Biofilm inactivation compositions and methods of inactivating, reducing, and / or removing adhered bacteria or biofilms from surfaces

Abstract

Biofilm inactivation compositions and methods for inactivating, reducing, and / or removing adherent bacteria or biofilms from surfaces are disclosed. The biofilm inactivation compositions comprise: at least one biocide, wherein the biocide is peracetic acid and / or peroctanoic acid; and a hydrated hydrogen ion source, wherein the hydrated hydrogen ion source is one or more strong acids selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, or hydroiodic acid, wherein the composition is provided in a working composition at a concentration of at least 100 ppm and provides a working pH of 2.5 or below and a reduction of at least 5-log in the population of microorganisms and pathogens in the biofilm, and wherein the hydrated hydrogen ion source is provided in the working composition at a concentration of at least 0.003 M hydrated hydrogen ions.

Description

[0001] This application is a divisional application of the invention patent application with application number 202180032549.7, application date May 28, 2021, entitled "Biocidal composition with hydrated hydrogen ion source for biofilm control". Cross-references to related applications

[0002] This application claims priority to provisional application serial number 62 / 704,813, filed May 29, 2020, pursuant to 35 USC § 119, which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention relates to the use of biocides for biofilm control, specifically the synergistic combination of biocides and hydrated hydrogen ions to treat and / or inactivate biofilms. Compositions comprising hydrated hydrogen ions and one or more biocides are effective against biofilms. Methods for inactivating, removing, and / or preventing biofilms using said compositions are also provided. Background Technology

[0004] A biofilm is a biological aggregate containing pathogens such as bacteria and other microorganisms embedded in a matrix of extracellular polymeric substances (EPS). Besides bacteria, other microorganisms are commonly found in biofilms, including fungi, molds, algae, protozoa, archaea, and mixtures of these. Microorganisms form biofilms on surfaces and produce a protective extracellular polymeric matrix. In most cases, biofilms typically form on surfaces in contact with water, providing a hydrated matrix of polysaccharides to offer structural protection against biocides, making biofilms more difficult to kill than other pathogens. Biofilms are also often referred to as biomass accumulations, which are accumulations of microorganisms and / or extracellular material containing dirt and debris trapped within the biomass. Biofilm biomass is a highly resilient assembly of microorganisms within these biomass, extremely difficult to eradicate, and the bacteria living in biofilms are more resistant to host defenses and treatment with antibiotics or antimicrobial agents. Some microorganisms attach to inert surfaces, forming aggregates with a complex matrix composed of extracellular polymeric substances (EPS). This union of attached microorganisms and associated EPS is commonly referred to as a biofilm. Biocides have difficulty penetrating biofilms and removing them from the surface.

[0005] Microbial contamination and biofilm formation pose serious complications in many industries. Although biofilms are known to exist in a variety of environmental conditions, industries such as food processing are particularly affected because they most commonly form on surfaces exposed to bacteria and water. The presence of microorganisms in commercial and industrial waters is especially challenging because they are difficult to completely eliminate even with excessive use of chemical biocides. The most common method for controlling biofouling is through the application of chemical biocides, such as chlorine (e.g., hypochlorite) or other corrosive compositions, bromine, isothiazolone, glutaraldehyde, or other antimicrobial agents. In bulk solution systems, the traditional indicator of biocidal efficacy is the killing of microorganisms suspended in the solution, known as planktonic microorganisms. Removing planktonic microorganisms, or inhibiting biofilm formation, is the preferred approach because it prevents bacteria from adhering to surfaces (i.e., colonizing). However, microorganisms aggregated on surfaces and biofilms, known as sessile microorganisms, have a significant impact on the processes and operations of systems including water systems.

[0006] Although biofilms are known to exist in a variety of environmental conditions, they are most commonly found on surfaces exposed to bacteria and water, making industries such as food processing particularly susceptible to their effects. For example, Listeria monocytogenes (BMC) is a common example. Listeria monocytogenes Biofilms thrive in cool, damp environments, such as floor drains, pipes, and other surfaces in food processing facilities. This provides potential points of contamination for processing plant environments and the food produced therein. However, biofilms can also form on the inert surfaces of everyday household items. Exposure to these microorganisms through skin contact can lead to infections and endanger public health. Therefore, controlling biofilm formation is an ideal way to reduce exposure to infectious microorganisms.

[0007] Therefore, the purpose of the compositions described herein is to provide synergistic efficacy in utilizing the combination of hydrated hydrogen ions and biocides to inactivate, remove and / or prevent biofilms, including biofilms on any surface.

[0008] A further objective is to provide methods for removing and / or preventing biofilms from surfaces, including those in commercial and industrial water systems.

[0009] A further objective is to provide compositions and methods for effectively mitigating and / or eliminating biofilms from surfaces.

[0010] Other objects, advantages and features of the present invention will become clear from the following description in conjunction with the appended examples. Summary of the Invention

[0011] The advantages of this invention are that it provides a synergistic effect of inactivating biofilms through a combination of a hydrated hydrogen ion source and a biocide, and inactivating, reducing, or removing microbial communities from a variety of surfaces. The synergistic compositions and methods advantageously overcome the traditional limitations of requiring excessive doses of biocides to provide biofilm control and effective surface disinfection. Advantageously, the combinations can utilize a variety of biocides, which may be preferred depending on the application and specific industry. Advantageously, the methods described herein provide for the treatment and inactivation of biofilms.

[0012] In one embodiment, the biofilm inactivation composition comprises: at least one biocide, wherein the biocide is a peroxide compound, a fatty acid, an anionic surfactant, and / or a quaternary ammonium compound; and a hydrated hydrogen ion source, wherein the hydrated hydrogen ion source is a strong acid including one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, or methanesulfonic acid, wherein a solution of the composition in use at a concentration of at least about 100 ppm provides at least a 5-log reduction. In an embodiment, the peroxide compound biocide is peroxycarboxylic acid, hydrogen peroxide, percarbonate, persulfate, perborate, permanganate, urea peroxide, and / or alkyl peroxide. In an embodiment, in a solution of the composition in use, the peroxycarboxylic acid is provided at a concentration of at least about 100 ppm, at least about 150 ppm, or at least about 200 ppm, or about 100 ppm to about 500 ppm. In an embodiment, in a solution of the composition in use, the fatty acid is provided at a concentration of at least about 100 ppm, or about 100 ppm to about 500 ppm. In embodiments, the anionic surfactant is provided in the use solution of the composition at a concentration of at least about 1000 ppm, about 1000 ppm to about 5000 ppm, or about 1000 ppm to about 2000 ppm. In embodiments, the quaternary ammonium compound is provided in the use solution of the composition at a concentration of at least about 500 ppm, about 500 ppm to about 5000 ppm, or about 1000 ppm to about 2000 ppm. In embodiments, the hydrated hydrogen ion source is provided in the use solution of the composition at a concentration of at least about 0.003 M hydrated hydrogen ions, about 0.003 M to about 0.1 M hydrated hydrogen ions, or about 0.005 M to about 0.1 M hydrated hydrogen ions. In embodiments, at least one additional functional ingredient, such as a stabilizer, is included.

[0013] In another embodiment, the method of inactivating, reducing, and / or removing surface-adhered bacteria or biofilms includes: contacting the microbial community with the composition described herein; and reducing and / or eliminating the microbial community. In embodiments, the microbial community is located on a hard surface and / or within a water system. In embodiments, the surface is a food surface, and optionally, the food surface is poultry. In embodiments, the surface is in contact with a water system or water source, wherein the water system or water source is one or more of the following: oilfield drilling fluids and mud; oil extraction processes; mining pipelines; water-bearing pipelines; fire-fighting water; industrial lubricants; cutting fluids; heat transfer systems; cooling towers; gas scrubber systems; latex systems; clay and pigment systems; cooling systems; cooling towers; water for food, beverage, and industrial processing; pulp and paper systems; brewery pasteurizers; sweet water systems; air scrubber systems; decorative fountains; inlet pipes; ballast tanks; and ship storage tanks. In embodiments, the surface is a drain pipe. In embodiments, the microbial community is a planktonic or attached microbial community, or a biofilm comprising one or more bacteria, including Escherichia coli (Escherichia coli). Escherichia coli ), Pseudomonas aeruginosa ( Pseudomonas aeruginosa Staphylococcus spp. Staphylococcal Bacteria, Enterobacteriaceae ( Enterobacteriaceae Bacteria and Streptococcus ( Streptococcus Bacteria. According to any of the methods described herein, the composition may be provided as (a) using or concentrating the composition or (b) adding at least one biocide and a source of hydrated hydrogen ions to contact the microbial community sequentially or simultaneously.

[0014] While several embodiments have been disclosed, other embodiments will become apparent to those skilled in the art from the following detailed description which illustrates and describes illustrative embodiments. Therefore, the detailed description is considered to be illustrative in nature rather than limiting. Detailed Implementation

[0015] The embodiments described are not limited to specific biocidal compositions containing a hydrated hydrogen ion source and a biocide, and / or methods for using them to inactivate, remove, eliminate, and / or prevent biofilm formation on surfaces. The embodiments can be varied and will be understood by those skilled in the art. Surprisingly, it has been found that combining a hydrated hydrogen ion source with at least one biocide can synergistically inactivate biofilms that are difficult to penetrate and treat, and prevent biofilm growth on water sources and / or surfaces.

[0016] It should also be understood that all terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limited in any manner or scope. For example, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” as used in this specification and the appended claims may include plural referents. Furthermore, all units, prefixes, and symbols may be represented in their SI-acceptable form. Numerical ranges listed in the specification include values ​​within the defined range. Throughout this disclosure, various aspects are presented in range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation of the scope of the invention. Therefore, the description of ranges should be considered to have all possible sub-ranges of the specific disclosure and the various numerical values ​​within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0017] To facilitate a clearer understanding of the invention, certain terms are first defined. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of the invention pertain. Many similar, modified, or equivalent methods and materials may be used in the implementation of the embodiments without excessive experimentation, but preferred materials and methods are described herein. In the description of embodiments and in the pursuit of patent protection, the following terms will be used in accordance with the definitions set forth below.

[0018] As used herein, the term "about" refers to variations in quantities that may occur, for example, through typical measurement and liquid handling steps used in the production of concentrates or the use of solutions in the real world; through negligible errors in these steps; through differences in the purity of the components used in the manufacture, sourcing, or production of these compositions or the execution of these methods. The term "about" also includes amounts that may vary due to different equilibrium conditions used for compositions formed from a particular initial mixture. Whether or not modified by the term "about," the claims include equivalents of these quantities.

[0019] The terms “actives” or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refer to the concentration of those ingredients involved in cleaning, expressed as a percentage after subtracting inert components such as water or salt.

[0020] As used herein, the term "biofilm" refers to an extracellular matrix in which a microbial community disperses and / or forms colonies and / or adheres to a surface. Biofilms are understood to be typically composed of polysaccharides and other macromolecules, often referred to as extracellular polysaccharides, which concentrate at the interface (typically solid / liquid) and act as binding agents surrounding these microbial communities. Biofilms are further understood to be complex combinations comprising cells, extracellular products, and debris (or inactive particulate organic material) that is trapped within or released from cells within the biofilm. As used herein, the term biofilm further refers to the ASTM definition of a biofilm as an accumulation of bacterial cells anchored to a substrate and embedded in an organic polymer matrix of microbial origin. Biofilms are understood to be dynamic, self-organizing accumulations of microorganisms and microbial and environmental byproducts determined by the environment in which the biofilm inhabits. According to the present invention, the phrases "biofilm remediation," "biofilm removal," "biofilm reduction," etc., shall refer to the use of chemical biocides according to the present invention, which result in a reduction in the rate or extent of biofilm growth, removal of existing biofilm or partial biofilm on a surface, and / or eradication of existing biofilm on a treated surface. According to the present invention, the biocidal compositions disclosed herein physically remove and kill biofilms.

[0021] As used herein, the term "water" includes cooling tower water and water used in food processing or transportation. Cooling tower water includes water used in scrubbers, cooling towers, etc., and includes water used in places where it performs functions such as collecting impurities, capturing products, and / or cooling equipment. Water used in food processing or transportation includes water used for production and transportation (e.g., as seen in water tanks, pipeline transportation, cutters, slicing knives, blanching devices, distillation systems, scrubbers, etc.), water drip trays with sprayers, shoe and hand washing basins, third-tier rinsing water, etc., used in food transport routes. Water also includes domestic and recreational water, such as pools, spas, leisure pools and waterways, fountains, etc.

[0022] As used herein, the terms “weight percent,” “% of weight,” “percent by weight,” “% of weight,” and their variations refer to the concentration of a substance, which is the weight of the substance divided by the total weight of the composition and multiplied by 100. It should be understood that, as used herein, “percentage,” “%,” etc., are intended to be synonymous with “weight percent,” “% of weight,” etc.

[0023] These methods and compositions may include, or consist essentially of, these components and ingredients as well as other components described herein. As used herein, “consisting essentially of” means that the methods and compositions may include additional steps or components, provided that the additional steps or components do not materially alter the essential characteristics and novelty of the claimed methods and compositions.

[0024] The biocidal compositions according to the embodiments described herein demonstrate significant improvements over the prior art and represent a significant shift in the industry requiring biofilm cleaning and disinfection products. Biocidal compositions effective against biofilms eliminate the need for many biofilm reducers that, alone and / or in combination, cannot completely remove and / or kill biofilms. These biocidal compositions provide superior biocide products, resulting in increased biofilm kill rates compared to known chemical and biological removal or reduction methods. This is a beneficial result of the biocidal compositions having a “killing mechanism” capable of penetrating all layers of the biofilm composition and reaching the matrix surface. Based on the description contained herein, these and other benefits of biofilm removal methods and biocidal compositions will become apparent, providing improved compositions and methods for treating ubiquitous biofilms.

[0025] Various biofilm reducing agents are known to provide some beneficial effects in reducing and / or preventing biofilm formation. For example, chelating agents such as EDTA and EGTA, chlorine, iodine, and hydrogen peroxide have previously been used as biofilm reducing agents. Chelating agents destabilize the outer cell membrane of biofilms. Chlorine, iodine, and hydrogen peroxide remove biofilms by depolymerizing the matrix. Furthermore, biofilm reducing agents may contain antimicrobial proteins, such as those found in *Streptococcus lactis* (Lactococcus lactis). Lactococcus lactus The biofilm can produce nisin. Biocides or antimicrobial agents can also be used as biofilm reducers; however, they are ineffective in completely removing biocides. However, as described herein, the biocidal compositions and methods described herein provide an enhanced antimicrobial “killing” mechanism superior to previous biofilm reducers. According to preferred embodiments, the biocidal compositions and methods provide at least a 5-log or 6-log reduction in the population of microorganisms and pathogens in the biofilm compared to the optimal 3-log reduction observed using conventional biofilm reducers. Without limiting to a particular mechanism of action, the beneficial results of the biocidal compositions according to the embodiments described herein arise from the composition penetrating all layers of the biofilm to the matrix surface, thereby providing complete killing of microorganisms located in such biofilms.

[0026] biocidal composition According to embodiments, the biocidal composition comprises at least one biocidal agent and a source of hydrated hydrogen ions. These alkaline detergent compositions may contain additional functional ingredients and may be provided in the form of a concentrate or a composition for use. According to another embodiment, the biocidal composition comprises at least one biocidal peroxide compound, a biocidal fatty acid, a biocidal anionic surfactant and / or a biocidal quaternary ammonium compound, and a source of hydrated hydrogen ions from an acid. These alkaline detergent compositions may contain additional functional ingredients and may be provided in the form of a concentrate or a composition for use. Exemplary biocidal compositions in solution are shown in Tables 1A to 1D, providing an use pH of about 2.5 or less in defined measurements (including ppm, moles, weight %).

[0027] biocides Peroxide biocides Peroxide biocides may comprise peroxide compounds or peroxide-generating chemicals and may also be used as biocides in the compositions described herein. Exemplary peroxide compounds comprise compositions of substances containing two or more oxygen atoms in the form of oxygen-oxygen bonds, and compositions of substances that induce a higher oxidation state in a composition of another substance, including, but not limited to: hydrogen peroxide, percarbonates, persulfates, perborates, permanganates, urea peroxide, and alkyl peroxides, such as tert-butyl hydrogen peroxide and potassium monopersulfate, and any compound of the formula R--(COOOH)n, wherein R may be hydrogen, alkyl, alkenyl, alkyne, acyl, alicyclic, aryl, heteroaryl, or heterocyclic, n is 1, 2, or 3, and is named by adding a peroxide prefix before the parent acid, and those sulfonated carboxylic acid compositions as disclosed in U.S. Patent Application Publications 2010 / 0021557, 2010 / 0048730, and 2012 / 0052134. In a particular embodiment, the biocidal peroxide is a peroxycarboxylic acid composition containing a peroxide compound (such as hydrogen peroxide).

[0028] Peroxycarboxylic acid composition Peroxycarboxylic acids or peroxycarboxylic acid compositions can be used as biocides for the compositions described herein. Peroxycarboxylic acids (or percarboxylic acids) typically have the formula R(CO3H)n, where, for example, R is an alkyl, aralkyl, cycloalkyl, aromatic, or heterocyclic group, n is mono, di, or tri, and the parent acid is named by the peroxy prefix. The R group can be saturated or unsaturated, substituted or unsubstituted. The composition may comprise a mixture or combination of several different peroxycarboxylic acids, including those with different chain lengths, such as C1-C22. Such compositions are generally referred to as mixed peroxycarboxylic acids or mixed peroxycarboxylic acid compositions. For example, in some preferred embodiments, the composition comprises one or more C1 to C4 peroxycarboxylic acids and one or more C5 to C22 peroxycarboxylic acids.

[0029] As described herein, the methods of use and compositions may comprise peroxycarboxylic acids (or peroxycarboxylic acid compositions comprising peroxycarboxylic acids, carboxylic acids, hydrogen peroxide, water, and optional additional components), or mixed peroxycarboxylic acids (or mixed peroxycarboxylic acid compositions comprising more than one peroxycarboxylic acid, more than one carboxylic acid, hydrogen peroxide, water, and optional additional components). Peroxycarboxylic acid compositions may be formed by combining one or more carboxylic acids with an oxidizing agent (e.g., hydrogen peroxide).

[0030] In a preferred embodiment, the peroxycarboxylic acid composition includes peracetic acid and / or peroxyoctanoic acid.

[0031] In some embodiments, peroxycarboxylic acid is included in the peroxycarboxylic acid forming composition or biocidal composition in amounts of at least about 5% to about 50% by weight, about 5% to about 40% by weight, about 5% to about 20% by weight, or about 5% to about 15% by weight. Furthermore, without being limited by the invention, all ranges described include numbers defining the range and are included within integers within the defined range.

[0032] In another embodiment, peroxycarboxylic acid is included in the biocidal composition at an amount of at least about 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, or 100 ppm, preferably in its solution of use. In another embodiment, peroxycarboxylic acid is included in the biocidal composition at an amount of at least about 100 ppm, at least about 150 ppm, or at least about 200 ppm, or about 100 ppm to about 500 ppm, preferably in its solution of use. Furthermore, without being limited by the invention, all ranges described include the numbers defining the range and are included within the integers of the defined range. It will be appreciated by those skilled in the art that the concentration of peroxycarboxylic acid can be provided at increased concentrations; however, the benefit of synergistic efficacy of the biocidal composition is achieved without excessive doses or concentrations of peroxycarboxylic acid.

[0033] carboxylic acid Peroxycarboxylic acid biocides can be provided as peroxycarboxylic acid compositions comprising carboxylic acids, such as compositions formed by combining at least one carboxylic acid with an oxidizing agent. In some embodiments, at least two, at least three, or at least four or more carboxylic acids may be used. The carboxylic acid used in the compositions of the present invention is a C1 to C22 carboxylic acid. In some embodiments, the carboxylic acid used in the compositions of the present invention is a C5 to C11 carboxylic acid. In some embodiments, the carboxylic acid is a C1 to C5 carboxylic acid. Examples of suitable carboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid and their branched isomers, lactic acid, maleic acid, ascorbic acid, citric acid, glycolic acid, neopentanoic acid, neoheptanoic acid, neodecanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid and mixtures thereof. Preferred carboxylic acids comprise organic compounds and / or those approved as organic, such as acetic acid used in the production of peracetic acid.

[0034] In some embodiments, the carboxylic acid is included in the peroxycarboxylic acid forming composition or biocidal composition in an amount of at least about 5% to about 50% by weight, about 15% to about 50% by weight, about 15% to about 40% by weight, or about 15% to about 30% by weight. Furthermore, without being limited by the invention, all ranges described include numbers defining the range and are included within integers within the defined range.

[0035] Oxidizing agent Peroxycarboxylic acid biocides can be provided as peroxycarboxylic acid compositions containing oxidants, such as peroxycarboxylic acid compositions formed by combining at least one carboxylic acid with an oxidant. Examples of inorganic oxidants include compounds of the following types or sources of these compounds, or alkali metal salts containing these types of compounds, or adducts thereof: hydrogen peroxide, or hydrogen peroxide donors of the following: Group 1 (IA) oxidants, such as lithium peroxide, sodium peroxide; Group 2 (IIA) oxidants, such as magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; Group 12 (IIB) oxidants, such as zinc peroxide; Group 13 (IIIA) oxidants, such as boron compounds, such as perborates, such as sodium perborate hexahydrate of the formula Na2[B2O4(OH)4].6H2O (also known as sodium perborate tetrahydrate); Na2[(BO2)2 Sodium perborate tetrahydrate of formula (OH)4].4H2O (also known as sodium perborate trihydrate); sodium perborate of formula Na2[(BO2)2(OH)4] (also known as sodium perborate monohydrate); Group 14 (IVA) oxidants, such as persilicates and percarbonates, also known as percarbonates, such as alkali metal persilicates or percarbonates; Group 15 (VA) oxidants, such as peroxynitrite and its salts; peroxyphosphoric acid and its salts, such as superphosphate; Group 16 (VIA) oxidants, such as persulfate and its salts, such as peroxymonosulfate and peroxydisulfate, and its salts, such as persulfates, such as sodium persulfate; and Group VIIa oxidants, such as sodium periodate and potassium perchlorate. Other active inorganic oxygen compounds may include transition metal peroxides; and other such peroxide compounds, and mixtures thereof.

[0036] In some embodiments, the compositions and methods of the present invention employ one or more of the inorganic oxidants listed above. Suitable inorganic oxidants include ozone, hydrogen peroxide, hydrogen peroxide adducts, Group IIIA or VIA oxidants, Group VA oxidants, Group VIIA oxidants, or hydrogen peroxide 30 donors of mixtures thereof. Suitable examples of such inorganic oxidants include percarbonates, perborates, persulfates, superphosphates, persilicates, or mixtures thereof.

[0037] Hydrogen peroxide is a suitable example of an inorganic oxidizing agent. Hydrogen peroxide can be provided as a mixture of hydrogen peroxide and water, for example, as liquid hydrogen peroxide in an aqueous solution. Hydrogen peroxide is commercially available in water at concentrations of 35%, 40-70%, and 90%. For safety, 35-50% is typically used.

[0038] Preferred oxidants include organic compounds and / or those approved as organic, such as hydrogen peroxide.

[0039] In some embodiments, the oxidant is included in the peroxycarboxylic acid forming composition or biocidal composition in an amount of at least about 10% to about 70% by weight, about 15% to about 70% by weight, about 20% to about 70% by weight, or about 25% to about 65% by weight. Furthermore, without being limited by the invention, all ranges described include numbers defining the range and are included within integers within the defined range.

[0040] fatty acid biocides Fatty acid biocides can be used as biocides in the compositions described herein. Exemplary fatty acids comprise an aliphatic chain having at least 5 carbon atoms or a carboxylic acid between C5 and C22. Examples of suitable carboxylic acids include, but are not limited to, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid and their branched isomers, lactic acid, maleic acid, ascorbic acid, citric acid, glycolic acid, neovaleric acid, neoheptanoic acid, neodecanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, and mixtures thereof.

[0041] In embodiments, fatty acids are included in the biocidal composition in amounts of at least about 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, or 100 ppm, preferably in its solution of use. In other embodiments, fatty acids are included in the biocidal composition in amounts of at least about 100 ppm, at least about 150 ppm, or at least about 200 ppm, or about 100 ppm to about 500 ppm, preferably in its solution of use. Furthermore, without being limited by the invention, all ranges described include the numbers defining the range and are included within the integers of the defined range. It will be appreciated by those skilled in the art that fatty acid concentrations can be provided at increased concentrations; however, the benefit of synergistic efficacy with the biocidal composition is achieved without excessive doses or concentrations of fatty acids.

[0042] Anionic surfactants and biocides Anionic surfactant biocides can be used as biocides in the compositions described herein. The anionic surfactant used in the biocidal composition must be compatible with hydrated hydrogen ions and possess biocidal efficacy under acidic pH conditions.

[0043] Suitable anionic surfactants include sulfonates and sulfates, including, for example, alkane sulfonates, alkyl aryl sulfonates, secondary alkane sulfonates, alkyl methyl ester sulfonates, α-olefin sulfonates, alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil alkenylglycerol 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, alcohol sulfates, 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 (typically having 1 to 6 vinyl oxide groups per molecule). Anionic sulfonate surfactants suitable for use in this composition also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents. Some commercially available sulfate or sulfonated anionic surfactants include X-AES (C12-14—(PO)16-(EO)2-sulfate, available from Huntsman Chemical), SLS (sodium lauryl sulfate), SLES (sodium lauryl ether sulfate), LAS (linear alkyl benzyl sulfonate), and AOS (alpha-olefin sulfonate).

[0044] Exemplary alkyl aryl sulfonates that can be used have an alkyl group containing 6 to 24 carbon atoms, and the aryl group can be at least one of benzene, toluene, and xylene. Suitable alkyl aryl sulfonates include linear alkylbenzene sulfonates. Suitable linear alkylbenzene sulfonates include linear dodecylbenzenemethyl sulfonate, which can be provided as an acid to be neutralized to form a sulfonate. Other suitable alkyl aryl sulfonates include xylene sulfonate and cumene sulfonate. Suitable alkane sulfonates that can be used in cleaning compositions may have an alkane group containing 6 to 24 carbon atoms. Suitable alkane sulfonates that can be used include secondary alkane sulfonates.

[0045] Suitable anionic surfactants further comprise carboxylic acids (and salts) and sulfonated carboxylic acids (and salts), such as alkyl acids (and alkylates), ester carboxylic acids (e.g., alkyl succinates) and sulfonated ester carboxylic acids, ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleic acid, etc. Such carboxylates include alkyl ethoxycarboxylates, alkyl aryl ethoxycarboxylates, alkyl polyethoxypolycarboxylates surfactants, and soaps (e.g., alkyl carboxyl groups). Useful secondary carboxylates comprise carboxylates containing a carboxyl unit attached to a secondary carbon. The secondary carbon can be located in a ring structure, for example in p-octylbenzoic acid, or as in alkyl-substituted cyclohexylcarboxylates. Secondary carboxylate surfactants typically lack ether bonds, ester bonds, and hydroxyl groups. Furthermore, they typically lack a nitrogen atom in the head group (amphiphilic moiety). Suitable secondary soap surfactants typically contain a total of 11-13 carbon atoms, but more carbon atoms (e.g., up to 16) can be present. Suitable carboxylates also include acyl amino acids (and salts), such as acylglutamate, acyl peptides, sarcosinates (e.g., N-acylsarcosinate), taurates (e.g., N-acyltaurate and methyltauryl fatty acid amide), etc.

[0046] Suitable anionic surfactants comprise alkyl or alkylaryl ethoxycarboxylate salts of the following formula: R - O -(CH2CH2O) n (CH2) m - CO2X, where R is a C8-C22 alkyl group or Wherein R1 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 counter ion, 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. Such alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically obtained in acidic forms that can be readily converted into anionic or salt forms.

[0047] Other suitable anionic surfactants include alcohol ethoxylates, including alcohol ethoxycarboxylates and alcohol ethoxyphosphates. In one embodiment, the anionic surfactant is a weak acid anion, such as a phosphate ester or an alcohol ethoxyphosphate ester.

[0048] In embodiments, the anionic surfactant is included in the biocidal composition, preferably in its solution of use, at an amount of at least about 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, or 1000 ppm. In other embodiments, the anionic surfactant is included in the biocidal composition, preferably in its solution of use, at an amount of at least about 1000 ppm, about 1000 ppm to about 5000 ppm, or about 1000 ppm to about 2000 ppm. Furthermore, without being limited by the invention, all ranges stated include the numbers defining the range and are included within the defined integers. It will be appreciated by those skilled in the art that the concentration of the anionic surfactant can be increased, however, the benefit of synergistic efficacy of the biocidal composition is achieved without excessive doses or concentrations of fatty acids.

[0049] Quaternary ammonium compounds biocides Quaternary ammonium compounds can be used as biocides in the compositions described herein. Therefore, a variety of quaternary ammonium compounds with antimicrobial activity can be used in the compositions. The terms "quaternary ammonium compound" or "quaternary ammonium salt" generally refer to any composition having the following formula:

[0050] R1-R4 are alkyl groups that may be identical or different, substituted or unsubstituted, saturated or unsaturated, branched or unbranched, and cyclic or acyclic, and may contain ether, ester, or amide bonds; they may be aromatic or substituted aromatic groups. In one aspect, groups R1, R2, R3, and R4 each have a chain length less than C20. X is an anionic counterion. The term "anionic counterion" includes any ion that can form a salt with quaternary ammonium. Examples of suitable counterions include halide ions such as chloride and bromide ions, propionate, methylsulfate, urate, ethylsulfate, hydroxide, acetate, phosphate, carbonate (as commercially available from Lonza as Carboquat H), and nitrate. Preferably, the anionic counterion is chloride.

[0051] In some embodiments, quaternary ammonium compounds having carbon chains of less than 20 or C2-C20 are included in the compositions of the present invention. In other embodiments, quaternary ammonium compounds having carbon chains of C6-C18, C12-C18, C12-C16, and C6-C10 are included in the compositions. Examples of suitable quaternary ammonium compounds for use in the present invention include, but are not limited to, alkyldimethylbenzylammonium chloride, alkyldimethylethylbenzylammonium chloride, octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride, and disecyldimethylammonium chloride. A single quaternary ammonium compound or a combination of more than one quaternary ammonium compound may be included in the compositions of the present invention. Other examples of quaternary ammonium compounds include, but are not limited to, benzyl chloride, ethylbenzyl chloride, myristin trimethylammonium chloride, methylbenzyl chloride, citrate chloride, cetrimonium bromide (CTAB), carnitine, dophamium chloride, tetraethylammonium bromide (TEAB), domiphen bromide, benzoyl chloride, benzoyl chloride, choline, cocamidopropyl betaine (CAPB), and benzodinammonium.

[0052] In some embodiments, quaternary ammonium compounds having carbon chains of less than 20 or C2-C20 are included in the compositions of the present invention. In other embodiments, quaternary ammonium compounds having carbon chains of C6-C18, C12-C18, C12-C16, and C6-C10 are included in the compositions of the present invention.

[0053] In some embodiments, depending on the nature of the R group, the anion, and the number of quaternary nitrogen atoms present, antimicrobial quaternary ammonium compounds can be classified into one of the following categories: monoalkyltrimethylammonium salts; monoalkyldimethylbenzylammonium salts; dialkyldimethylammonium salts; heteroaromatic ammonium salts; polysubstituted quaternary ammonium salts; bisquaternary ammonium salts; and polymerized quaternary ammonium salts. Each category will be discussed herein.

[0054] Monoalkyltrimethylammonium salts contain one R group as a long-chain alkyl group, and the remaining R groups are short-chain alkyl groups, such as methyl or ethyl. Some non-limiting examples of monoalkyltrimethylammonium salts include hexadecyltrimethylammonium bromide, commercially available under the trade names Rhodaquat M242C / 29 and Dehyquart A; alkyltrimethylammonium chloride, commercially available under the name Arquad 16; alkylaryltrimethylammonium chloride; and hexadecyldimethylethylammonium bromide, commercially available under the name Ammonyx DME. 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.

[0055] Monoalkyl dimethyl benzyl ammonium salts are generally compatible with nonionic surfactants, detergent builders, fragrances, and other ingredients. Some non-limiting examples of monoalkyl dimethyl benzyl ammonium salts include alkyl dimethyl benzyl ammonium chloride, commercially available from Lonza at Barquat; and benzyl chloride, commercially available from Lonza at Lonzagard. Additionally, monoalkyl dimethyl benzyl ammonium salts can be substituted. Non-limiting examples of such salts include dodecyl dimethyl-3,4-dichlorobenzyl ammonium chloride. Finally, mixtures of alkyl dimethyl benzyl and alkyl dimethyl-substituted benzyl (ethylbenzyl) ammonium chloride exist, commercially available from Stepan Company at BTC 2125M and from Lonza at Barquat 4250.

[0056] Dialkyl dimethyl ammonium salts contain two R groups as long-chain alkyl groups, and the remaining R groups are short-chain alkyl groups, such as methyl. Some non-limiting examples of dialkyl dimethyl ammonium salts include dialcyl dimethyl ammonium halide, commercially available from Lonza under Bardac 22; dialcyl dimethyl ammonium chloride, commercially available from Lonza under Bardac 2250; dioctyl dimethyl ammonium chloride, commercially available from Lonza under Bardac LF and Bardac LF-80; and octyl decyl dimethyl ammonium chloride, sold as a mixture with dialcyl and dioctyl dimethyl ammonium chloride, commercially available from Lonza under Bardac 2050 and 2080.

[0057] Heteroaromatic ammonium salts contain one R group as a long-chain alkyl group, with the remaining R groups provided by some aromatic system. Therefore, the quaternary nitrogen attached to the R group is part of an aromatic system such as pyridine, quinoline, or isoquinoline. Some non-limiting examples of heteroaromatic ammonium salts include hexadecylpyridinium halide, commercially available from Zeeland Chemical Inc. under Sumquat 6060 / CPC; 1-[3-chloroalkyl]-3,5,7-triaza-1-adamantane, commercially available from Dow Chemical Company under Dowicil 200; and alkyl isoquinoline bromides.

[0058] Polysubstituted quaternary ammonium salts are monoalkyltrimethylammonium salts, monoalkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, or heteroaromatic ammonium salts, wherein the anionic portion of the molecule is a large, high molecular weight (MW) organic ion. Some non-limiting examples of polysubstituted quaternary ammonium salts include alkyldimethylbenzylsulfonate ammonium and dimethylethylbenzylcyclohexylaminosulfonate ammonium.

[0059] Diquaternary ammonium salts contain two symmetrical quaternary ammonium moieties, and their general formula is as follows:

[0060] The R group can be a long-chain or short-chain alkyl group, a benzyl group, or provided by an aromatic system. Z is a carbon-hydrogen chain linked to each quaternary nitrogen. Some non-limiting examples of bisquaternary 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 trobiammonium chloride.

[0061] In one respect, quaternary ammonium compounds are medium- to long-chain alkyl R groups, such as 8 to about 20 carbons, 8 to about 18 carbons, about 10 to about 18 carbons, and about 12 to about 16 carbons, and provide solubility and good antimicrobial properties.

[0062] In one aspect, the quaternary ammonium compound is a short dialkyl chain quaternary ammonium compound having an R group, such as 2 carbons to about 12 carbons, 3 carbons to about 12 carbons, or 6 carbons to about 12 carbons.

[0063] On the one hand, quaternary ammonium compounds are blends or mixtures of alkylbenzylammonium chloride, dialkylbenzylammonium chloride, alkylbenzylammonium chloride and dialkylbenzylammonium chloride, dialkyldimethylammonium chloride, dioctyldimethylammonium chloride, dialkyltrimethylammonium chloride and dioctyldimethylammonium chloride.

[0064] In embodiments, the quaternary ammonium compound is included in the biocidal composition, preferably in its solution of use, at an amount of at least about 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, or 1000 ppm. In other embodiments, the quaternary ammonium compound is included in the biocidal composition, preferably in its solution of use, at an amount of at least about 1000 ppm, about 1000 ppm to about 5000 ppm, or about 1000 ppm to about 2000 ppm. Furthermore, without being limited by the invention, all ranges stated include the numbers defining the range and are included within the defined integers. It will be appreciated by those skilled in the art that the concentration of the quaternary ammonium compound can be provided at increased concentrations; however, the benefit of synergistic efficacy with the biocidal composition is achieved without excessive doses or concentrations of fatty acids.

[0065] Sources of hydrated hydrogen ions Combining a hydrated hydrogen ion source with the biocide described herein provides synergistic biocide efficacy against biofilms. The hydrated hydrogen ion source may comprise providing protonated water molecules (H3O) to the solution of use. +Any compound that appears in aqueous acids. In one embodiment, the source of hydrated hydrogen ions may be any compound capable of releasing / generating hydrated hydrogen ions in aqueous solution. In one embodiment, the source of hydrated hydrogen ions is an acid, preferably a strong acid. Exemplary strong acids include sulfuric acid, hydrogen sulfate, phosphoric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, methanesulfonic acid, or combinations thereof.

[0066] In an embodiment, the biocidal composition preferably contains hydrated hydrogen ions in its solution of use at an amount of at least about 0.003 moles (M) of hydrated hydrogen ions. In an embodiment, the biocidal composition contains hydrated hydrogen ions in its solution of use at an amount of about 0.003 to about 0.1 moles (M) of hydrated hydrogen ions.

[0067] In a preferred embodiment, the biocidal composition solution contains a combination of hydrated hydrogen ions and peroxides in an amount of about 0.003 to about 0.1 moles (M) of hydrated hydrogen ions, preferably about 0.005 M to about 0.1 M.

[0068] In a preferred embodiment, the biocidal composition solution contains a combination of hydrated hydrogen ions and fatty acid compounds in an amount of about 0.003 to about 0.1 moles (M) of hydrated hydrogen ions, preferably about 0.005 M to about 0.1 M.

[0069] In a preferred embodiment, the biocidal composition solution contains a combination of hydrated hydrogen ions and anionic surfactant compounds in an amount of about 0.005 to about 0.1 moles (M) of hydrated hydrogen ions, preferably about 0.007 M to about 0.1 M.

[0070] In a preferred embodiment, the biocidal composition solution contains a combination of hydrated hydrogen ions and a quaternary ammonium compound in an amount of about 0.003 to about 0.1 moles (M) of hydrated hydrogen particles, preferably about 0.005 M to about 0.1 M.

[0071] water In some embodiments, the biocidal composition may contain water. Water may be added to the composition independently or may be provided in the composition due to its presence in the aqueous material added to the composition.

[0072] In some embodiments, the composition contains sufficient water to constitute the remainder of the composition; in other embodiments, it contains about 0% to about 30% by weight, about 0.1% to about 30% by weight, about 0.1% to about 20% by weight, or about 0.5% to about 15% by weight of water. It should be understood that the invention covers all values ​​and ranges between these values ​​and ranges.

[0073] Additional functional ingredients The components of the biocidal composition may be further combined with various functional components suitable for the uses disclosed herein. In some embodiments, the composition comprising a biocidal agent and a source of hydrated hydrogen ions constitutes a majority or even almost all of the total weight of the composition. For example, in some embodiments, few or no additional functional ingredients are included.

[0074] In other embodiments, additional functional ingredients may be included in the biocidal composition. Functional ingredients provide the composition with desired properties and functions. For the purposes of this application, the term "functional ingredient" includes materials that provide advantageous properties for a particular application when dispersed or dissolved in a solution of use and / or a concentrated solution (e.g., an aqueous solution). Some specific embodiments of functional materials are discussed in more detail below; however, the specific materials discussed are given by way of example only, and a wide variety of other functional ingredients may be used.

[0075] In some embodiments, the composition may comprise 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 sequestrants or peracid stabilizers (e.g., DPA, HEDP, or other stabilizers such as those disclosed in U.S. Patent No. 9,902,627, which is incorporated herein by reference in its entirety), corrosion inhibitors, sequestrants and / or chelating agents, curing agents, sheeting flow aids, pH-modifying components including alkalinity and / or acidity sources, aesthetic enhancers (i.e., colorants, odorants, or fragrances), other cleaning agents, water-soluble agents or coupling agents, buffers, etc. Additionally, the composition may be used in combination with one or more conventional cleaning agents.

[0076] Other functional ingredients may be included in the biocidal composition in amounts of at least about 0% to about 50% by weight, about 0% to about 40% by weight, about 0% to about 30% by weight, or about 0% to about 20% by weight. Furthermore, without being limited by the invention, all ranges described include numbers defining the range and are included within integers within the defined range.

[0077] How to use This invention provides biocidal compositions that effectively inactivate biofilms and have numerous applications. The methods described herein should be understood as encompassing the treatment (i.e., inactivation), removal, and prevention of microbial communities that form and adhere to biofilms. Commercially, inactivation / removal of biofilms is preferred over prevention because preventing biofilm formation requires continuous (in some cases, continuous) administration of the biocidal composition, which can result in extremely high doses of chemical agents. Advantageously, since the biocidal compositions and methods described herein provide effective treatment and removal, commercial prevention is virtually unnecessary. Methods employing biocidal compositions are suitable for a variety of applications in industrial or commercial water systems and / or water sources, serving as drainage cleaners, hard surface cleaners and disinfectants, in-situ cleaning (CIP) disinfectants, etc., in industrial and / or commercial applications. For example, the compositions are suitable for system sanitation (e.g., tank / container / pipeline sanitation). In other embodiments, the compositions are suitable for biofilm inactivation (i.e., inactivation), reduction, and removal in water, paper, pulp processing, etc. In a variety of other industrial and consumer applications, the compositions are suitable for biofilm inactivation, reduction, and removal.

[0078] According to one embodiment, a method is provided for inactivating, reducing, and / or removing microbial communities in a water system or on a surface. According to another embodiment, a method is provided for inactivating, reducing, and / or removing biofilms from a water system or surface. In some aspects, the method is effective in killing one or more pathogenic bacteria associated with biofilm formation. Such bacteria include a variety of microorganisms, such as aerobic and anaerobic bacteria, including Gram-positive bacteria and Gram-negative bacteria, yeasts, molds, bacterial spores, viruses, etc. In another aspect, in addition to the microbial communities associated with biofilms, the method is effective in removing slime.

[0079] The advantage of this invention is that it effectively manages or kills planktonic and attached microorganisms by using the biocidal compositions described herein.

[0080] In one embodiment, the method is applicable to inactivating, reducing, and / or removing microbial communities (i.e., biofilms) in water systems and / or water sources to maintain the operation and performance of water systems. Water systems and / or water sources include, but are not limited to, cooling systems, including but not limited to cooling towers, cooling pools, and reactor cooling systems; food, beverage, and industrial processing water; pulp and paper systems; brewery pasteurizers; sweet water systems; air scrubber systems; oilfield drilling fluids and mud; oil extraction processes; mining pipelines; aquifers; fire-fighting water; industrial lubricants; cutting fluids; heat transfer systems; cooling systems; cooling towers; gas scrubber systems; latex systems; clay and pigment systems; decorative fountains; inlet pipes; ballast tanks; and ship storage tanks.

[0081] In one embodiment, the method is also applicable to inactivating, reducing, and / or removing microbial communities from various hard surfaces, including carcass tissues (or proteins or meat), including, for example, poultry. In an exemplary embodiment, the biocidal composition contacts the surface (e.g., poultry) in any manner to ensure good contact between the carcass and the composition, and optionally provides at least some minimum mechanical work to result in at least one log10 reduction in the microbial community within a 30-second contact time for disinfection treatment, preferably at least two log10 reductions, more preferably three log10 reductions, more preferably four log10 reductions, and most preferably five log10 reductions. The method is not limited to a range of carcass tissues such as beef, pork, veal, buffalo, lamb, seafood, and poultry, including but not limited to chicken, turkey, ostrich, hen, squab, or pheasant.

[0082] The method may include, consist of, and / or substantially consist of: adding a biocidal composition (or components of the biocidal composition added in one or more portions) to a water system or surface where microbial communities or biofilms require inactivation, reduction, and / or removal. For clarity, the biocidal composition may be provided as (a) a used or concentrated composition or (b) at least one biocide and a source of hydrated hydrogen ions, to contact the microbial community sequentially or simultaneously, individually. The contact method and / or the order in which the components of the biocidal composition are added are not intended to limit the methods described herein.

[0083] On one hand, adding a biocidal composition (or a component of the biocidal composition) to a water source or surface contaminated by a microbial community or biofilm (i.e., a drain or pipe) can reduce the colonization of target microorganisms (e.g., within a biofilm) by at least 20%, at least 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or about 100%. In some embodiments, contacting the biocidal composition with the microbial community or biofilm can completely remove the microbial community or biofilm (i.e., the composition is toxic to more than 90%, 99%, or 99.9% of the bacterial cells in the biofilm). On the other hand, the reduction and / or removal of microorganisms within the biofilm is achieved over at least 1 day, at least 2 days, at least 3 days, at least 4 days, at least 5 days, at least 6 days, or at least 7 days. In one embodiment, the biocidal composition is administered to a water source or surface contaminated by a biofilm at least once a week to reduce and / or remove microorganisms within the biofilm. In some embodiments, the target organism includes one or more Escherichia coli, Pseudomonas aeruginosa, Staphylococcus spp., Enterobacteriaceae, and Streptococcus spp. In some embodiments, the target organism includes Pseudomonas aeruginosa.

[0084] In one embodiment of the method, a biocidal composition is introduced into a container or system / equipment for a water system to disinfect surfaces against unwanted bactericides. The biocidal composition is introduced to remove biofilms from various hard surfaces, which may include in-situ cleaning systems (CIP) and / or translocation cleaning systems (COP). For water system treatment, a COP system may include, for example, an easily accessible system comprising tanks / containers, removable system components, etc. For water system treatment, a CIP system may include internal components of tanks, pipelines, pumps, and other treatment equipment for treating typical liquid product flows. Advantageously, the treatment of the various CIP and / or COP sections of the system is particularly suitable for water systems that heavily rely on internally recirculated water. Such internal recirculation is well-suited to methods using biocidal compositions because these compositions have sufficient lifetime and compatibility with water system sources / materials.

[0085] In another embodiment of the method, the biocidal composition is introduced into a water source, which includes water that is a byproduct of oilfield applications. This water is reused, recycled, or reinjected into treatment wells. In the presence of water, bacteria can form a colonized biofilm that is detrimental to such reuse, recycling, and / or reinjection. Introducing the biocidal composition helps to disrupt and remove biofilms from the treated water source and surfaces in contact with the water source.

[0086] In a preferred aspect, the biocidal composition is introduced (e.g., injected) into the water system, such as through pipes or containers. In another aspect, the biocidal composition is introduced upstream from a storage tank. Such introduction can be further combined with conventional cleaning and sanitation practices, which are typically carried out on water systems.

[0087] In some embodiments, the biocidal composition is discharged from the moving water system. However, in others, the biocidal composition (or a portion thereof) remains in the container or water system rather than being discharged from it. Stagnant water systems can take advantage of not requiring the discharge of the composition. The amount of biocidal composition remaining in the container can vary depending on the desired level of disinfection and on the stability of the biocidal composition.

[0088] In another embodiment of the method, the biocidal composition is introduced onto a hard surface or carcass surface, such as that of poultry, by immersing the surface in a shell containing the biocidal composition. Alternatively, the biocidal composition can be applied to the surface, such as by spraying. In one embodiment, spraying may involve pressurizing the biocidal composition onto the carcass, the surface of which may optionally be moved by mechanical action, preferably by agitation, friction, brushing, etc. Agitation can be performed by physically scrubbing the carcass, by the action of the spray solution under pressure, or by other means. In some embodiments, agitation increases the efficacy of the spray solution in killing microorganisms and / or reduces the required contact time. In some embodiments, the spray solution may also be heated to a temperature of about 15°C to 20°C, preferably about 20°C to 50°C, before application to enhance efficacy. After sufficient time has been spent killing microorganisms on the carcass, the spray solution can be rinsed off the animal carcass. Further disclosure of means of contacting a biocidal composition with a carcass is provided, for example, in U.S. Patent No. 9,770,040, which is incorporated herein by reference in its entirety. In other embodiments, rinsing is not required.

[0089] It should be understood that the method employs an aqueous biocidal composition, which may be provided as a concentrate or a working solution. Such compositions can be applied to or come into contact with an object using any conventional method or equipment for applying antimicrobial or cleaning compounds to an object. For example, the object may be poured onto the composition, foamed onto the composition, and / or immersed in the composition or a working solution made from the composition. The composition may be sprayed onto a surface; the composition may be allowed to flow over the surface; or the surface may be immersed in the composition. These and other methods of contacting an object or surface with the biocidal composition are within the scope of this invention. Contact may be performed manually or by machine.

[0090] The method may involve introducing the biocidal composition within a temperature range of about 0°C to 150°C, about 4°C to 150°C, or about 4°C to 60°C, depending on the application. After introducing the biocidal composition, the composition (e.g., a solution) is held in the container and / or circulated throughout the system for a sufficient time to remove biofilm and / or disinfect (e.g., kill unwanted microorganisms).

[0091] The contact time can vary based on the concentration of the biocidal composition, the method of application of the composition, temperature conditions, the amount of soil, microorganisms, or contaminants on the surface or equipment to be treated, etc. In some aspects, the biocidal composition can be retained in the water system. In some aspects, the exposure time can be at least about 60 seconds or longer. In some aspects, the contact can be carried out under conditions that effectively treat biofilms, such as 5 minutes to 5 hours, 10 minutes to 5 hours, 20 minutes to 5 hours, or 1 hour to 3 hours. As those skilled in the art will determine from the disclosure of the method, the amount of contact time can vary based on factors including temperature, the concentration of the biocidal composition, whether the treatment is stagnant or in a moving water system, etc. After removing biofilm and / or slime, the biocidal composition in the system can be removed (e.g., discharged from the system) or retained (entirely or partially) to obtain additional cleaning and / or disinfection benefits.

[0092] In some embodiments, the method may further utilize pressure and / or mechanical action to apply the biocidal composition. As those skilled in the art will understand, mechanical action may include, for example, agitation, friction, scrubbing, etc. Agitation can be performed by physically scrubbing surfaces (e.g., in a storage tank), by applying the solution under pressure, by ultrasound, or other methods. Agitation can enhance the microbial efficacy of the spray solution, possibly due to better exposure of the solution to cracks or small colonies containing microorganisms. Heating the spray solution before application may also enhance efficacy.

[0093] As will be known to those skilled in the art, within the scope of this invention, the amount of biocidal composition supplied to a water system will vary based on a number of factors. For example, size, structural orientation, materials used therein, and the level of contamination in the system will affect the amount (and / or concentration) of the biocidal composition applied thereto. In some aspects, hundreds of gallons of biocidal composition (e.g., a solution) may be supplied to a water system. In other aspects, thousands of gallons of biocidal composition (e.g., a solution) may be supplied to a water system.

[0094] Example The embodiments of the invention are further defined in the following non-limiting examples. It should be understood that these examples, while disclosing certain embodiments of the invention, are given by way of illustration only. From the foregoing discussion and these examples, those skilled in the art can recognize the essential characteristics of the invention, and various changes and modifications can be made to the embodiments of the invention to adapt them to various uses and conditions without departing from its spirit and scope. Therefore, in addition to what is described herein, various modifications to the embodiments of the invention will be apparent to those skilled in the art based on the foregoing description. Such modifications are intended to also fall within the scope of the appended claims.

[0095] Example 1 According to the standard test method ASTM E3161-18 (Preparation of Pseudomonas aeruginosa or Staphylococcus aureus using a CDC biofilm reactor) Staphylococcus aureus The efficacy of the biofilm was determined using the standard practice for biofilms and ASTM E2871-19 (Standard Test Method for Determining the Disinfectant Efficacy of Biofilms Grown in a CDC Biofilm Reactor Using a Single-Tube Method). *Pseudomonas aeruginosa* (ATCC 15442) biofilms were used to determine the efficacy of the composition against biofilms on rigid, non-porous surfaces. The composition efficacy was determined according to the outline in ASTM E3161-18. 10 µL of thawed frozen stock culture was inoculated into 10 mL of sterile 100 mg / L trypsin-soy broth (TSB) and incubated at 35 ± 2 °C for 24 ± 2 h. After growth, 1 mL of this initial culture sample was inoculated into a CDC biofilm reactor containing a borosilicate glass slide and 500 mL of sterile 300 mg / L TSB. Following ASTM E3161-18, the reactor system was allowed to incubate in the batch phase for 24 ± 2 hours at room temperature (i.e., 21 ± 2 °C) with a baffle rotation speed of 125 ± 5 RPM. After the batch phase growth, continuous flow phase growth was initiated by continuously pumping 100 mg / L TSB into the reactor system at an appropriate flow rate to ensure a residence time of 30 ± 2 minutes for the test organism. Following ASTM E3161-18, the reactor system was allowed to incubate in the continuous flow phase for 24 ± 2 hours at room temperature (i.e., 21 ± 2 °C) with a baffle rotation speed of 125 ± 5 RPM. After growth, the biofilm test carriers were removed from the CDC biofilm reactor, rinsed in sterile buffer to remove any non-adherent cells, and individual carriers were placed in sterile 50 mL conical tubes for composition processing. The composition efficacy against *Pseudomonas aeruginosa* biofilms was determined according to the overview in ASTM E2871-19. Pipette 4 mL of sample (or sterile buffer of control carrier) of each composition into the corresponding tube containing the test carrier. Analyze the triphosphate test carrier according to the composition or control. Allow the test and control carriers to be exposed at room temperature (i.e., 21 ± 2 °C) for 10 minutes. After exposure, neutralize each carrier appropriately with 36 mL of neutralizing broth. Vortex mix and sonicate the neutralized carriers as outlined in ASTM E2871-19 to remove / depolymerize the biofilm on the carrier surface. Depolymerized biofilm samples are serially diluted in sterile buffer and spread onto appropriate agar plates to determine plate counts. The Log reduction for each composition is determined by comparing the calculated Log10 of the recovered control carrier group with the average Log10 of the recovered composition carrier group. In addition to the carrier control determination, appropriate neutralization confirmation controls are performed for each composition to ensure that the selected neutralizing broth is properly neutralized for the test solution.

[0096] Various combinations of biocide and hydrated hydrogen ions (both derived from sulfuric acid) were evaluated at the application concentration (ppm biocide), pH, and molar number of hydrated hydrogen ions in the application concentration (as shown in Table 2). The mean log reduction for each tested combination (or the control using only biocide) was measured, as shown in Table 2.

[0097]

[0098] There is one outlier (*), indicating that the microefficiency at pH should be significantly better. Replicated data show a decrease in logarithmic efficiency.

[0099] The data in Table 2 show that, at the same concentration, neither peroxyacids nor hydrated hydrogen ions alone effectively provided a log reduction of at least about 6 log. Instead, unique efficacy was achieved due to the synergistic effect of peroxyacids and hydrated hydrogen ions against biofilms. The data further indicate that biocides combined with hydrated hydrogen ions are effective when using fatty acids, anionic surfactants, and / or quaternary ammonium-based biocides, providing various benefits for formulating compositions containing multiple biocides compatible with hydrated hydrogen ions and offering unexpected synergistic effects against biofilms.

[0100] The data in Table 2 further demonstrate that synergistic effects occur when hydrated hydrogen ions from an acid source combine with biocides at acidic pH to provide synergistic effects and effective log reductions, such as at least about 5 log reductions, or preferably at least about 6 log reductions. Although different regulatory agencies will require specific log reductions for microefficacy, i.e., biofilm control and disinfection efficacy, surprisingly, microefficacy is significantly enhanced when combined with a source of hydrated hydrogen ions. In some embodiments, at least 5-log reductions, or preferably at least 6-log reductions, are achieved.

[0101] For example, at 220 ppm (the desired concentration range for food contact), using POAA without hydrated hydrogen ions does not provide sufficient microefficacy. However, increasing the hydrated hydrogen ion concentration and decreasing the pH synergistically enhance microefficacy, outweighing any benefit gained by increasing the percarboxylic acid concentration. Increasing the percarboxylic acid concentration above 220 ppm (including 320 ppm, 420 ppm, and even 520 ppm) does not yield any biocidal activity benefit. The same synergistic combination is also observed with increasing the hydrated hydrogen ion concentration in POOA and quaternary ammonium chloride. This microefficacy performance is unexpected, as we would expect an increase in microefficacy resulting from an increase in biocide concentration, which is not the result shown in Table 2.

[0102] The results in Table 2 further demonstrate that pH (including that provided by sulfuric acid) can be used to modulate the surface activity of the biocidal components. It is anticipated that additional acid sources can be used to further increase or modulate surface activity, while providing the same range of biocidal compounds and hydrated hydrogen ions.

[0103] Example 2 The testing of the biofilm inactivation composition also demonstrated its further application in treating surfaces containing adhered cells, such as tissue surfaces (e.g., poultry).

[0104] Advantageously, direct application of the composition to the surface to be treated can achieve at least a 1-log reduction on tissue surfaces, which is a commercially relevant biocidal efficacy. Advantageously, the biocidal composition providing synergistically increased efficacy can be used in routine short-contact treatments of poultry (and tissues or carcasses) without further causing any negative sensory effects. It is further desirable that the biocidal composition can be provided as (a) an application or concentrated composition, or (b) at the point of application, sequentially or simultaneously, as a component of the biocidal agent and a source of hydrated hydrogen ions.

[0105] The present invention also relates to the following specific embodiments: 1. A biofilm inactivation composition, comprising: At least one biocide, wherein the biocide is a peroxide compound, a fatty acid, an anionic surfactant, and / or a quaternary ammonium compound; and The source of hydrated hydrogen ions, wherein the source of hydrated hydrogen ions is one or more strong acids selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, or methanesulfonic acid. The use of a solution of the composition at a concentration of at least about 100 ppm provides at least a 5-log reduction.

[0106] 2. The composition according to claim 1, wherein the peroxide biocide is a peroxycarboxylic acid, hydrogen peroxide, percarbonate, persulfate, perborate, permanganate, urea peroxide, and / or alkyl peroxide.

[0107] 3. The composition according to claim 2, wherein the peroxide biocide is a C1-C22 peroxycarboxylic acid or a C1-C22 peroxycarboxylic acid composition comprising hydrogen peroxide, a C1-C22 carboxylic acid and the C1-C22 peroxycarboxylic acid.

[0108] 4. The composition according to claim 3, wherein the peroxycarboxylic acid is peracetic acid and / or peroxyoctanoic acid.

[0109] 5. The composition according to any one of claims 1 to 4, wherein the peroxycarboxylic acid is provided in the solution of the composition at a concentration of at least about 100 ppm, at least about 150 ppm, or at least about 200 ppm, or about 100 ppm to about 500 ppm.

[0110] 6. The composition according to claim 1, wherein the fatty acid biocide is a C5 to C22 carboxylic acid.

[0111] 7. The composition according to claim 6, wherein the fatty acid is provided in the solution of the composition at a concentration of at least about 100 ppm or from about 100 ppm to about 500 ppm.

[0112] 8. The composition according to claim 1, wherein the anionic surfactant biocide is a sulfonate and / or sulfate, a carboxylate and / or a polycarboxylate, a sulfonate carboxylic acid, an ether carboxylic acid, a sulfonated fatty acid, an alcohol ethoxylate, and / or a combination thereof.

[0113] 9. The composition according to claim 8, wherein the anionic surfactant is an alkane sulfonate.

[0114] 10. The composition according to any one of claims 8 to 9, wherein the anionic surfactant is provided in the solution of use of the composition at a concentration of at least about 1000 ppm, about 1000 ppm to about 5000 ppm, or about 1000 ppm to about 2000 ppm.

[0115] 11. The composition according to claim 1, wherein the quaternary ammonium compound biocide has the general formula R1-R4 each have a chain length less than C20 and can be the same or different substituted or unsubstituted, saturated or unsaturated, branched or unbranched and cyclic or acyclic alkyl groups, and can contain ether, ester or amide bonds, and can be aromatic or substituted aromatic groups, and X- is an anionic counterion.

[0116] 12. The composition according to claim 11, wherein the quaternary ammonium compound is provided in a solution of the composition at a concentration of at least about 500 ppm, about 500 ppm to about 5000 ppm, or about 1000 ppm to about 2000 ppm.

[0117] 13. The composition according to any one of claims 1 to 12, wherein in the solution of the composition, the source of hydrated hydrogen ions is provided at a concentration of at least about 0.003 M hydrated hydrogen ions, about 0.003 M to about 0.1 M hydrated hydrogen ions, or about 0.005 M to about 0.1 M hydrated hydrogen ions.

[0118] 14. The composition according to any one of claims 1 to 13, further comprising at least one additional functional ingredient.

[0119] 15. The composition according to claim 14, wherein the additional functional component is a stabilizer.

[0120] 16. A method for inactivating, reducing, and / or removing adhered bacteria or biofilm from a surface, the method comprising: Contacting the microbial community with the composition according to any one of claims 1 to 15; and Reduce and / or eliminate the microbial community.

[0121] 17. The method according to claim 17, wherein the microbial community is located on a hard surface and / or within a water system.

[0122] 18. The method according to claim 17, wherein the surface is a food surface, and optionally the food surface is poultry.

[0123] 19. The method of claim 17, wherein the surface is in contact with a water system or water source, wherein the water system or water source is one or more of the following: oilfield drilling fluids and mud; oil extraction processes; mining pipelines; water-bearing pipelines; fire-fighting water; industrial lubricants; cutting fluids; heat transfer systems; cooling towers; gas scrubber systems; latex systems; clay and pigment systems; cooling systems; cooling towers; water for food, beverage and industrial processing; pulp and paper systems; brewery pasteurizers; sweet water systems; air scrubber systems; decorative fountains; inlet pipes; ballast tanks; and ship storage tanks.

[0124] 20. The method according to claim 17, wherein the surface is a drain pipe.

[0125] 21. The method according to any one of claims 16 to 20, wherein the microbial community is a planktonic or attached microbial community, or a biofilm comprising one or more bacteria, including *Escherichia coli* (…). Escherichia coli ), Pseudomonas aeruginosa ( Pseudomonas aeruginosa Staphylococcus spp. Staphylococcal Bacteria, Enterobacteriaceae ( Enterobacteriaceae Bacteria and Streptococcus ( Streptococcus )bacteria.

[0126] 22. The method according to any one of claims 16 to 21, wherein the composition is provided as (a) a used or concentrated composition or (b) at least one biocide and the source of hydrated hydrogen ions, to contact the microbial community sequentially or simultaneously.

[0127] It should be understood that although the invention has been described in conjunction with a detailed description, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other embodiments, advantages, and modifications are within the scope of the following claims. Furthermore, the contents of all patent publications discussed above are incorporated herein by reference in their entirety.

[0128] As appropriate, features disclosed in the foregoing description or appended claims (either in their specific form or in terms of the means for performing the disclosed function or the method or process for obtaining the disclosed result) may be used alone or in any combination of such features to implement the invention in its different forms.

Claims

1. A biofilm inactivation composition, comprising: At least one biocide, wherein the biocide is peracetic acid and / or peroctanoic acid; as well as The source of hydrated hydrogen ions, wherein the source of hydrated hydrogen ions is one or more strong acids selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, or hydroiodic acid. The composition is provided in a concentration of at least 100 ppm and provides an application pH of 2.5 or below and a reduction of at least 5-log in the population of microorganisms and pathogens in the biofilm. The hydrated hydrogen ion source is provided in the composition for use at a concentration of at least 0.003 M hydrated hydrogen ions.

2. The composition according to claim 1, wherein the biocide is peracetic acid and peroctanoic acid.

3. The composition according to claim 1 or 2, wherein the peracetic acid and / or peroctanoic acid are provided at a concentration of at least 100 ppm in the solution of the composition.

4. The composition of claim 1, wherein the biocide further comprises a C5-C22 fatty acid, and wherein the C5-C22 fatty acid is provided in the solution of the composition at a concentration of at least 100 ppm.

5. The composition according to claim 1, wherein the biocide further comprises a quaternary ammonium compound biocide having the general formula R1-R4 each have a chain length less than C20 and can be the same or different substituted or unsubstituted, saturated or unsaturated, branched or unbranched and cyclic or acyclic alkyl groups, and can contain ether, ester or amide bonds, and can be aromatic or substituted aromatic groups, and X- is an anionic counterion.

6. The composition according to claim 5, wherein the quaternary ammonium compound is provided in the solution of the composition at a concentration of at least 500 ppm.

7. The composition according to any one of claims 1 to 6, wherein in the solution of the composition, the source of hydrated hydrogen ions is provided at a concentration of 0.003 M to 0.1 M hydrated hydrogen ions.

8. The composition according to any one of claims 1 to 7, further comprising at least one additional functional ingredient.

9. The composition according to claim 8, wherein the additional functional component is a stabilizer.

10. The composition according to claim 1, wherein when the biocide is peracetic acid and / or peroxyoctanoic acid, the biocide further comprises peroxycarboxylic acid, hydrogen peroxide, percarbonate, persulfate, perborate, permanganate, urea peroxide and / or alkyl peroxide.

11. A method for inactivating, reducing, and / or removing adhered bacteria or biofilm from a surface, the method comprising: Contact the microbial community with the composition according to any one of claims 1 to 10; as well as Reduce and / or eliminate the microbial community.

12. The method of claim 11, wherein the microbial community is located on a hard surface and / or within a water system.

13. The method of claim 11, wherein the surface is a food surface, and optionally the food surface is poultry.

14. The method of claim 11, wherein the surface is in contact with a water system or water source, wherein the water system or water source is one or more of the following: oilfield drilling fluids and mud; oil extraction processes; mining pipelines; water-bearing pipelines; fire-fighting water; industrial lubricants; cutting fluids; heat transfer systems; cooling towers; gas scrubber systems; latex systems; clay and pigment systems; cooling systems; cooling towers; water for food, beverage and industrial processing; pulp and paper systems; brewery pasteurizers; sweet water systems; air scrubber systems; decorative fountains; inlet pipes; ballast tanks; and ship storage tanks.

15. The method of claim 11, wherein the surface is a drain pipe.

16. The method according to any one of claims 11 to 15, wherein the microbial community is a planktonic or attached microbial community, or a biofilm comprising one or more bacteria, said bacteria including *Escherichia coli* (…). Escherichia coli ), Pseudomonas aeruginosa ( Pseudomonas aeruginosa Staphylococcus spp. Staphylococcal Bacteria, Enterobacteriaceae ( Enterobacteriaceae Bacteria and Streptococcus ( Streptococcus )bacteria.

17. The method according to any one of claims 11 to 16, wherein the composition may be provided as (a) a use composition or a concentrated composition or (b) at least one biocide and the source of hydrated hydrogen ions, to contact the microbial community sequentially or simultaneously, individually.

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