results evaluated are provided in Table 19.
[0434] Table 19
[0435]
[0436] These results demonstrate that many non-molar quaternary ammonium salt / anionic surfactant combinations (more quaternary ammonium salt than anionic surfactant) pass the 500 ppm water hardness suspension test at neutral and acidic pH, according to the molar ratio of the composition of the present invention. However, the surfactant benefit becomes increasingly less as the composition moves away from the molar ratio, indicating a trade-off between pH dependency and desired surfactant / wetting.
[0437] Example 16
[0438] Dynamic surface tension of Bardac LF80 and anionic polymers
[0439] The SITA Scientific Series T60 measures the dynamic surface tension of liquids up to the semi-static range. Bubbles are generated from a capillary of known radius. The bubble pressure is measured as a function of the bubble lifetime, which can be related to the surface tension according to the Young-Laplace equation. Dynamic surface tension gives an understanding of the dynamic behavior of surfactants and other surface-active compounds under dynamic conditions, i.e. how quickly the surfactant reaches the surface. The dynamic surface tension behavior of surfactants is particularly important in applications where a fast-responding surfactant is required, for example, in the short rinse cycle of automatic dishwashing.
[0440] Equipment and Materials
[0441] 1. SITA T60 (Sita Messtechnik, Germany)
[0442] 2. Oil bath with stirring bar
[0443] 3. Heat and stir the plate
[0444] 4. Glass beaker
[0445] 5. Glass vial (20mL)
[0446] The SITA Scientific Series T60 is calibrated with deionized water. The clean water sample after calibration should have a surface tension of 72.0 ± 1.0 mN / m (depending on mass and temperature). After calibration, SITA is programmed to take readings at the desired time intervals (i.e., 0.3, 1.6, 3.0, 9.1 seconds). To determine the effect of Bardac LF80 and different concentrations of Acusol 445 on dynamic surface tension, the following five solutions were analyzed at pH 7.0; 100 ppm Bardac LF80; 10 ppm Acusol 445; 100 ppm Bardac LF80 + 10 ppm Acusol 445; 100 ppm Bardac LF80 + 30 ppm Acusol 445; and 100 ppm Bardac LF80 + 75 ppm Acusol 445.
[0447] Transfer 10-15mL to a 20mL vial and immerse in an oil bath heated to 72°C (160°F) ± 2°C. Allow the samples to equilibrate for 10-15 minutes. Remove the samples from the oil bath individually and test them in the SITA. After testing each sample, perform the SITA cleaning procedure and then check the surface tension of the deionized water to ensure that the SITA is adequately clean. If the deionized water measurement is not within the range of 72.0 ± 1.0 mN / m, perform the cleaning procedure again. Record the surface tension (mN / m) and bubble life at 160°F and show it in Fig.10 middle.
[0448] The data from these experiments indicate that Bardac LF80 by itself exhibits slow dynamic surfactant activity. Likewise, Acusol 445 alone exhibits very little surfactant activity. However, the combination of Bardac LF80 and Acusol 445 is more dynamically active than either component alone. Furthermore, it can be seen that the synergy between Bardac LF80 and increasing levels of Acusol 445 increases, but the synergy level is cut off between 30ppm and 75ppm of Acusol 445.
[0449] Further tests of dynamic surface activity were performed to assess the synergistic effects of other Bardac LF80 and polymer combinations. According to the above procedure, the surface activity of the following five solutions at pH 7.0 was determined; 100 ppm Bardac LF80; 100 ppm Bardac LF80 + 75 ppm PSO; 100 ppm Bardac LF80 + 75 ppm Acusol 445; and 100 ppm Bardac LF80 + 75 ppm AR-801. These results are provided in Fig.11 middle.
[0450] and Fig.10 The results provided in are consistent with Fig.11 The data in clearly show the synergy between Bardac LF80 and the anionic polymers tested (Acusol 445, PSO and AR-801). The quaternary ammonium salt-anionic polymer solution increased the dynamic surface activity compared to the quaternary ammonium salt solution alone. All three polymers at the tested concentrations were able to increase the dynamic surface activity of Bardac LF80 at comparable rates.
[0451] To determine whether the enhancement in surface activity observed in Bardac LF80-anionic polymer solutions was pH dependent, the following solutions were tested according to the above procedure at pH 11.0: 100 ppm Bardac LF80; 10 ppm Acusol 445; 100 ppm Bardac LF80 + 10 ppm Acusol 445; 100 ppm Bardac LF80 + 75 ppm Acusol 445. The results of this experiment are provided in Fig.12 middle.
[0452] From this data, it can be seen that a change in pH to 11.0 had no observable effect on the surface activity of Acusol 445 alone. Fig.11 When looking at the results of , the surface activity of Bardac LF80 alone appears to increase at pH 11.0. However, a synergistic effect between the anionic polymer and the quaternary ammonium salt is still observed, indicating a synergistic increase in surface activity independent of pH.
[0453] Example 17
[0454] Dynamic Surface Tension of Quaternary Ammonium Salts and Anionic Polymers
[0455] Dynamic surface tension studies of quaternary ammonium salt-anionic polymer pairs were continued at pH 7.0 as described in Example 16 for the following solutions: 100 ppm Bardac 2250; 100 ppm Bardac 2250 + 75 ppm PSO; 100 ppm Bardac 2250 + 75 ppm Acusol 445; 100 ppm Bardac 2250 + 75 ppm AR-801. Data from this experiment are provided in Fig.13 middle. Fig.13 The results in show that when combined with Fig.10 When looking at the data from the 2014 study, the fundamental difference for Bardac 2250 is apparent. This indicates the difference in surface activity of C10 vs. C8 quats in combination with anionic polymers. While Bardac 2250 appears to be synergistic with the smaller PSO and AR-801, it is clearly inactivated by the larger anionic polymer, Acusol 445.
[0456] To further test the activation of Bardac 2250 by Acusol 445, the procedure of Example 16 was used at pH 7.0 for the following solutions: 100 ppm Bardac 2250; 10 ppm Acusol 445; 100 ppm Bardac 2250 + 10 ppm Acusol 445; 100 ppm Bardac 2250 + 20 ppm Acusol 445; and 100 ppm Bardac 2250 + 50 ppm Acusol 445. The results are provided in Fig.14 From this data, it can be seen that Acusol 445 shows a dose-dependent inactivation of Bardac 2250 in terms of dynamic surfactant activity. As the concentration of Acusol 445 increases, the rate at which the surface tension of Bardac 2250 decreases during the bubble lifetime decreases.
[0457] To determine whether Acusol 445-mediated inactivation of Bardac 2250 dynamic surface tension was dependent on solution pH, further testing was performed using the procedure outlined in Example 16, except that solutions at pH 7.0 and pH 11.0 were compared side by side. Specifically, the following three solutions were analyzed; 100 ppm Bardac 2250; 100 ppm Bardac 2250 + 50 ppm Acusol 445 at pH 7.0; and 100 ppm Bardac 2250 + 50 ppm Acusol 445 at pH 11.0. The results are provided in Fig.15 The data show that the inactivation of Bardac 2250 by Acusol 445 is maintained at pH 11.0. Regardless of the pH, the surface tension of the solution of Bardac 2250 combined with Acusol 445 decreases at a comparable rate. The surface tension of Bardac 2250 alone decreases rapidly during the bubble life.
[0458] The dynamic surface tension of the quaternary ammonium salt-anionic polymer pairs was further evaluated using the procedure described in Example 16 to assess the effects of combinations of C8-C10 quaternary ammonium compounds on activation or deactivation. For these experiments, the following solutions were prepared at pH 7.0; 100 ppm Bardac 205M; 100 ppm Bardac 205M+75 ppm PSO; 100 ppm Bardac 205M+75 ppm Acusol 445; and 100 ppm Bardac 205M+75 ppm AR-801 ( Fig.16) or 100ppm UniquatQAC50; 100ppm Uniquat QAC50+75ppm PSO; 100ppm Uniquat QAC50+75ppm Acusol 445; and 100ppm Uniquat QAC50+75ppm AR-801( Fig.17 ). Check the data for Bardac 205M-anionic polymer pairs provided in Fig.16 , while the results for the Uniquat QAC50-anionic polymer pair are provided in Fig.17 middle.
[0459] and Fig.13 Consistent with the results of , the mixture of Bardac 205M also synergizes with the smaller anionic polymers PSO and AR-801. The combination of PSO and AR-801 with Bardac 205M shows a decrease in dynamic surface tension compared to Bardac 205M alone. Although the larger anionic polymer Acusol 445 has an inactivating effect on the dynamic surface tension of Bardac 205M, Fig.13 In addition, the Uniquat QAC50 solution followed a similar trend, with the smaller anionic polymers, PSO and AR-801 showing synergistic surface activity. However, the mixture of Acusol 445 and Uniquat QAC50 showed a mildly inactivated surface activity ( Fig.17 ).
[0460] The results of Example 16 and Example 17, when viewed together, show that the combination of Bardac LF80 (C8) and anionic polymers exhibits synergistic surfactant enhancing properties independent of pH or polymer size. However, Bardac 2250, Bardac 205M, and Uniquat QAC50 also show synergistic surfactant enhancing effects when mixed with smaller anionic polymers (PSO and AR-801), but show antagonistic trends (i.e., inactivation) as a function of polymer concentration and pH when mixed with the larger anionic polymer Acusol 445.
[0461] Example 18
[0462] Dynamic Surface Tension of Quaternary Ammonium Salt-Chelating Agent Solutions
[0463] Combinations of quaternary ammonium salt-anion chelating agent solutions were analyzed using a SITA Scientific Series t60 system and the procedure described in Example 16. Specifically, the following solutions were analyzed at pH 7.0; 100 ppm Bardac LF80; 100 ppm Bardac LF80 + 10 ppm HEDP; 100 ppm Bardac LF80 + 20 ppm HEDP; 100 ppm Bardac LF80 + 50 ppm HEDP; and 100 ppm Bardac LF80 + 75 ppm HEDP. These results are shown in Fig.18 These results indicate an increase in dynamic surface activity of Bardac LF80 in combination with HEDP. A synergistic trend appears to be a function of chelator concentration, but it is a subtle trend.
[0464] Additional quaternary ammonium compounds in combination with anionic chelating agents were tested according to the procedure outlined in Example 16. The following solutions were prepared for testing: 100 ppm Bardac 2250; 100 ppm Bardac 2250 + 75 ppm Dequest 2000; and 100 ppm Bardac 2250 + 75 ppm Trilon M ( Fig.19 ) or 100ppm Uniquat QAC50; 100ppm UniquatQAC50+75ppm Dequest 2000; and 100ppm Uniquat QAC50+75ppm Trilon M ( Fig. 20 The results for the Bardac 2250-anionic chelator combination are provided in Fig.19 , while the results for the Uniquat QAC50-anionic chelator combination were provided in Fig. 20 middle.
[0465] The data from this experiment show the synergistic surface activity enhancing properties of the quaternary ammonium salt-anion chelating agent solution. For both Bardac 2250 and Uniquat QAC50, an increase in surface activity was observed when combined with Dequest 2000 or Trilon M. Although both anion chelating agents were able to reduce the surface tension of all three quaternary ammonium compounds tested (Bardac LF80, Bardac 2250 and Uniquat QAC50), Trilon M consistently produced lower surface tension during the bubble life when compared to the quaternary ammonium salt-Dequest 2000 combination.
[0466] To determine whether the observed synergistic effect of the quaternary ammonium salt-anion chelator combination was dependent on the pH of the solution, further testing was performed using the procedure outlined in Example 16, except at different pHs. The following solutions were analyzed; 100 ppm Bardac LF80 pH 7.0; 100 ppm Bardac LF80 + 100 ppm Trilon M pH 3.0; 100 ppm Bardac LF80 + 100 ppm Trilon M pH 9.0; and 100 ppm Bardac LF80 + Trilon M pH 11.0. The data from this experiment is shown in Fig.21 From these results, it can be seen that the synergistic trend between Bardac LF80 and Trilon M seems to be independent of pH, as the pH of the solution has little effect on the dynamic surface activity of the measured solutions.
[0467] When the experimental results of Example 18 are viewed in combination, it can be seen that the quaternary ammonium salts (Bardac LF80, Bardac 2250, and Uniquat QAC50) and anionic chelating agents (Dequest 2000 and Trilon M) when combined show synergistic surface activity enhancing performance compared to the quaternary ammonium salt solutions alone, as shown in FIG. Figure 18-20 In addition, the synergistic trend of quaternary ammonium salts and anionic chelators is a function of chelator concentration and does not seem to be pH-dependent, respectively. Fig.18 and Fig.21 shown.
[0468] Example 19
[0469] Solubility of quaternary ammonium salt-anionic polymer solutions
[0470] The general solution behavior using 1% quaternary ammonium salt and 100 ppm polymer was analyzed. The results are provided in Table 20.
[0471] Table 20
[0472]
[0473] The further solution behavior using 500 ppm quaternary ammonium salt and maximum amount of added polymer before phase transition (precipitation point) was analyzed. The polymer was added to the maximum concentration (insoluble point). The results are provided in Table 21.
[0474] Table 21
[0475]
[0476] The results of these experiments show that shorter quaternary ammonium chain lengths facilitate higher levels of polymer incorporation.
[0477] Example 20
[0478] Mineral deposit removal
[0479] To determine the efficacy of quaternary ammonium salt-anionic chelating agent and quaternary ammonium salt-anionic polymer combinations in removing dirt from surfaces, the following procedure was used. Using an automatic dip tester unit, pre-soiled polypropylene coupons (mineral deposits) were immersed in solutions of water, 50ppm chelating agent (GLDA), and 100ppm Bardac LF80 + 50ppm chelating agent (GLDA). The solutions were prepared and stirred in separate beakers. The soiled tiles were immersed in beakers of various cleaning compositions for a period of 10 minutes. The tiles were then visually analyzed to assess the cleanliness of the tiles, i.e., mineral deposit removal. The visual observations of this descaling of the quaternary ammonium salt-anionic chelating agent solution and the quaternary ammonium salt-anionic polymer solution are shown in Fig. 22 middle.
[0480] Using the same automatic dip tester unit, pre-soiled polypropylene coupons (mineral deposits) were immersed in solutions of water, 25 ppm Acusol 445, 100 ppm Bardac LF80 + 25 ppm Acusol 445, and 100 ppm nonionic surfactant (Surfonic 12-6) + 25 ppm Acusol 445. Visual observations of scale removal for the quaternary ammonium salt-anionic chelant solution and the quaternary ammonium salt-anionic polymer solution are shown in Fig.23 middle.
[0481] The result shows, uses the benefit of the synergistic combination of quaternary ammonium salt and anionic polymer / chelating agent according to the embodiment of the present invention.The combination improves the detergency of chelating agent and polymer, more than the non-synergistic nonionic surfactant (as shown in 100ppm nonionic surfactant (Surfonic 12-6)+25ppm Acusol 445) combined with anionic polymer.Not subject to the specific mechanism of action of the present invention or theoretical constraints, quaternary ammonium salt and anionic polymer / chelating agent form more surface-active complex with chelating agent or polymer, and it effectively seeks dirt on the surface by surface excess and / or less charge repulsion mechanism.Although non-synergistic surfactant (i.e. nonionic surfactant) can improve wettability, there is no surface excess and / or less charge repulsion of chelating agent and / or polymer.
[0482] The present invention may also relate to the following specific embodiments:
[0483] 1. An antimicrobial composition comprising:
[0484] Quaternary ammonium compounds having the formula:
[0485]
[0486] wherein the radicals R1, R2, R3 and R4 each have a chain length of less than C20, and
[0487] An anionic surfactant, anionic polymer or anionic chelating agent having a C6-C18 chain length; wherein the composition is a ready-to-use solution, or a solid or liquid concentrate soluble in water, has a pH of about 1 to about 12, and is substantially free of silanes and oxidizing agents.
[0488] 2. The antimicrobial composition according to embodiment 1, wherein the anionic surfactant is a carboxylate and / or a phosphate.
[0489] 3. The antimicrobial composition of any one of embodiments 1 to 2, wherein the pH is between about 1 and about 10.
[0490] 4. The antimicrobial composition of any one of embodiments 1 to 2, wherein the pH is between about 1 and about 7.
[0491] 5. The antimicrobial composition according to any one of embodiments 1 to 4, wherein the anionic surfactant is an alkoxylated or unalkoxylated linear or branched carboxylate.
[0492] 6. The antimicrobial composition according to any one of embodiments 1 to 4, wherein the anionic surfactant is an alkoxylated or non-alkoxylated linear surfactant.
[0493] 7. The antimicrobial composition of any one of embodiments 1 to 6, wherein the anionic surfactant is a primary linear carboxylate.
[0494] 8. The antimicrobial composition of any one of embodiments 1 to 7, wherein the anionic surfactant is a medium chain surfactant having a C6-C10 chain length.
[0495] 9. The antimicrobial composition of any one of embodiments 1 to 7, wherein the anionic surfactant is a medium chain surfactant having a C8-C10 chain length.
[0496] 10. The antimicrobial composition of embodiment 1, wherein the anion chelating agent or polymer is an aminocarboxylate or a derivative thereof, a phosphonic acid or a phosphonate.
[0497] 11. An antimicrobial composition according to any one of embodiments 1 to 10, wherein the molar ratio of anionic surfactant, chelating agent or polymer to quaternary ammonium is from about 10 moles of anionic surfactant, chelating agent or polymer to about 1 mole of quaternary ammonium to about 1 mole of anionic surfactant, chelating agent or polymer to about 10 moles of quaternary ammonium.
[0498] 12. The antimicrobial composition of any one of embodiments 1 to 10, wherein the molar ratio of anionic surfactant, chelating agent or polymer to quaternary ammonium is about 1 mole of anionic surfactant, chelating agent or polymer to about 1 mole of quaternary ammonium.
[0499] 13. An antimicrobial composition according to any one of embodiments 1 to 12, wherein the quaternary ammonium compound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, multi-substituted quaternary ammonium salts, diquaternary ammonium salts, polymeric quaternary ammonium salts and combinations thereof.
[0500] 14. An antimicrobial composition according to any one of embodiments 1 to 12, wherein the quaternary ammonium compound is composed of one or more of dialkyl quaternary ammonium and alkyl benzyl quaternary ammonium, and wherein the anionic surfactant is composed of one or more of octanoic acid, nonanoic acid or capric acid.
[0501] 15. An antimicrobial composition according to any one of embodiments 1 to 14, wherein the quaternary ammonium compound groups R1, R2, R3 and R4 each have a chain length of less than C10.
[0502] 16. An antimicrobial composition according to embodiment 15, wherein the quaternary ammonium compound is dioctyl (C8) dimethyl ammonium chloride, didecyl (C10) dimethyl ammonium chloride, dialkyl benzyl ammonium chloride and / or alkyl benzyl ammonium chloride, and wherein the anionic surfactant, chelating agent or polymer is a polyacrylic acid polymer, phosphosuccinate adduct / oligomer (PSO) and / or a polycarboxylate.
[0503] 17. The antimicrobial composition of any one of embodiments 1 to 16, further comprising an acidifier.
[0504] 18. An antimicrobial composition according to any one of embodiments 1 to 17, wherein the quaternary ammonium has a carbon chain length of 8 to 20 carbon atoms.
[0505] 19. The antimicrobial composition of any one of embodiments 1 to 16, wherein the quaternary ammonium has a carbon chain length of 8 to 16 carbon atoms.
[0506] 20. The antimicrobial composition of any one of embodiments 1 to 19, wherein the composition provides from about 50 ppm to about 400 ppm of the quaternary ammonium compound and at least about 10 ppm of the anionic surfactant, chelating agent or polymer in a use solution.
[0507] 21. An antimicrobial composition according to any one of embodiments 1 to 20, further comprising additional functional ingredients selected from the group consisting of additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, stabilizers, corrosion inhibitors, sequestering agents and / or chelating agents, curing agents, tableting, pH adjusting components, fragrances and / or dyes, hydrotropes or coupling agents, buffers, and combinations thereof.
[0508] 22. A method for killing microorganisms, comprising:
[0509] applying the antimicrobial composition according to any one of embodiments 1 to 21 to a substrate;
[0510] wherein the composition provides at least 5 log kill and / or reduction of soil deposits on the treated surface.
[0511] 23. The method of embodiment 22, wherein the pH of the composition is between about 1 and about 7.
[0512] 24. The method of embodiment 22, wherein the pH of the combination is between about 1 and about 6.
[0513] 25. The method of any one of embodiments 22 to 24, wherein the use solution conditions have a water hardness of at least about 500 ppm water hardness ions, and wherein the composition tolerates water conditions up to about 500 ppm water hardness.
[0514] 26. The method of any one of embodiments 22 to 25, wherein the use solution condition has a water hardness greater than 5 grains per gallon (gpg).
[0515] 27. The method of any one of embodiments 22 to 25, wherein the use solution conditions have a water hardness of about 5 grains per gallon (gpg) to about 15 grains per gallon (gpg) of water.
[0516] 28. A method for rapidly solubilizing fatty acids to enhance antimicrobial efficacy,
[0517] It contains:
[0518] To the fatty acid is added a quaternary ammonium having the formula:
[0519]
[0520] wherein the radicals R1, R2, R3 and R4 each have a chain length of less than C20,
[0521] The solubilization thereby deodorizes the unpleasant fatty acid odor.
[0522] 29. The method of embodiment 28, wherein the fatty acid is a carboxylic fatty acid.
[0523] 30. The method of embodiment 28, wherein the combination of the fatty acid and the quaternary ammonium is in water.
[0524] 31. The method of embodiment 28, wherein the solubilized fatty acid and the quaternary ammonium provide a synergistic antimicrobial efficacy as measured by enhanced efficacy compared to the individual components or combinations.
[0525] 32. The method of embodiment 28, wherein the molar ratio of carboxylic acid fatty acid to quaternary ammonium is from about 2 moles of carboxylic acid fatty acid to about 1 mole of quaternary ammonium to about 1 mole of carboxylic acid fatty acid to about 10 moles of quaternary ammonium.
[0526] 33. The method of embodiment 28, wherein the molar ratio of carboxylic acid fatty acid to quaternary ammonium is about 1 mole of carboxylic acid fatty acid to about 1 mole of quaternary ammonium.
[0527] 34. A method for inactivating an antimicrobial quaternary composition using anionic surfactants, comprising:
[0528] Treating a water source or waste stream containing a quaternary ammonium compound having the formula:
[0529]
[0530] wherein the groups R1, R2, R3 and R4 each have a chain length less than C20, and the anionic surfactant has a chain length of at least C12 and less than C20;
[0531] wherein the anionic surfactant has a pH of about 1 to about 12, and
[0532] Wherein the water source or waste stream contains bacteria which are not destroyed by the inactivating composition.
[0533] 35. A method according to embodiment 34, wherein the anionic surfactant is a sulfate and / or sulfonate anionic surfactant or a polyacrylic acid polymer having a molecular weight greater than about 4000.
[0534] 36. A method according to embodiment 34, wherein the anionic surfactant of the inactivated antimicrobial composition comprises embodiment 1, wherein the anionic surfactant is selected from the group consisting of SLS (sodium lauryl sulfate), SLES (sodium lauryl ether sulfate), LAS (linear alkyl benzyl sulfonate) and AOS (alpha olefin sulfonate).
[0535] 37. The method according to embodiment 34, wherein the anionic surfactant is a linear or branched, alkoxylated or non-alkoxylated sulfate or sulfonate.
[0536] 38. The method of embodiment 34, wherein the anionic surfactant is a linear, non-alkoxylated sulfate or sulfonate.
[0537] 39. The method of any one of embodiments 34 to 38, wherein the inactivated antimicrobial composition is effective under hard water conditions.
[0538] 40. The method of any one of embodiments 34 to 39, wherein the molar ratio of anionic surfactant to quaternary ammonium compound is from about 10 moles of anionic surfactant to about 1 mole of quaternary ammonium compound to about 1 mole of anionic surfactant to about 10 moles of quaternary ammonium, and wherein the molar ratio controls the degree of inactivation of the quaternary ammonium compound.
[0539] 41. The method of any one of embodiments 34 to 39, wherein the molar ratio of anionic surfactant to quaternary ammonium compound is about 1 mole of anionic surfactant to about 1 mole of quaternary ammonium compound, and wherein the molar ratio controls the degree of inactivation of the quaternary ammonium compound.
[0540] 42. The method according to any one of embodiments 34 to 41, wherein the quaternary ammonium compound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, multi-substituted quaternary ammonium salts, diquaternary ammonium salts, polymeric quaternary ammonium salts, and combinations thereof.
[0541] 43. The method according to any one of embodiments 34 to 41, wherein the quaternary ammonium compound consists of a mixture of dialkyl quaternary ammonium and alkyl benzyl quaternary ammonium and has a chain length of less than 10 carbon atoms.
[0542] 44. The method according to any one of embodiments 34 to 43, wherein the inactivated antimicrobial composition further comprises additional functional ingredients selected from the group consisting of additional surfactants, thickeners and / or viscosity modifiers, solvents, solubility modifiers, humectants, metal protectants, stabilizers, corrosion inhibitors, sequestering agents and / or chelating agents, solidifying agents, tableting, pH adjusting components (acidifiers), fragrances and / or dyes, hydrotropes or coupling agents, buffers, and combinations thereof.
[0543] 45. A kit for inactivating a surfactant and / or antimicrobial composition comprising a quaternary ammonium compound, comprising:
[0544] (a) anionic surfactants having a chain length of at least C12 and less than C20; and
[0545] (b) a measuring device and / or a dosing device for determining and / or providing the molar ratio of the anionic surfactant to the quaternary ammonium compound having the formula:
[0546]
[0547] wherein the radicals R1, R2, R3 and R4 each have a chain length of less than C20,
[0548] The molar ratio of the anionic surfactant to the quaternary ammonium compound is about 1 mole of the anionic surfactant to about 1 mole of the quaternary ammonium compound.
[0549] 46. The kit of embodiment 45, further comprising instructions.
[0550] Having thus described the present invention, it will be apparent that the present invention may be varied in many ways. Such variations are not to be considered as departing from the spirit and scope of the present invention, and all such modifications are intended to be included within the scope of the appended claims. The above description provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments may be made without departing from the spirit and scope of the present invention, the present invention belongs to the claims.
Claims
1. An antimicrobial composition comprising: Quaternary ammonium compounds having the formula: wherein the radicals R1, R2, R3 and R4 each have a chain length of less than C20, and Anionic polymers or anionic chelating agents; The composition is a ready-to-use solution, or a solid or liquid concentrate soluble in water, has a pH of about 1 to about 12, and is substantially free of silanes and oxidizing agents.
2. The antimicrobial composition of claim 1, wherein the pH is from about 1 to about 10.
3. The antimicrobial composition of any one of claims 1 to 2, wherein the pH is from about 1 to about 7.
4. The antimicrobial composition according to any one of claims 1 to 3, wherein the anionic polymer is a polyacrylic acid polymer, a polymaleic acid polymer, a phosphosuccinate adduct or a phosphosuccinate oligomer.
5. The antimicrobial composition of claim 1, wherein the anion chelating agent is an aminocarboxylate or a derivative thereof, a phosphonic acid or a phosphonate.
6. An antimicrobial composition according to any one of claims 1 to 5, wherein the molar ratio of anionic chelating agent or polymer to quaternary ammonium is from about 10 moles of anionic chelating agent or polymer to about 1 mole of quaternary ammonium to about 1 mole of anionic chelating agent or polymer to about 10 moles of quaternary ammonium.
7. The antimicrobial composition of any one of claims 1 to 5, wherein the molar ratio of anionic chelating agent or polymer to quaternary ammonium is about 1 mole of anionic chelating agent or polymer to about 1 mole of quaternary ammonium.
8. The antimicrobial composition of any one of claims 1 to 7, wherein the quaternary ammonium compound is selected from the group consisting of monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, heteroaromatic ammonium salts, polysubstituted quaternary ammonium salts, diquaternary ammonium salts, polymeric quaternary ammonium salts, and combinations thereof.
9. The antimicrobial composition according to any one of claims 1 to 7, wherein the quaternary ammonium compound is composed of one or more of dialkyl quaternary ammonium and alkyl benzyl quaternary ammonium.
10. An antimicrobial composition according to any one of claims 1 to 9, wherein the quaternary ammonium compound groups R1, R2, R3 and R4 each have a chain length of less than C10.
11. An antimicrobial composition according to claim 9, wherein the quaternary ammonium compound is dioctyl (C8) dimethyl ammonium chloride, didecyl (C10) dimethyl ammonium chloride, dialkyl benzyl ammonium chloride and / or alkyl benzyl ammonium chloride, and wherein the anion chelating agent or polymer is a polyacrylic acid polymer, phosphosuccinate adduct / oligomer (PSO) and / or a polycarboxylate.
12. The antimicrobial composition according to any one of claims 1 to 11, further comprising an acidifying agent.
13. An antimicrobial composition according to any one of claims 1 to 12, wherein the quaternary ammonium has a carbon chain length of 8 to 20 carbon atoms.
14. An antimicrobial composition according to any one of claims 1 to 13, wherein the quaternary ammonium has a carbon chain length of 8 to 16 carbon atoms.
15. The antimicrobial composition of any one of claims 1 to 14, wherein the composition provides from about 50 ppm to about 400 ppm of the quaternary ammonium compound and at least about 10 ppm of the anion chelating agent or polymer in a use solution.
16. An antimicrobial composition according to any one of claims 1 to 15, further comprising an additional functional ingredient selected from the group consisting of: a surfactant, a thickener and / or a viscosity modifier, a solvent, a solubility modifier, a humectant, a metal protectant, a stabilizer, a corrosion inhibitor, a sequestering agent and / or a chelating agent, a curing agent, a tableting agent, a pH adjusting component, a fragrance and / or a dye, a hydrotrope or a coupling agent, a buffer and a combination thereof.
17. A method for killing microorganisms, comprising: Applying the antimicrobial composition according to any one of claims 1 to 16 to a substrate; wherein the composition provides at least 5 log kill and / or reduction of soil deposits on the treated surface.
18. The method of claim 17, wherein the pH of the composition is from about 1 to about 7.
19. The method of claim 17, wherein the pH of the combination is from about 1 to about 6.
20. The method of any one of claims 17 to 19, wherein the use solution conditions have a water hardness of at least about 500 ppm water hardness ions, and wherein the composition tolerates water conditions up to about 500 ppm water hardness.
21. The method of any one of claims 17 to 20, wherein the use solution condition has a water hardness greater than 5 grains per gallon (gpg).
22. The method of any one of claims 17 to 20, wherein the use solution condition has a water hardness of about 5 grains per gallon (gpg) to about 15 grains per gallon (gpg) of water.
23. A method for rapidly solubilizing fatty acids to enhance antimicrobial efficacy, It contains: To the fatty acid is added a quaternary ammonium having the formula: wherein the radicals R1, R2, R3 and R4 each have a chain length of less than C20, The solubilization thereby deodorizes the unpleasant fatty acid odor.
24. The method of claim 23, wherein the fatty acid is a carboxylic fatty acid.
25. The method of claim 23, wherein the combination of the fatty acid and the quaternary ammonium is in water.
26. The method of claim 23, wherein said solubilized fatty acid said quaternary ammonium provides a synergistic antimicrobial efficacy as measured by enhanced efficacy compared to the individual components or combinations.
27. The method of claim 23, wherein the molar ratio of carboxylic acid fatty acid to quaternary ammonium is from about 2 moles of carboxylic acid fatty acid to about 1 mole of quaternary ammonium to about 1 mole of carboxylic acid fatty acid to about 10 moles of quaternary ammonium.
28. The method of claim 23, wherein the molar ratio of carboxylic fatty acid to quaternary ammonium is about 1 mole of carboxylic fatty acid to about 1 mole of quaternary ammonium.
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