Solid peroxo alpha hydroxy carboxylic acid generating compositions and uses thereof

Abstract

Disclosed are peroxyl hydroxycarboxylic acid forming compositions and methods of forming, preferably in situ, peroxyl hydroxycarboxylic acids using the same. Also disclosed are methods of using the peroxyl hydroxycarboxylic acids, including for treating surfaces or targets in need of antimicrobial or disinfecting treatment. Specific applications are disclosed for the use of odorless, low volatile peroxyl hydroxycarboxylic acid disinfectants for direct food contact.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 199,856, filed January 29, 2021, pursuant to 35 USC § 119, which is incorporated herein by reference in its entirety. This application also relates to U.S. Publication No. 2021 / 0238135, filed January 29, 2021, which claims priority to U.S. Provisional Application Serial No. 62 / 968,597, filed January 31, 2020, entitled "Generation of Peroxyhydroxycarboxylic Acid and the Use Thereof". Each of these two patent applications, including but not limited to the description, claims, and abstract, and any drawings, tables, or examples thereof, is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure relates throughout to peroxyhydroxycarboxylic acid forming compositions, specifically solid peroxyα-hydroxycarboxylic acid forming compositions, and methods for using said solid compositions to form, preferably in situ, peroxyhydroxycarboxylic acids (i.e., peroxyα-hydroxycarboxylic acids). This disclosure also relates to methods for using said compositions to form peroxyhydroxycarboxylic acids for treating surfaces or targets requiring antimicrobial treatment. Applications of odorless, low-volatility peroxyhydroxycarboxylic acid disinfectants include their use as direct food contact disinfectants. Background Technology

[0004] Peroxycarboxylic acid compositions are typically prepared via acid-catalyzed equilibrium reactions. In most cases, peroxycarboxylic acids are generated in chemical plants and then transported to the customer's site for use. Due to the limited storage stability of peroxycarboxylic acids, they must be packaged in special containers and transported according to strict Department of Transport (DOT) guidelines. Furthermore, excess reagents (e.g., acids, oxidants, and stabilizers) are present in the composition during transport to prevent decomposition. For these reasons, the need for on-site generation of peroxycarboxylic acids persists.

[0005] Percarboxylic acids are increasingly used as antimicrobial agents, disinfectants, and bleaching agents in various applications due to their high efficacy against a broad spectrum of microorganisms, color-safe properties, low residues, and non-toxic decomposition products. Peracetic acid is the most commonly used percarboxylic acid. Because of its broad antimicrobial efficiency, peracetic acid is increasingly used as a direct food contact disinfectant, and importantly, it decomposes into acetic acid, water, and oxygen without leaving toxic residues. However, its use has drawbacks: peracetic acid has a relatively high vapor pressure, a strong pungent odor, and is irritating to tissues when inhaled. Therefore, in the United States, the Occupational Safety and Health Administration (OSHA) has set concentration limits for peracetic acid in the air. For example, in open systems where it is applied at relatively high concentrations, and in places where large amounts of peracetic acid are used (such as in poultry processing plants), the concentration of peracetic acid in the air can pose serious safety problems for workers. Therefore, there is a need to find alternative effective and odorless antimicrobial agents that do not leave toxic residues and have very low vapor pressures.

[0006] Hydroxycarboxylic acids, including α-hydroxycarboxylic acids (such as lactic acid), are readily available compounds that can be produced from food-grade raw materials. They are widely used in the food industry as acidifying agents and antimicrobial agents. Hydroxycarboxylic acids have very low vapor pressures and no pungent odor. While α-hydroxycarboxylic acids (such as lactic acid) are known to possess antimicrobial properties, their antimicrobial efficacy is relatively low, requiring at least a certain percentage level of the compound to achieve the desired effect. This is a significant limitation to their widespread use as antimicrobial agents for food safety. Therefore, attempts have been made to enhance the antimicrobial efficacy of lactic acid by converting it to perlactic acid. These attempts involve reacting lactic acid with hydrogen peroxide (such as using acetic acid to generate peracetic acid). This has proven unsuccessful because, unlike simple alkane carboxylic acids (such as acetic acid), α-hydroxycarboxylic acids are weak reducing agents and are therefore readily oxidized by hydrogen peroxide during the reaction to generate the corresponding peroxy-α-hydroxycarboxylic acid. This requires high concentrations of hydrogen peroxide, and the reaction can take hours to days, resulting in a lack of adaptability for use in the industry. A further reason for the lack of adaptation and use is that the oxidation of α-hydroxycarboxylic acids by hydrogen peroxide leads to numerous stability problems, and some oxidized substances may be unsafe for direct food use. As another drawback, conventional methods for generating peroxyhydroxycarboxylic acids (such as peroxylactic acid) cause the composition to begin decomposing at a rate as fast as the formation rate, thus providing an insufficient concentration of peroxyhydroxycarboxylic acids in the composition.

[0007] There is a need to find alternative methods for generating peroxyhydroxycarboxylic acids (such as peroxylactic acid), including generation from solid compositions containing precursor materials, to react and form the desired peroxyhydroxycarboxylic acid. This disclosure addresses this problem and related needs using peroxyhydroxycarboxylic acids, particularly those exhibiting improved antimicrobial efficacy compared to their corresponding α-hydroxycarboxylic acids.

[0008] It is also necessary to generate a stoichiometric amount of peroxyhydroxycarboxylic acid from the solid composition such that one mole of lactone precursor will generate one mole of the corresponding peroxyα-hydroxycarboxylic acid plus one mole of α-hydroxycarboxylic acid.

[0009] Another need is for a method that generates peroxyhydroxycarboxylic acid from a solid composition in a faster reaction, which takes minutes instead of hours or days.

[0010] Additionally, in-situ generation of peroxyhydroxycarboxylic acids is required, the generation including a color indicator suitable for detecting the formation of peroxyhydroxycarboxylic acids in a liquid medium.

[0011] Additionally, in-situ generation of peroxyhydroxycarboxylic acids from the solid composition is required, which can then be used on-site or immediately after generation to avoid oxidation of α-hydroxycarboxylic acids.

[0012] This document provides various requirements and implementation schemes, including solid or liquid compositions for the in-situ generation of peroxyhydroxycarboxylic acids. Summary of the Invention

[0013] This disclosure relates in its entirety to a peroxy α-hydroxycarboxylic acid forming composition, a method for forming a peroxy α-hydroxycarboxylic acid from the composition using the peroxy α-hydroxycarboxylic acid forming composition, preferably in situ forming a peroxy α-hydroxycarboxylic acid, and a method and use of the peroxy α-hydroxycarboxylic acid preferably in situ for treating a surface or target.

[0014] In an embodiment, a method for forming a peroxy α-hydroxycarboxylic acid from a peroxy α-hydroxycarboxylic acid forming composition includes a contact step, said contact step being any of the following: (a) contacting a solid peroxy α-hydroxycarboxylic acid forming composition with a liquid, wherein the solid composition comprises a diester of a lactone of an α-hydroxycarboxylic acid, an alkalinity source, and / or a substance that generates hydrogen peroxide upon contact with the liquid, and forming a liquid containing the peroxy α-hydroxycarboxylic acid and having a pH less than about 8 within about 5 minutes after the solid composition is contacted with the liquid; or (b) contacting a liquid peroxy α-hydroxycarboxylic acid forming composition comprising a diester of a lactone of an α-hydroxycarboxylic acid dissolved together with a solvent with an alkalinity source and / or hydrogen peroxide, and forming a liquid containing the peroxy α-hydroxycarboxylic acid and having a pH less than about 8 within about 5 minutes after the solution is contacted with the alkalinity source and / or hydrogen peroxide; and forming at least about 1 ppm of the peroxy α-hydroxycarboxylic acid within less than 1 minute of the start of said contact step.

[0015] In another embodiment, the peroxy α-hydroxycarboxylic acid forming composition comprises: a) a diester of an α-hydroxycarboxylic acid lactone, b) an alkalinity source and / or a substance that generates hydrogen peroxide upon contact with a liquid; and c) an optional additional functional ingredient; wherein the composition is a liquid when the diester of the α-hydroxycarboxylic acid lactone is dissolved in a solvent, and wherein, upon contact of the diester of the α-hydroxycarboxylic acid lactone with the alkalinity source and / or the hydrogen peroxide-generating substance, the composition reacts within about 5 minutes to form the peroxy α-hydroxycarboxylic acid with a pH less than about 8; or wherein the composition is a solid, and wherein the solid composition reacts upon dissolution in a liquid to form the peroxy α-hydroxycarboxylic acid and has a pH less than about 8 within about 5 minutes after the diester of the α-hydroxycarboxylic acid lactone is contacted with the alkalinity source and / or the hydrogen peroxide-generating substance.

[0016] In other embodiments, the peroxy α-hydroxycarboxylic acid composition is formed by combining a solid composition as described herein with water or a non-aqueous liquid.

[0017] In other embodiments, the method for treating a target includes contacting the target with an effective amount of a peroxy α-hydroxycarboxylic acid as described herein to form a treated target composition, wherein the treated target composition contains about 0.1 ppm to about 10,000 ppm of the peroxy α-hydroxycarboxylic acid, and the contact lasts for a sufficient time to bleach, remove dirt, sterilize the target or the treated target composition, and / or stabilize or reduce the microbial community therein and / or on them.

[0018] While several embodiments have been disclosed, other embodiments of the invention will become apparent to those skilled in the art from the following detailed description of the illustrative embodiments shown and described. Therefore, the drawings and detailed descriptions are considered to be illustrative rather than restrictive in nature. Attached Figure Description

[0019] Figure 1 The perhydrolysis of lactide according to the embodiments described herein is demonstrated, wherein the perhydrolysis forms peroxylactic acid.

[0020] Figure 2 The perhydrolysis of glycolide according to the embodiments described herein is demonstrated, the perhydrolysis forming perglycolic acid.

[0021] Figure 3 It demonstrated the efficacy of low concentrations of peroxylactic acid, particularly against Listeria.

[0022] Various embodiments of the invention will be described in detail with reference to the accompanying drawings, wherein the same reference numerals denote the same parts in several views. References to various embodiments do not limit the scope of the invention. The accompanying drawings illustrated herein are not limiting to various embodiments according to the invention, but are presented for illustrative purposes only. Detailed Implementation

[0023] Embodiments of the present invention are not limited to specific solid peroxy α-hydroxycarboxylic acid forming compositions, methods for forming peroxy α-hydroxycarboxylic acids from said solid compositions, the formed peroxy α-hydroxycarboxylic acids, and methods of using them; these can vary and are understood by those skilled in the art. 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, all units, prefixes, and symbols may be represented in a form acceptable to them in SI. The numerical ranges listed in the specification include the numbers defining the ranges and include every integer within the defined range.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. All patents, applications, publications, and other publications mentioned herein are incorporated herein by reference in their entirety. If a definition set forth in this section contradicts or otherwise contradicts a definition set forth in a patent, application, publication, or other publication incorporated herein by reference, the definition set forth in this section shall prevail. To facilitate a clearer understanding of the invention, certain terms are defined first. 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 embodiments of the invention pertain. Many methods and materials similar to, modified from, or equivalent to those described herein can be used in the practice of embodiments of the invention without requiring extensive experimentation; preferred materials and methods are described herein. In describing and claiming embodiments of the invention, the following terms will be used according to the definitions stated below.

[0025] It should be noted that, unless the context clearly indicates otherwise, the singular forms "a / an" and "the" as used in this specification and the appended claims include plural references. Thus, for example, references to compositions containing "compound" include compositions having two or more compounds. It should also be noted that, unless the content clearly indicates otherwise, the term "or" is generally used in the sense of including and / or.

[0026] As used herein, the term "about" refers to a possible variation in numerical quantity, for example, through typical measurement and liquid handling procedures used in the preparation of concentrates or the use of solutions in the real world; through errors due to negligence in these procedures; through differences in the manufacture, origin, or purity of the ingredients used to prepare the composition or to carry out the method; and so on. The term "about" also covers amounts that differ due to different equilibrium conditions for the composition resulting from a particular initial mixture. Whether or not modified by the term "about," the claims contain equivalents of the quantity.

[0027] The terms “surfactant” or “surfactant percentage” or “surfactant weight percentage” or “surfactant concentration” are used interchangeably herein and refer to the concentration of those ingredients involved in cleaning, expressed as a percentage after subtracting inert ingredients such as water or salt.

[0028] As used herein, the term "cleaning" means performing or assisting in the removal of dirt, bleaching, reduction of microbial communities, or a combination thereof. For the purposes of this patent application, microbial reduction is successfully achieved when the microbial community is reduced by at least about 50%, or significantly more than that achieved by rinsing with water. A substantial reduction in the microbial community provides a higher level of protection.

[0029] As used herein, "consistent with" means that a method or composition may include additional steps, components or ingredients, provided that the additional steps, components and / or ingredients do not materially alter the essential and novel features of the claimed method composition.

[0030] As used herein, the term "dimensional stability" or "dimensional stability" refers to the structural integrity of a solid that ensures it does not soften, absorb moisture, and / or swell. A solid product with suitable dimensional stability has a growth index of less than about 5%, or preferably less than about 3%. The growth index refers to the percentage of growth or swelling of a product over a period of time (such as 7 or 14 days) after it has cured under normal transport / storage conditions. Because normal transport / storage conditions typically subject the composition to high temperatures, the growth index of a solid product can be determined by measuring one or more dimensions of the product before and after heating between about 100°F and 122°F. The one or more dimensions measured depend on the shape of the solid product and its swelling pattern. For tablets, changes in both diameter and height are typically measured, and the growth index measured each time must be less than a defined measurement value to meet the thresholds for both growth index and dimensional stability. For capsules, typically only the diameter is measured. If a solid product swells after curing (i.e., the measured growth index), various problems can occur, including but not limited to decreased density, integrity, and appearance; and the inability to dispense or package the solid product.

[0031] As used herein, the term "bactericide" refers to an agent that kills all vegetative cells, including most identified pathogenic microorganisms, using the procedures described in AOAC's "AOC Care Dilution Methods, paragraph 955.14 and applicable sections, 15th edition, 1990 (EPA Guideline 91-2)". As used herein, the terms "high-level bactericide" or "high-level bactericide" refer to an agent that kills substantially all organisms except for high levels of bacterial spores and is used according to the procedures described by the Food and Drug Administration (FDA). The Drug Administration (DGA) sells compounds or compositions that are chemically controlled disinfectants as sterilizing agents. As used herein, the terms "intermediate level disinfectant" or "intermediate level disinfectant" refer to compounds or compositions that, as registered with the Environmental Protection Agency (EPA) as tuberculosis-killing agents, kill mycobacteria, most viruses, and bacteria using chemical disinfectants. As used herein, the terms "low level disinfectant" or "low level disinfectant" refer to compounds or compositions that, as registered with the EPA as hospital disinfectants, kill some viruses and bacteria using chemical disinfectants.

[0032] As used herein, the phrase "food processing surface" refers to the surface of tools, machinery, equipment, structures, buildings, etc., that is used as part of food or beverage processing, preparation, or storage activities. Food processing surface is intended to encompass all surfaces used in brewing (including beer brewing and the preparation of spirits and baijiu) and brewing processes (e.g., bright beer tanks and production lines, fermentation vessels, mashing tanks, bottling equipment, piping, and storage containers). Examples of food processing surfaces include food processing utensils (e.g., appliances, cutlery, washing utensils, and bar glasses), food processing or preparation equipment (e.g., boiling, fermentation, slicing, canning, or conveying equipment containing chutes), and the surfaces of floors, walls, or fixtures of structures where food processing takes place. Food processing surfaces are found and used in food preservation air circulation systems, aseptic packaging disinfection, food refrigerator and cooler cleaners and disinfectants, utensil washing and disinfection, scalding and disinfection, food packaging materials, cutting board additives, third-level water tank disinfection, beverage coolers and insulators, meat cooling or scalding water, automatic dish disinfectants, disinfectant gels, cooling towers, food processing antimicrobial clothing sprays, and non-aqueous to low-aqueous food preparation lubricants, oils, and rinsing additives.

[0033] As used herein, the phrase “food” includes any food that may require treatment with antimicrobial agents or compositions and may be consumed with or without further preparation. Food includes meats (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, corn, flowers, sprouts, seasonings, or combinations thereof. The term “agricultural products” refers to food, such as fruits and vegetables, and plants or plant-derived materials that are typically sold uncooked and generally unpackaged and are sometimes edible raw.

[0034] As used herein, the terms "free of," "not," "substantially not," or "substantially free of" mean a composition, mixture, or ingredient that does not contain a specific compound or has not yet been added to, or contains, a specific compound. In some embodiments, the reduction and / or elimination of hydrogen peroxide according to the embodiment provides a composition that is free of or substantially free of hydrogen peroxide. If a specific compound is present by contamination and / or the use of a minimum amount of the composition, mixture, or ingredient, the amount of the compound should be less than about 3% by weight. More preferably, the amount of the compound is less than 2% by weight, less than 1% by weight, and most preferably, the amount of the compound is less than 0.5% by weight.

[0035] The term "hard surface" refers to a solid, substantially non-flexible surface, such as countertops, tiles, floors, walls, panels, windows, sanitary ware, kitchen and bathroom furniture, appliances, engines, circuit boards, instruments, and dishes. Hard surfaces can also include, for example, healthcare surfaces and food processing surfaces.

[0036] As used herein, the term "microbe" refers to any noncellular or single-celled (including colonies) organism. Microbes include all prokaryotes. Microbes include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, prions, viroids, viruses, bacteriophages, and some algae. As used herein, the term "microbe" is synonymous with "microorganism."

[0037] As used herein, the term "peroxy α-hydroxycarboxylic acid" (or peracid) includes any compound of the formula R-CR′(OH)-(COOOH)n, wherein R and R′ can be hydrogen, alkyl, alkenyl, alkyne, acyl, alicyclic, aryl, heteroaryl, or heterocyclic, and n is 1, 2, or 3, and is named by adding the peroxy prefix before the parent acid. Preferably, R comprises hydrogen, alkyl, or alkenyl. The terms "alkyl", "alkenyl", "alkyne", "acyl", "alicyclic", "aryl", "heteroaryl", and "heterocyclic" are as defined herein. As used herein, the term "alkyl" includes a straight-chain or branched saturated aliphatic hydrocarbon chain having 1 to 22 carbon atoms, such as methyl, ethyl, propyl, isopropyl (1-methylethyl), butyl, tert-butyl (1,1-dimethylethyl), etc. The term "alkyl (alkyl / alkyl group)" also refers to a saturated hydrocarbon having one or more carbon atoms, including straight-chain alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl (or "cycloalkyl" or "alicyclic" or "carbocyclic") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched alkyl (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl (e.g., alkyl-substituted cycloalkyl and cycloalkyl-substituted alkyl).

[0038] Unless otherwise stated, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl". As used herein, the term "substituted alkyl" refers to an alkyl group in which one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone are replaced by substituents. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkyl carbonyloxy, aryl carbonyloxy, alkoxy carbonyloxy, aryloxy, aryloxy carbonyloxy, carboxylic acid ester, alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, amino carbonyl, alkyl amino carbonyl, dialkyl amino carbonyl, alkyl thio carbonyl, alkoxy, phosphate ester, phosphonic acid, phosphonite, cyano, amino (including alkyl amino, dialkyl amino, aryl amino, diaryl amino and alkyl aryl amino), amide (including alkyl carbonyl amino, aryl carbonyl amino, carbamoyl and urea), imino, mercapto, alkyl thio, aryl thio, thiocarboxylic acid ester, sulfate ester, alkyl sulfinyl, sulfonate, aminosulfonyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkyl aryl or aromatic (including heteroaromatic) groups.

[0039] The term "alkenyl" encompasses an unsaturated aliphatic hydrocarbon chain having 2 to 12 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, etc. Alkyl or alkenyl groups can be terminally substituted with heteroatoms such as nitrogen, sulfur, or oxygen atoms to form aminoalkyl, alkoxy, or thioalkyl groups, such as aminomethyl, thioethyl, propoxy, etc. Similarly, the aforementioned alkyl or alkenyl groups can be interrupted by heteroatoms in the chain to form alkylaminoalkyl, alkylthioalkyl, or alkoxyalkyl groups, such as methylaminoethyl, ethylthiopropyl, methoxymethyl, etc.

[0040] Further, as used herein, the term "alicyclic" encompasses any cyclic hydrocarbon group containing 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropane, cyclobutane, cyclopentane, etc. The term "heterocyclic" encompasses any closed-ring structure similar to a carbocyclic group in which one or more carbon atoms in the ring are elements other than carbon (heteroatoms), such as nitrogen, sulfur, or oxygen atoms. Heterocyclic groups can be saturated or unsaturated. Examples of suitable heterocyclic groups include, for example, aziridine, ethylene oxide (epoxide, ethylene oxide), cyclothioethane (cyclosulfide), diethylene oxide, aziridine, oxobutane, thiobutane, dioxobutane, dithiobutane, dithiocyclobutene, aziridine, pyrrolidine, pyrrololine, oxopentane, dihydrofuran, and furan. Other examples of suitable heterocyclic groups include groups derived from tetrahydrofuran, furan, thiophene, pyrrolidine, piperidine, pyridine, pyrrole, methylpyridine, coumarin, etc.

[0041] In some embodiments, the alkyl, alkenyl, alicyclic, and heterocyclic groups may be unsubstituted or substituted with, for example, aryl, heteroaryl, C1-4 alkyl, C1-4 alkenyl, C1-4 alkoxy, amino, carboxyl, halogen, nitro, cyano, -SO3H, phosphonyl, or hydroxyl groups. When the alkyl, alkenyl, alicyclic, or heterocyclic group is substituted, the substituent is preferably C1-4 alkyl, halogen, nitro, amide, hydroxyl, carboxyl, sulfonyl, or phosphonyl. In one embodiment, R comprises an alkyl group substituted with a hydroxyl group. The term "aryl" comprises an aromatic hydrocarbon group comprising a fused aromatic ring, such as phenyl and naphthyl. The term "heteroaryl" comprises a heterocyclic aromatic derivative having at least one heteroatom, such as nitrogen, oxygen, phosphorus, or sulfur, and comprises, for example, furanyl, pyrroleyl, thiopheneyl, oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, etc. The term "heteroaryl" also includes fused rings in which at least one ring is aromatic, such as indolyl, purinyl, benzofuranyl, etc.

[0042] In some embodiments, the aryl and heteroaryl groups may be unsubstituted on the ring or substituted with, for example, aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxyl, halogen, nitro, cyano, -SO3H, phosphonyl, or hydroxyl groups. When the aryl, aralkyl, or heteroaryl group is substituted, the substituent is preferably a C1-4 alkyl, halogen, nitro, amide, hydroxyl, carboxyl, sulfonyl, or phosphonyl group. In one embodiment, R comprises an aryl group substituted with a C1-4 alkyl group.

[0043] As used herein, the term "disinfectant" refers to an agent that reduces the number of bacterial contaminants to a level deemed safe according to public health requirements. In one embodiment, the disinfectant used in this invention will provide a reduction of at least 99.999% (a reduction of 5 log units). These reductions can be evaluated using the procedures described in *Germicidaland Detergent Sanitizing Action of Disinfectants*, Official Analytical Methods of the Association of Official Analytical Chemists, paragraph 960.09 and applicable sections, 15th edition, 1990 (EPA Guideline 91-2). According to that reference, the disinfectant should provide a reduction of 99.999% (a reduction of 5 log units) against several test organisms at room temperature (25 ± 2 °C) for 30 seconds.

[0044] The distinction between "cidal" and "static" activity of antimicrobial agents, the definition describing the degree of efficacy, and the official laboratory protocols used to measure this efficacy are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of microbial cell damage. The first is a lethal, irreversible effect, leading to complete destruction or incapacitation of the microbial cell. The second type of cell damage is reversible, allowing the organism to reproduce again if the agent is not present. The former is called cidal, and the latter is called static. By definition, disinfectants and bactericides are agents that provide antimicrobial or cidal activity. In contrast, preservatives are often described as inhibitors or static compositions.

[0045] As used herein, “percentage by weight”, “% by weight”, “percentage by weight”, “% by weight” and its variations refer to the concentration of the substance when the weight of the substance is 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 “percentage by weight”, “% by weight”, etc.

[0046] It should be understood that the aspects and embodiments of the invention described herein include "consisting of aspects and embodiments" and / or "consisting substantially of aspects and embodiments".

[0047] Throughout this disclosure, all aspects of the invention are presented in scope. It should be understood that the use of scope format is merely for convenience and clarity and should not be construed as a rigid limitation on the scope of the invention. Therefore, descriptions of scopes should be considered as explicitly disclosing all possible sub-scopes and individual numerical values ​​within those scopes. For example, descriptions of scopes such as 1 to 6 should be considered as explicitly disclosing sub-scopes such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and individual numbers within those scopes, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the scope.

[0048] Other objects, advantages and features of the invention will become apparent from the following description taken in conjunction with the accompanying drawings.

[0049] The peroxy-alpha-hydroxycarboxylic acid forming compositions provide any one of the following forming compositions, which generate peroxy-alpha-hydroxycarboxylic acids having low vapor pressures and being odorless, and are therefore particularly suitable for applications involving contact with certain surfaces and targets. Exemplary peroxy-alpha-hydroxycarboxylic acids and their corresponding vapor pressure and odor characteristics are shown in Table 1. The methods described herein provide peroxy-alpha-hydroxycarboxylic acid forming compositions (liquid or solid) that generate peroxy-alpha-hydroxycarboxylic acids having low vapor pressures and being odorless to suit their applications involving direct contact (e.g., inhalation) with food, hard surfaces, and human tissue. As defined herein, low vapor pressure means a compound with a vapor pressure of less than about 1 kPa at 20°C. In preferred embodiments, the formed peroxy-alpha-hydroxycarboxylic acids have vapor pressures of less than about 1 kPa, 0.5 kPa, 0.1 kPa, or 0.01 kPa.

[0050] Table 1 - Physical properties of exemplary α-carboxylic acids and peroxyα-carboxylic acids

[0051] Acetic acid 1.56 sour Peracetic acid 2.06 Sharp and pungent lactic acid 0.01 No irritating odor peroxylactic acid NA Tasteless glycolic acid 0.003 Tasteless perglycolic acid NA Tasteless

[0052] Exemplary peroxy-α-hydroxycarboxylic acid forming compositions are provided, which generate peroxy-α-hydroxycarboxylic acids having low vapor pressure and being odorless. According to embodiments, the solid compositions comprise a lactone precursor of the α-hydroxycarboxylic acid, an alkalinity source and / or a substance that generates hydrogen peroxide (or a single substance that both provides alkalinity and generates peroxide, such as sodium percarbonate), and optional additional functional ingredients. Exemplary compositions are shown in Tables 2A and 2B by weight percentage. The exemplary compositions are shown as solid compositions. Alternatively, liquids can be used to generate peroxy-α-hydroxycarboxylic acids, wherein the lactone of the α-hydroxycarboxylic acid is dissolved together with a solvent (instead of the solid precursor).

[0053] Table 2A

[0054]

[0055] Table 2B

[0056]

[0057] The solid composition can be in various solid forms, including, for example, powder, powder or other solids in capsules or pouches, PVA or other dosage packages, tablets, pellets, or other solid forms. Exemplary solids can be compressed, cast, or extruded solids. The resulting solids can take, but are not limited to, flakes, granules, pellets, tablets, rhomboid tablets, ice-ball-shaped lumps, clumps, blocks, or another solid form known to those skilled in the art. In a preferred embodiment, the solid is dimensionally stable, as measured by a growth index of less than 5%, or less than 3% if heated to a temperature between about 100°F and about 122°F, taking into account any dimensional changes in the solid composition.

[0058] Solids can have a size range between about 1 gram and about 50 grams. Alternatively, solid tablets can have a size between about 50 grams and about 250 grams. Solid blocks can have a weight of about 250 grams or more.

[0059] Any suitable lactone precursor of α-hydroxycarboxylic acid can be used in the method of the present invention. In embodiments, the lactone precursor is a diester of a lactone. A lactone refers to a cyclic carboxylic acid ester containing a (-C=O)-O- structure, and the diester of the lactone has two carboxylic acid ester groups, such as those shown in the following general formula: Wherein R is H, CH3, or an alkyl group. In a preferred embodiment of the diester of the lactone, R is H or CH3. In another embodiment, the diester of the α-hydroxycarboxylic acid lactone is lactide (C6H8O4) or glycolide (C4H4O4). In embodiments, the lactide or glycolide reagent is provided in powder or solid form to provide a solid peroxy α-hydroxycarboxylic acid forming composition.

[0060] In one embodiment, the lactone precursor of the α-hydroxycarboxylic acid is not a monolactone, but rather a diester of the lactone precursor of the α-hydroxycarboxylic acid. Excluding monolactones provides a significant improvement in reactivity for forming the precursor of the peroxy α-hydroxycarboxylic acid. Specifically, the diester of the lactone precursor provides improved reactivity with hydrogen peroxide, resulting in faster formation of the corresponding peroxy α-hydroxycarboxylic acid. In another embodiment, the lactone precursor of the α-hydroxycarboxylic acid does not include glycolactones. Excluding glycolactones provides a significant cost improvement for the composition. Exemplary glycolactones include those such as: hexose-δ-lactones, including gluconic acid-δ-lactone, galactonic acid-δ-lactone, and mannolic acid-δ-lactone, or aldonic acid lactones, including allonic acid lactone, adalginate lactone, gluconic acid lactone, mannolic acid lactone, gulonic acid lactone, idulonic acid lactone, galactonic acid lactone, taronic acid lactone, and their salts. U.S. Patent No. 10,487,297 discloses the use of monolactones and glycolactones, which hydrolyze multiple hydroxyl groups on the lactone and provide pH stability.

[0061] Any suitable hydrogen peroxide or substance that generates hydrogen peroxide can be used as a reagent. Substances that generate hydrogen peroxide upon contact with a liquid include, for example, alkali metal carbonates, alkali metal percarbonates, alkali metal perborates, and peroxides such as sodium percarbonate, sodium perborate, calcium peroxide, magnesium peroxide, urea peroxide, peroxide salts, and PVP peroxide. In a preferred embodiment of the solid peroxy-α-hydroxycarboxylic acid composition, the hydrogen peroxide-generating substance is utilized in powder or other solid form.

[0062] Any suitable alkalinity source can be used as a reagent to increase the pH of the reaction conditions. Suitable alkalinity sources may include, but are not limited to, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal silicates, alkali metal carbonates or percarbonates, borates, amines, amides, or other basic nitrogen sources, and mixtures thereof. Suitable alkali metal hydroxides include, but are not limited to, sodium hydroxide, such as sodium hydroxide beads. Suitable alkali metal silicates include, but are not limited to, sodium silicate and its derivatives. Suitable amines include, but are not limited to, primary, secondary, or tertiary amines and diamines carrying at least one nitrogen-linked hydrocarbon group, wherein the hydrocarbon group represents a saturated or unsaturated straight-chain or branched alkyl group having at least one carbon atom. Amines may further include alkanolamines, including, for example, monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, etc.

[0063] In a preferred embodiment, the alkalinity source is an alkali metal hydroxide, an alkaline earth metal hydroxide, or an alkali metal carbonate or percarbonate. In another preferred embodiment, the alkalinity source is an alkali metal carbonate or percarbonate. In some embodiments, the alkalinity source is also a substance that generates hydrogen peroxide upon contact with a liquid, such as sodium percarbonate or urea peroxide.

[0064] In some embodiments, the alkalinity source and the substance that generates hydrogen peroxide are single agents in the solid composition. For example, an alkali metal percarbonate, preferably sodium percarbonate.

[0065] Method for preparing peroxyhydroxycarboxylic acid

[0066] Peroxyhydroxycarboxylic acid is formed by the perhydrolysis of a corresponding lactone precursor according to the method described herein. The method includes the steps of contacting a reagent containing a lactone of an α-hydroxycarboxylic acid, an alkalinity source, and a substance that generates hydrogen peroxide upon contact with a liquid to form a liquid containing peroxyα-hydroxycarboxylic acid. In an embodiment, the method includes the steps of contacting a solid composition with a liquid, wherein the solid composition contains a lactone of an α-hydroxycarboxylic acid, an alkalinity source and / or a substance that generates hydrogen peroxide, and optionally an additional functional ingredient, and generating a liquid containing peroxyα-hydroxycarboxylic acid, wherein the liquid has a pH of less than about 8 or less than about 7 within about 5 minutes of the contact step between the solid composition and the liquid. Not limited to a specific mechanism of action, diester lactones (such as lactide) can also act as acidifiers to lower the pH of the resulting peracidic solution. The method further includes generating at least about 1 ppm of peroxyα-hydroxycarboxylic acid within less than 1 minute after the solid composition is contacted with the liquid.

[0067] The methods described herein are suitable for forming peroxy-α-hydroxycarboxylic acids by reacting a solid or liquid composition. While examples involve the use of a solid, liquid compositions can also be used within the scope of this invention. The composition comprises a diester of a lactone of an α-hydroxycarboxylic acid, an alkalinity source and / or a substance that generates hydrogen peroxide upon contact with a liquid, and optionally additional functional ingredients. In embodiments where the composition is liquid, the diester of the lactone of the α-hydroxycarboxylic acid is dissolved in a solvent, and upon contact with the alkalinity source and / or the hydrogen peroxide-generating substance, the composition reacts within about 5 minutes to form a peroxy-α-hydroxycarboxylic acid with a pH less than about 8. In embodiments where the composition is solid, the solid composition reacts upon dissolution in a liquid to form a peroxy-α-hydroxycarboxylic acid and has a pH less than about 8 within about 5 minutes after contact with the diester of the lactone of the α-hydroxycarboxylic acid and / or the hydrogen peroxide-generating substance.

[0068] Advantageously, lactones of α-hydroxycarboxylic acids (such as lactide) are used. Figure 1 (as shown) and glycolide (as shown) Figure 2 As shown), hydrogen peroxide (or, in the solid embodiment, the substance that generates hydrogen peroxide) is used as a raw material, and the corresponding peroxy-α-hydroxycarboxylic acid is efficiently generated through the perhydrolysis of hydrogen peroxide in a stoichiometric reaction. Using one mole of lactone in a stoichiometric reaction will generate one mole of the corresponding peroxy-α-hydroxycarboxylic acid and one mole of α-hydroxycarboxylic acid, as shown. Figures 1 to 2 As shown.

[0069] A method for forming a peroxyhydroxycarboxylic acid includes contacting a solid composition with a liquid, said contact comprising dissolving the solid composition in the liquid to form an aqueous solution or suspension with a pH of at least neutral (such as greater than or equal to about pH 7) to alkaline, thereby providing milder reaction conditions compared to previous reactions used to generate peroxycarboxylic acid compositions. In embodiments, the method for forming a peroxyhydroxycarboxylic acid includes contacting a solid composition with a liquid to form an aqueous solution or suspension with a pH of at least about 5 or greater. As those skilled in the art will determine, the solution pH for the reaction to generate peroxy-α-hydroxycarboxylic acid derives from the components of the solid composition rather than from the liquid (e.g., water) itself. In embodiments, the pH of the liquid having the dissolved solid composition is about 7 to 12, about 7 to 11, about 7 to 10, about 8 to 12, about 8 to 11, or about 8 to 10 (or any range thereof).

[0070] As will be apparent to those skilled in the art from the disclosure herein, the solid composition dissolved in the liquid begins to form a peroxycarboxylic acid composition upon solid dissolution. For clarity, the entire solid composition does not need to be dissolved prior to the step of forming peroxy-α-hydroxycarboxylic acid.

[0071] The method for forming peroxyalpha-hydroxycarboxylic acid is a rapid reaction because once the reagents are dissolved in a liquid, they begin to generate peroxyalpha-hydroxycarboxylic acid almost immediately under mild conditions. In one embodiment, the method generates peroxyalpha-hydroxycarboxylic acid in a liquid solution containing peroxyalpha-hydroxycarboxylic acid at concentrations of about 0.1 ppm to about 100,000 ppm, about 0.1 ppm to about 90,000 ppm, about 0.1 ppm to about 80,000 ppm, about 0.1 ppm to about 70,000 ppm, about 0.1 ppm to about 60,000 ppm, about 0.1 ppm to about 50,000 ppm, about 0.1 ppm to about 40,000 ppm, about 0.1 ppm to about 30,000 ppm, about 0.1 ppm to about 20,000 ppm, or about 0.1 ppm to about 10,000 ppm.

[0072] The method of the present invention can be used to form a liquid, such as a solution, comprising any suitable concentration of peroxy-α-hydroxycarboxylic acid within any suitable time period. For example, reagents can be contacted with each other to form a liquid, such as a solution, comprising any suitable concentration of peroxy-α-hydroxycarboxylic acid, such as at least about 1 ppm of peroxy-hydroxycarboxylic acid, for example, at least about 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm within 1 minute of contact time. ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1,000ppm, 2,000ppm, 3,000ppm, 4,000ppm, 5,000ppm, 6,000ppm, 7,000ppm, 8,000ppm, 9,000ppm, 10,000ppm, 20,000ppm, 30,000ppm, 40,000ppm, 50,000ppm, 60,000ppm, 70,000ppm, 80,000ppm, 90,000ppm, or 100,000ppm (or a range thereof).

[0073] On one hand, at least about 1 ppm of peroxy-α-hydroxycarboxylic acid is generated within less than 1 minute of contact with the reagent. On another hand, at least about 1 ppm of peroxy-α-hydroxycarboxylic acid is generated within a time of less than about 55 seconds, 50 seconds or less, 45 seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5 seconds or less. On another hand, the reaction forming a liquid containing at least about 1 ppm of peroxy-α-hydroxycarboxylic acid is almost instantaneous. Advantageously, using a diester lactone of an α-hydroxycarboxylic acid to generate peroxy-α-hydroxycarboxylic acid provides an almost instantaneous reaction, unlike reactions with monoester precursors or corresponding hydroxycarboxylic acids.

[0074] In one aspect, at least about 100 ppm, at least about 500 ppm, at least about 1,000 ppm, at least about 10,000 ppm, or at least about 20,000 ppm of peroxy α-hydroxycarboxylic acid are generated within a contact time of about 10 minutes or less, about 5 minutes or less, about 3 minutes to about 5 minutes, or about 3 minutes or less. In another aspect, at least about 100 ppm, at least about 500 ppm, at least about 1,000 ppm, at least about 10,000 ppm, or at least about 20,000 ppm of peroxy α-hydroxycarboxylic acid are generated within a contact time of less than about 4 minutes, 3 minutes or less, 2 minutes or less, or 1 minute or less. As those skilled in the art will determine with the solid embodiment, the reagent will therefore require time to dissolve before the reaction to generate the peroxy α-hydroxycarboxylic acid begins.

[0075] Because the methods for forming peroxy α-hydroxycarboxylic acids are rapid reactions, they begin to generate peroxy α-hydroxycarboxylic acids and lower the pH value almost immediately under mild conditions. In one embodiment, the method generates peroxy α-hydroxycarboxylic acids and the pH of the peroxy α-hydroxycarboxylic acid composition decreases to less than about 8, less than about 7, or less than about 6 within about 1 minute, about 2 minutes, or about 3 minutes after the reagents come into contact with each other.

[0076] In some embodiments, the pH of the formed peroxy-α-hydroxycarboxylic acid liquid may change to about 8 or less, about 7 or less, or about 6 or less within about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, or 50 seconds after the reagents come into contact with each other. In other embodiments, the pH of the formed peroxy-α-hydroxycarboxylic acid liquid may change to about less than about 8, 7, 6, 5, 4, 3, or 2 within about 1 minute, about 2 minutes, or about 3 minutes after the reagents come into contact with each other. In one aspect, the pH of the formed peroxy-α-hydroxycarboxylic acid liquid changes to about 8 or less, about 7 or less, or about 6 or less within about 1 minute or less. On one hand, the pH of the formed peroxy-α-hydroxycarboxylic acid changes to about 8 or lower, about 7 or lower, or about 6 or lower within a time interval of about 45 seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5 seconds or less. On the other hand, the pH of the formed peroxy-α-hydroxycarboxylic acid liquid changes to about 8 or less, about 7 or less, or about 6 or less almost instantaneously.

[0077] In one embodiment, the formed peroxy α-hydroxycarboxylic acid liquid maintains a pH less than about 8, 7, 6, 5, 4, 3, or 2 for about 1 second to about 10 hours after being generated by reagent contact. In other embodiments, the formed peroxy α-hydroxycarboxylic acid liquid maintains a pH less than about 8, 7, 6, 5, 4, 3, or 2 for about 60 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.

[0078] The reagents can come into contact with each other to form a liquid, such as a solution, comprising peroxy-α-hydroxycarboxylic acid under any suitable conditions or temperature. In some embodiments, the reagents come into contact with each other under ambient conditions. In other embodiments, the reagents come into contact with each other in a temperature range of about -2°C to about 60°C, 0°C to about 60°C, or preferably about 4°C to about 60°C, for example, about -2°C to 0°C, 0°C to 4°C, 4°C to 5°C, 5°C to 10°C, 10°C to 15°C, 15°C to 20°C, 20°C to 25°C, 25°C to 30°C, 30°C to 35°C, 35°C to 40°C, 40°C to 45°C, 45°C to 50°C, 50°C to 55°C, or 55°C to 60°C.

[0079] The composition and method may further include the use of a catalyst or enzyme that catalyzes the formation of peroxy-α-hydroxycarboxylic acid from a lactone precursor of α-hydroxycarboxylic acid and hydrogen peroxide. The method of the present invention may use any suitable catalyst or enzyme, such as perhydrolases, lipases, crown enzymes, pentylases, or disaccharidases. - In some embodiments, other peracid precursors ("activators") (such as TAED) may be included in the composition (including solid compositions), and such compositions, when dissolved in water, will generate peroxy-α-carboxylic acid and other peracids (such as peracetic acid).

[0080] In some embodiments, the compositions and methods do not include the use of hydrolases. For example, in some cases, the methods of the present invention do not include the use of carbohydrate esterase (CE-7) or a member of the family 7 of hydrolases disclosed in U.S. Patent No. 8,865,436.

[0081] In some embodiments, the compositions and methods do not include the use of activators, such as conventional peroxycarboxylic acid activators, including, for example, monoacetate, diacetate, triacetate, glucose pentaacetate, lactose octaacetate, mannitol hexaacetate, sucrose octaacetate, N,N,N′N′-tetraacetylethylenediamine (TAED), N,N,N′N′-tetraacetylmethylenediamine (TAMD), N-acetylglycine, N-acetylmethionine, 6-acetaminohexanoic acid, N-acetyl-L-cysteine, 4-acetylaminophenol, N-acetyl-L-glutamine, N,N′,N″,N″′-tetraacetylglycourea (TAGU), etc.

[0082] Advantageously, the compositions and methods do not require the use of stabilizers for peroxy-α-hydroxycarboxylic acids, stabilizers for hydrogen peroxide, and / or pH buffers. However, one or more stabilizers may be used in other embodiments. As mentioned herein, stabilizers include phosphonate-based stabilizers, including phosphonates, phosphoric acids and salts, pyrophosphates and salts, and most commonly 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts, pyridinecarboxylic acids, and / or heterocyclic dicarboxylic acids, such as pyridinedicarboxylic acid, pyridinecarboxylic acid and salts, pyridine-2,6-dicarboxylic acid and salts. Commonly used stabilizers in peroxycarboxylic acid compositions include HEDP and 2,6-pyridinedicarboxylic acid (DPA).

[0083] In embodiments where pH buffers are used in the compositions and methods, these may include any reagent compatible with the lactone precursor. Exemplary buffers include organic amines, such as triethanolamine, imidazole, carbonates, phosphates, etc.

[0084] The compositions and methods of the present invention can use any suitable stabilizer for hydrogen peroxide. Exemplary stabilizers for hydrogen peroxide include phosphonates, heterocyclic carboxylic acids, and mixtures thereof. In some embodiments, the stabilizer for hydrogen peroxide may be Dequest 2010, Dequest 2066, pyridinedicarboxylic acid, etc. Stabilizers for hydrogen peroxide may be included in any suitable reagent.

[0085] The method can use any suitable dose of a solid composition containing a reagent for generating peroxy-α-hydroxycarboxylic acid. In one embodiment, the method can use a single dose of a solid composition (e.g., a single solid tablet or other solid form) to contact a liquid and generate peroxy-α-hydroxycarboxylic acid. In another embodiment, the method can use or administer multiple doses of a solid composition during the contact step. The multiple doses of the solid composition can contain one or more different lactone precursor reagents, or they can be the same lactone precursor. In another embodiment, the multiple doses of the lactone precursor reagent can include lactone precursors of different α-hydroxycarboxylic acids. The multiple doses of the lactone precursor reagent can include the same or different concentrations of the lactone precursor.

[0086] Because the method can use any suitable concentration of precursor, the composition and method can use any suitable concentration of lactone of the α-hydroxycarboxylic acid precursor. For example, the lactone of the α-hydroxycarboxylic acid reagent in the peroxyhydroxycarboxylic acid forming composition can be at any suitable concentration, such as about 10 wt% to about 70 wt%, about 20 wt% to about 70 wt%, about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%. In some embodiments, the amount of lactone of the α-hydroxycarboxylic acid reagent in the liquid formed for generating peroxyα-hydroxycarboxylic acid can be about 1 ppm to about 500,000 ppm or about 10 ppm to about 500,000 ppm. For example, the lactone of the α-hydroxycarboxylic acid reagent in the formed liquid can account for about 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm m to 300ppm, 300ppm to 350ppm, 350ppm to 400ppm, 400ppm to 450ppm, 450ppm to 500ppm, 500ppm to 550ppm, 550ppm to 600ppm, 600ppm to 650ppm, 650ppm to 700ppm, 700ppm to 750ppm, 750ppm to 800ppm, 800ppm to 850ppm, 850ppm to 900ppm, 900ppm to 950ppm, 9 50ppm to 1,000ppm, 1,000ppm to 1,500ppm, 1,500ppm to 2,000ppm, 2,000ppm to 2,500ppm, 2,500ppm to 3,000ppm, 3,000ppm to 3,500ppm, 3,500ppm to 4,000ppm, 4,000ppm to 4,500ppm, 4,500ppm to 5,000ppm, 5,000ppm to 5,500ppm, 5,500ppm to 6,000ppm PM, 6,000ppm to 6,500ppm, 6,500ppm to 7,000ppm, 7,000ppm to 7,500ppm, 7,500ppm to 8,000ppm, 8,000ppm to 8,500ppm, 8,500ppm to 9,000ppm, 9,000ppm to 10,000ppm, 10,000ppm to 20,000ppm, 20,000ppm to 30,000ppm, 30,000ppm to 40,000ppm, 40,000ppm to 50,000ppm, 50,000ppm to 60,000ppm, 60,000ppm to 70,000ppm, 70,000ppm to 80,000ppm, 80,000ppm to 90,000ppm, 90,000ppm to 100,000ppm, 100,000ppm to 150,000ppm, 150,000ppm to 200,000ppm, 200,000ppm to 250,000ppm, 250,000ppm to 300,000ppm, 300,000ppm to 350,000ppm, 350,000ppm to 400,000ppm, 400,000ppm to 450,000ppm or 450,000ppm to 500,000ppm (and any other range between them). ,

[0087] Because the method can use any suitable concentration of precursor, the composition and method can employ any suitable concentration of the substance that generates hydrogen peroxide upon contact with a liquid. For example, the substance that generates hydrogen peroxide upon contact with a liquid can be present at any suitable concentration, such as about 1 wt% to about 80 wt%, about 10 wt% to about 80 wt%, about 20 wt% to about 80 wt%, about 20 wt% to about 70 wt%, about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%. In some embodiments, the amount of the substance that generates hydrogen peroxide upon contact with a liquid can be about 0.1 ppm to about 100,000 ppm or about 1 ppm to about 100,000 ppm.For example, the substance in the formed liquid that generates hydrogen peroxide upon contact with the liquid reagent may contain approximately 0.1 ppm to 1 ppm, 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm, 300 ppm to 350 ppm. ppm, 350ppm to 400ppm, 400ppm to 450ppm, 450ppm to 500ppm, 500ppm to 550ppm, 550ppm to 600ppm, 600ppm to 650ppm, 650ppm to 700ppm, 700ppm to 750ppm, 750ppm to 800ppm, 800ppm to 850ppm, 850ppm to 900ppm, 900ppm to 950ppm, 950ppm to 1,000ppm, 1,000ppm to 1,500ppm, 1,500ppm to 2,000ppm, 2,000ppm Up to 2,500ppm, 2,500ppm to 3,000ppm, 3,000ppm to 3,500ppm, 3,500ppm to 4,000ppm, 4,000ppm to 4,500ppm, 4,500ppm to 5,000ppm, 5,000ppm to 5,500ppm, 5,500ppm to 6,000ppm, 6,000ppm to 6,500ppm, 6,500ppm to 7,000ppm, 7,000ppm to 7,500ppm, 7,500ppm to 8,000ppm, 8,000ppm to 8,500ppm, 8,500ppm Hydrogen peroxide in concentrations of 1 pm to 9,000 ppm, 9,000 ppm to 10,000 ppm, 10,000 ppm to 20,000 ppm, 20,000 ppm to 30,000 ppm, 30,000 ppm to 40,000 ppm, 40,000 ppm to 50,000 ppm, 50,000 ppm to 60,000 ppm, 60,000 ppm to 70,000 ppm, 70,000 ppm to 80,000 ppm, 80,000 ppm to 90,000 ppm, or 90,000 ppm to 100,000 ppm (and any other range between them).

[0088] Because the method can use any suitable concentration of precursor, the composition and method can employ any suitable concentration of alkalinity source. For example, the alkalinity source can be present at any suitable concentration to provide the desired reaction pH conditions, such as about 1 wt% to about 80 wt%, about 10 wt% to about 80 wt%, about 20 wt% to about 80 wt%, about 20 wt% to about 70 wt%, about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%. In some embodiments, the amount of alkalinity source can be from about 0.1 ppm to about 100,000 ppm, or from about 1 ppm to about 100,000 ppm.For example, the alkalinity source reagent in the formed liquid may account for approximately 0.1 ppm to 1 ppm, 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm, 300 ppm to 350 ppm, or 350 ppm. Up to 400ppm, 400ppm to 450ppm, 450ppm to 500ppm, 500ppm to 550ppm, 550ppm to 600ppm, 600ppm to 650ppm, 650ppm to 700ppm, 700ppm to 750ppm, 750ppm to 800ppm, 800ppm to 850ppm, 850ppm to 900ppm, 900ppm to 950ppm, 950ppm to 1,000ppm, 1,000ppm to 1,500ppm, 1,500ppm to 2,000ppm, 2,000ppm to 2,500ppm ppm, 2,500ppm to 3,000ppm, 3,000ppm to 3,500ppm, 3,500ppm to 4,000ppm, 4,000ppm to 4,500ppm, 4,500ppm to 5,000ppm, 5,000ppm to 5,500ppm, 5,500ppm to 6,000ppm, 6,000ppm to 6,500ppm, 6,500ppm to 7,000ppm, 7,000ppm to 7,500ppm, 7,500ppm to 8,000ppm, 8,000ppm to 8,500ppm, 8,500ppm Alkalinity sources up to 9,000 ppm, 9,000 ppm to 10,000 ppm, 10,000 ppm to 20,000 ppm, 20,000 ppm to 30,000 ppm, 30,000 ppm to 40,000 ppm, 40,000 ppm to 50,000 ppm, 50,000 ppm to 60,000 ppm, 60,000 ppm to 70,000 ppm, 70,000 ppm to 80,000 ppm, 80,000 ppm to 90,000 ppm, or 90,000 ppm to 100,000 ppm (and any other range between them).

[0089] In some embodiments of the solid composition, the composition and method may use a single reagent that is both a hydrogen peroxide-generating substance and an alkalinity source, and the composition and method may include any suitable concentration thereof. For example, the reagent that is both a hydrogen peroxide-generating substance and an alkalinity source may be contained at suitable concentrations to provide the desired reaction pH conditions, such as about 10 wt% to about 80 wt%, about 20 wt% to about 80 wt%, about 20 wt% to about 70 wt%, about 20 wt% to about 60 wt%, or about 20 wt% to about 50 wt%, including any range between them. In some embodiments, the amount of the hydrogen peroxide-generating substance and the alkalinity source may be about 0.1 ppm to about 100,000 ppm or about 1 ppm to about 100,000 ppm.For example, the reagent in the formed liquid may contain approximately 0.1 ppm to 1 ppm, 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm, 300 ppm to 350 ppm, 350 ppm to 400 ppm. ppm, 400ppm to 450ppm, 450ppm to 500ppm, 500ppm to 550ppm, 550ppm to 600ppm, 600ppm to 650ppm, 650ppm to 700ppm, 700ppm to 750ppm, 750ppm to 800ppm, 800ppm to 850ppm, 850ppm to 900ppm, 900ppm to 950ppm, 950ppm to 1,000ppm, 1,000ppm to 1,500ppm, 1,500ppm to 2,000ppm, 2,000ppm to 2,500ppm, 2, 500ppm to 3,000ppm, 3,000ppm to 3,500ppm, 3,500ppm to 4,000ppm, 4,000ppm to 4,500ppm, 4,500ppm to 5,000ppm, 5,000ppm to 5,500ppm, 5,500ppm to 6,000ppm, 6,000ppm to 6,500ppm, 6,500ppm to 7,000ppm, 7,000ppm to 7,500ppm, 7,500ppm to 8,000ppm, 8,000ppm to 8,500ppm, 8,500ppm to 9,000ppm Substances that generate hydrogen peroxide and alkalinity (and any other ranges in between) at concentrations of m, 9,000 ppm to 10,000 ppm, 10,000 ppm to 20,000 ppm, 20,000 ppm to 30,000 ppm, 30,000 ppm to 40,000 ppm, 40,000 ppm to 50,000 ppm, 50,000 ppm to 60,000 ppm, 60,000 ppm to 70,000 ppm, 70,000 ppm to 80,000 ppm, 80,000 ppm to 90,000 ppm, or 90,000 ppm to 100,000 ppm.

[0090] The method can be used to generate peroxy-α-hydroxycarboxylic acids in any suitable manner or at any suitable location. In some embodiments, the method can be used to generate peroxy-α-hydroxycarboxylic acids in situ for application.

[0091] Advantageously, methods for forming peroxy-α-hydroxycarboxylic acids may include contacting a solid composition containing a reagent in powder form, a capsule, sleeve, or pouch containing powder or other solids, PVA or other dosage packaging, tablets, pellets, or other solid forms. In embodiments, all reagents may be provided as powders (as premixed compositions) or as various forms of solid compositions (e.g., tablets, pellets, blocks, etc.). In embodiments, the reagents are contained in capsules, sleeves, or pouches, which may include various packaging methods known in the art, including, for example, PVA or other dosage packaging, said packaging being water-soluble capsules for ease of handling and use. Various papers, coatings, and laminates with water-soluble composite materials are available. Various water-soluble capsules, sleeves, or pouches for dosage packaging provide a unit dose that is convenient for the user to store and administer to provide the desired peroxy-α-hydroxycarboxylic acid by reacting the reagent in such capsules or dosage packaging with a liquid. Advantageously, the reagent dissolves rapidly upon contact with a liquid (e.g., water) to obtain a liquid that generates peroxy-α-hydroxycarboxylic acid. The solid composition is further stable under environmental storage conditions, including dimensional stability. In the embodiments, the solid is dimensionally stable at room temperature for at least one year.

[0092] Peroxyhydroxycarboxylic acids and / or peroxyhydroxycarboxylic acid-forming compositions may further comprise additional peroxycarboxylic acids. Various embodiments relating to peroxyhydroxycarboxylic acids and / or peroxyhydroxycarboxylic acid-forming compositions are further understood to optionally comprise additional peroxycarboxylic acids. As used herein, the term “peracid” may also be referred to as “percarboxylic acid” or “peroxyacid”. Sulfonoperoxycarboxylic acids, sulfonated peracids, and sulfonated peroxycarboxylic acids are also included within the term “peracid” as used herein. The terms “sulfonoperoxycarboxylic acid,” “sulfonated peracid,” or “sulfonated peroxycarboxylic acid” refer to the peroxycarboxylic acid form of sulfonated carboxylic acids, as disclosed in U.S. Patent Publications 2010 / 0021557, 2010 / 0048730, and 2012 / 0052134, which are incorporated herein by reference in their entirety. Peracid refers to an acid in which the hydrogen atom of the hydroxyl group in a carboxylic acid is replaced by a hydroxyl group. Oxidized peracids may also be referred to herein as peroxycarboxylic acids.

[0093] In some embodiments, a peroxyhydroxycarboxylic acid having an additional peroxycarboxylic acid can be generated by mixing an ester of a polyol with a composition comprising a peroxycarboxylic acid and hydrogen peroxide to form a composition comprising both a peroxyhydroxycarboxylic acid (e.g., peroxylactic acid and / or peroxyglycolic acid) and other peroxycarboxylic acids. Examples of compositions comprising both peroxycarboxylic acid and hydrogen peroxide include peracetic acid compositions, peroxyoctanoic acid compositions, etc., all of which are commercially available from Ecolab Inc. In one embodiment, a reagent described herein comprising an α-hydroxycarboxylic acid lactone can be contacted, for example, mixed with Oxonia Active, Tsunami 100, Matrixx, TurboOxysan, and Octave to form a composition comprising both a peroxyhydroxycarboxylic acid and other desired peroxycarboxylic acids.

[0094] Suitable peracids include any peroxycarboxylic acid, including peroxycarboxylic acids and percarboxylic acids of varying lengths (e.g., C1-22), which can be prepared by the reaction of polyols and acid esters with hydrogen peroxide as described herein. Additional suitable peracids include those peracids involved in the acid-catalyzed equilibrium reaction between the carboxylic acids and hydrogen peroxide as described above. Peroxycarboxylic acids can also be prepared by the auto-oxidation of aldehydes or by the reaction of hydrogen peroxide with acyl chlorides, acid anhydrides, carboxylic anhydrides, or sodium alkoxides. Alternatively, peracids can be prepared by non-equilibrium reactions, which can be generated in situ for use, as disclosed in U.S. Patent Nos. 8,846,107 and 8,877,254, each entitled "In Situ Generation of Peroxycarboxylic Acids at Alkaline pH, and Methods of Use Thereof," which are incorporated herein by reference. Preferably, the composition of the present invention comprises peroxyformic acid, peracetic acid, peroxyoctanoic acid, peroxypropionic acid, peroxylactic acid, peroxyheptanoic acid, peroxyoctanoic acid and / or peroxynonanoic acid.

[0095] In some embodiments, the peroxycarboxylic acid comprises at least one water-soluble peroxycarboxylic acid, wherein R comprises an alkyl group having 1-22 carbon atoms. In another embodiment, R of the peroxycarboxylic acid is an alkyl group having 1-22 carbon atoms substituted with a hydroxyl group. Methods for preparing peracetic acid are known to those skilled in the art and are contained in the method disclosed in U.S. Patent No. 2,833,813, which is incorporated herein by reference.

[0096] In another embodiment, sulfoperoxycarboxylic acid has the following formula: Wherein R1 is hydrogen or a substituted or unsubstituted alkyl group; R2 is a substituted or unsubstituted alkylene group; X is hydrogen, a cationic group or an ester-forming moiety; or their salts or esters.

[0097] In other embodiments, a mixture of peracids is employed, such as peracids comprising at least one water-limited peroxycarboxylic acid (wherein R comprises an alkyl group of 5-22 carbon atoms) and at least one water-soluble peroxycarboxylic acid (wherein R comprises an alkyl group of 1-4 carbon atoms). For example, in one embodiment, the peroxycarboxylic acid comprises peracetic acid and at least one other peroxycarboxylic acid, such as those mentioned above. In further embodiments, the composition comprises peroxyhydroxycarboxylic acid, peracetic acid hydrochloride, and / or peroxyoctanoic acid. Other combinations of mixed peracids are well-suited for use in the methods and compositions described herein.

[0098] In some applications, combinations of peroxycarboxylic acids provide compositions with desired antimicrobial activity in the presence of high organic soil loads. Mixed peroxycarboxylic acid compositions typically offer synergistic microefficacy. Therefore, the compositions of the present invention may comprise a mixture of peroxyhydroxycarboxylic acids and one or more additional peroxycarboxylic acids.

[0099] Depending on the specific application, any suitable C1-C can be used. 22 Percarboxylic acid. In some implementations, C1-C 22 Percarboxylic acids are C2-C 20 Percarboxylic acid. In other embodiments, C1-C 22 Percarboxylic acids are C1, C2, C3, C4, C5, C6, C7, C8, C9, C6. 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 C 21 Or C 22 carboxylic acid.

[0100] Additional C1-C 22 Percarboxylic acids can be used at any suitable concentration. In some embodiments, C1-C 22 The concentration of the percarboxylic acid is from about 1% to about 40% by weight. In other embodiments, C1-C 22 The concentration of percarboxylic acid is from about 1% to about 20% by weight. In other embodiments, C1-C 22The concentration of percarboxylic acid is about 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, or 40 wt%. In yet other embodiments, C1-C 22 The concentration of percarboxylic acid is from about 0.1 ppm to about 10,000 ppm, for example, about 0.1 ppm to 1 ppm, 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 2 00ppm, 200ppm to 250ppm, 250ppm to 300ppm, 300ppm to 350ppm, 350ppm to 400ppm, 400ppm to 450ppm, 450ppm to 500ppm, 500ppm to 550ppm, 550ppm to 600ppm, 600ppm to 650ppm, 650ppm to 700ppm, 700ppm to 750ppm, 750ppm to 800ppm, 800ppm to 850ppm pm, 850ppm to 900ppm, 900ppm to 950ppm, 950ppm to 1,000ppm, 1,000ppm to 1,500ppm, 1,500ppm to 2,000ppm, 2,000ppm to 2,500ppm, 2,500ppm to 3,000ppm, 3,000ppm to 3,500ppm, 3,500ppm to 4,000ppm, 4,000ppm to 4,500ppm, or 4,500ppm to 5, 000ppm, 5,000ppm to 5,500ppm, 5,500ppm to 6,000ppm, 6,000ppm to 6,500ppm, 6,500ppm to 7,000ppm, 7,000ppm to 7,500ppm, 7,500ppm to 8,000ppm, 8,000ppm to 8,500ppm, 8,500ppm to 9,000ppm, 9,000ppm to 9,500ppm or 9,500ppm to 10,000ppm.

[0101] Additional optional ingredients for compositions and methods

[0102] The peroxy-α-hydroxycarboxylic acid forming composition may optionally include additional components to enhance the reaction and not generate peroxy-α-hydroxycarboxylic acids and / or enhance the composition for treating various surfaces and targets. Additional optional functional components may include, for example, stabilizers, emulsifiers, color indicator precursors, surfactants and / or additional antimicrobial agents (e.g., mixed peracids, biocides) for enhancing efficacy, defoamers, anti-redeposition agents, bleaching agents, dispersants or disintegrants (e.g., effervescent materials), solubility modifiers, wetting agents, metal protectants, multivalent chelating agents and / or chelating agents, fragrances and / or dyes, rheology modifiers, water-soluble growth promoters or coupling agents, buffers, solvents, acidifiers and / or catalysts (e.g., strong inorganic acids), additional carboxylic acids, etc. In one embodiment, no additional functional components are used. In other embodiments, buffers are used. In other embodiments, color indicator precursors are used. In other embodiments, dispersants or disintegrants (e.g., effervescent materials) are used to promote the dissolution of the solid composition. In still other embodiments, any combination of these additional functional components is used. In several embodiments, those skilled in the art will determine that various functional ingredients (e.g., buffers, disintegrants, and / or dispersants) do not affect the perhydrolysis reaction that produces peroxy-α-hydroxycarboxylic acid.

[0103] Added antimicrobial agents

[0104] Additional antimicrobial agents can be included in solid compositions and / or methods of use to enhance antimicrobial efficacy. In addition to using peroxyhydroxycarboxylic acid compositions, additional antimicrobial agents and biocides can be used to enhance antimicrobial efficacy and the efficacy lifespan after the generated peroxyhydroxycarboxylic acid degrades to the corresponding hydroxycarboxylic acid (e.g., perlactic acid degrades to lactic acid).

[0105] The additional biocide may include, for example, a quaternary ammonium compound disclosed in U.S. Patent No. 6,627,657, which is incorporated herein by reference in its entirety. Advantageously, the presence of the quaternary ammonium compound provides synergistic antimicrobial efficacy with peracids and maintains the long-term biocideic efficacy of the composition. In another embodiment, the additional biocide may include anionic surfactants as described herein in the “Anionic Surfactants” section, such as anionic carboxylates and alkyl sulfonates (linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents), such as linear alkylbenzene sulfonates (LAS) and sodium lauryl sulfate (SLS), or olefin sulfonates such as α-olefin sulfonates (AOS). In another embodiment, the additional biocide may include oxidant-compatible... Biocides, such as tributyltetradecyl chloride Biocides offer similar antimicrobial benefits to combinations of quaternary ammonium compounds and peracids. In some embodiments, the additional antimicrobial agent and biocide can be used in amounts sufficient to provide antimicrobial efficacy, which can vary depending on the application. Such agents can be present in the working solution in amounts of at least about 0.1 wt% to about 5 wt%, preferably at least about 0.1 wt% to about 2 wt%, more preferably about 0.1 wt% to about 1 wt%.

[0106] Acidifier

[0107] Advantageously, the methods and / or compositions described herein do not require an acidifier. However, in some embodiments where the pH of the peroxyhydroxycarboxylic acid, such as less than about 2.5 or less than about 2, is preferred, the acidifier is an effective component for lowering the pH of the composition. Therefore, in some embodiments, the acidifier may be included as an additional functional ingredient in the composition (peroxyhydroxycarboxylic acid composition or peroxyhydroxycarboxylic acid forming composition). In one aspect, strong inorganic acids, such as nitric acid or sulfuric acid, can be used. The combined use of strong inorganic acids with peracid compositions provides enhanced antimicrobial efficacy. In some embodiments, the compositions of the present invention do not contain mineral acids or strong mineral acids.

[0108] In one embodiment, the acidifying agent is included together with the hydrogen peroxide reagent. Any suitable acid may be included in the composition as an acidifying agent. In one embodiment, the acidifying agent is an acid or an acidic aqueous solution. In one embodiment, the acidifying agent includes an inorganic acid. In some embodiments, the acidifying agent is a strong inorganic acid. Suitable inorganic acids include, but are not limited to, sulfuric acid, sodium bisulfate, phosphoric acid, nitric acid, and hydrochloric acid. In some embodiments, the acidifying agent includes an organic acid. Suitable organic acids include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzenesulfonic acid, formic acid, acetic acid, monohalocarboxylic acids, dihalocarboxylic acids, or trihalocarboxylic acids, pyridinecarboxylic acid, pyridinedicarboxylic acid, and mixtures thereof.

[0109] The acidifier may be used in an amount sufficient to provide the desired antimicrobial efficacy. Such an agent may be present in the working solution in an amount of at least about 0.1% to about 10% by weight, preferably at least about 0.1% to about 5% by weight, and more preferably about 0.1% to about 1% by weight.

[0110] enzymes

[0111] In one aspect of the invention, an enzyme may be included in the solid composition, including, for example, catalase or peroxidase, which can be used to catalyze the reaction of peroxyhydroxycarboxylic acids and / or reduce and / or eliminate the concentration of hydrogen peroxide in the antimicrobial peracid composition. The enzyme catalyzes the decomposition of hydrogen peroxide into water and oxygen.

[0112] According to the present invention, catalases from various sources can be used, including: animal sources, such as bovine catalase isolated from bovine liver; fungal catalases isolated from fungi, including *Penicillium chrysogenum*, *Penicillium notatum*, and *Aspergillus niger*; plant sources; bacterial sources, such as *Staphylococcus aureus*, and their genetic variations and modifications. In one aspect of the invention, fungal catalases are used to reduce the hydrogen peroxide content of peracidic compositions. Catalases are commercially available in various forms, including liquid and spray-dried forms. Commercially available catalases include an active enzyme and additional components that enhance enzyme stability. Some exemplary commercially available catalases include Genencor CA-100 and CA-400, Mitsubishi Gas and Chemical (MGC) ASC super G and ASC super 200, and Optimase CA 400L from Genecor International. US Patent Publication No. 2009 / 0269324 discloses an additional description of a suitable catalase, which is incorporated herein by reference in its entirety.

[0113] In one aspect of the invention, catalase has a high capacity to decompose hydrogen peroxide. Advantageously, reducing or eliminating hydrogen peroxide from the oxidizing composition avoids various damages caused by oxidants. Specifically, the use of catalase in a peracidic composition provides enhanced antimicrobial benefits without causing the damage associated with conventional oxidants such as corrosion.

[0114] Peroxidases can also be used to decompose hydrogen peroxide from peracid compositions. While the primary function of peroxidases is to oxidize substrates with hydrogen peroxide, they are also suitable for effectively reducing the ratio of hydrogen peroxide to peracid in a composition. Peroxidases from various sources can be used according to the invention, including, for example, animal-derived, fungal peroxidases, as well as their genetic variations and modifications. Peroxidases are commercially available in various forms, including liquid and spray-dried forms. Commercially available peroxidases include active enzymes and additional components that enhance enzyme stability.

[0115] In some embodiments, catalase or peroxidase is capable of degrading at least about 50% of the initial concentration of hydrogen peroxide in the peracid composition. Preferably, the enzyme is provided in a sufficient amount to reduce the hydrogen peroxide concentration of the peracid composition by at least more than about 50%, more preferably at least about 60%, at least about 70%, at least about 80%, or at least about 90%. In some embodiments, the enzyme reduces the hydrogen peroxide concentration of the peracid composition by more than 90%.

[0116] In one aspect of the invention, the enzyme is suitable for use and has tolerance to a wide range of temperatures, including the temperature range for water treatment applications, which can be from about 0°C to 80°C. A suitable catalase will maintain at least 50% of its activity at such storage and / or application temperatures for at least about 10 minutes, preferably at least about 1 hour.

[0117] In one aspect of the invention, catalase or peroxidase is present in a sufficient amount in the use solution of the peracid composition to reduce the concentration of hydrogen peroxide in the peracid composition by at least 50% within about 10 minutes, preferably within about 5 minutes, preferably within about 2 to 5 minutes, and more preferably within about 1 minute. The concentration range of the enzyme will vary depending on the time required to remove 50% of the hydrogen peroxide from the peracid composition. In some aspects of the invention, catalase or peroxidase is present in the use solution composition comprising the water source to be treated at an amount of about 1 ppm to about 1,000 ppm, preferably about 5 ppm to 500 ppm, and more preferably about 10 ppm to about 100 ppm.

[0118] wetting agent

[0119] In one aspect, the wetting agent is present in a sufficient amount in the composition (peroxyhydroxycarboxylic acid composition or peroxyhydroxycarboxylic acid forming composition). The wetting agent is used to increase the surface contact or penetration activity of the peroxyhydroxycarboxylic acid composition. Available wetting agents include any components known in the art for improving the surface activity of a composition. In an exemplary aspect, the wetting agent is a sulfonic acid or a salt thereof (e.g., dodecylbenzenesulfonic acid, sodium salt). In some embodiments, the wetting agent is present in amounts of about 0.001 wt% to about 10 wt%, about 0.01 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, or about 0.1 wt% to about 0.5 wt%.

[0120] stabilizers and buffers

[0121] Advantageously, stabilizers are not required in the methods and / or compositions described herein. However, in some embodiments, the composition (peroxyhydroxycarboxylic acid composition or peroxyhydroxycarboxylic acid forming composition) may also contain stabilizers. In one aspect, the peroxyhydroxycarboxylic acid forming composition may also contain a pH buffer. The peroxyhydroxycarboxylic acid forming composition of the present invention may contain any suitable pH buffer stabilizer. Exemplary stabilizers contain one or more phosphonates and / or heterocyclic dicarboxylic acids, such as pyridinedicarboxylic acid. In some embodiments, the stabilizer is a pyridinecarboxylic acid-based stabilizer, such as pyridinecarboxylic acid and its salt, pyridine-2,6-dicarboxylic acid and its salt, and a phosphonate-based stabilizer, such as phosphoric acid and its salt, pyrophosphate and its salt, and most commonly 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and its salt. In other embodiments, the peroxyhydroxycarboxylic acid forming composition of the present invention comprises two or more stabilizers, such as HEDP and 2,6-pyridinedicarboxylic acid (DPA). In one aspect, stabilizers may be included in any suitable portion of the peroxyhydroxycarboxylic acid forming composition of the present invention.

[0122] In one aspect, the peroxyhydroxycarboxylic acid forming composition may also contain any suitable pH buffer. The pH buffer may include any reagent compatible with the lactone precursor in the peroxyhydroxycarboxylic acid forming composition. Exemplary buffers may be acids (e.g., citric acid), organic amines such as triethanolamine, imidazole, etc., or carbonates, phosphates, etc. The pH buffer may be included in any suitable portion of the peroxyhydroxycarboxylic acid forming composition of the present invention.

[0123] In one aspect, the peroxyhydroxycarboxylic acid forming composition may further include any suitable stabilizer for hydrogen peroxide. Exemplary stabilizers for hydrogen peroxide include phosphonates, heterocyclic carboxylic acids, and mixtures thereof. In some embodiments, the stabilizer for hydrogen peroxide may be Dequest 2010, Dequest 2066, pyridinedicarboxylic acid, etc. The stabilizer for hydrogen peroxide may be included in any suitable portion of the peroxyhydroxycarboxylic acid forming composition. In some embodiments, the second agent comprises the stabilizer for hydrogen peroxide. In other embodiments, the peroxyhydroxycarboxylic acid forming composition may further include a third agent comprising the stabilizer for hydrogen peroxide. In still other embodiments, the solid composition comprises the stabilizer for hydrogen peroxide.

[0124] surfactants

[0125] In some aspects of the invention, the solid composition may contain at least one surfactant. Preferably, a surfactant is included to increase the solubility of peroxyhydroxycarboxylic acids or to maintain the pH of the composition. According to one embodiment, the surfactant is a co-solubilizer or solubilizer that can be used to ensure that the composition remains phase-stable and in a single, highly active aqueous form. Such co-solubilizers or co-solubilizers can be used at concentrations that maintain phase stability without causing unwanted compositional interactions. Surfactants particularly suitable for use with the compositions of the invention include, but are not limited to, nonionic surfactants, anionic surfactants, amphoteric surfactants, and zwitterionic surfactants. Preferably, nonionic and / or anionic surfactants are used with the peracidic compositions of the invention. Exemplary surfactants that can be used are commercially available from many sources. For a discussion of surfactants, see Kirk-Othmer, *Encyclopedia of Chemical Technology*, 3rd Edition, Vol. 8, pp. 900-912.

[0126] Peracids are known to be strong oxidizing agents, and therefore many chemicals contain commonly used surfactants that are incompatible with concentrated peracids to prolong their presence. While it is ideal to use surfactants with peracids to deliver preferred properties such as cleaning, wetting, etc., the selection of surfactants for use in pre-formulated peracid formulations that meet the minimum shelf-life requirements for commercial use is very limited. For example, nonionic surfactants will be degraded by peracids, and cationic surfactants with halogen-counteracting anions will decompose peracids. Some anionic surfactants, namely unsubstituted alkyl sulfonates, such as linear alkylbenzene sulfonates, linear alkyl sulfonates, or olefin sulfonates, are more compatible with peracids and can be used in some peracid compositions, but these anionic surfactants cannot deliver the desired properties due to their undesirable properties (such as high foaming, water hardness, and regulatory requirements). In contrast, for peracid compositions generated in-situ as disclosed in the art, all the surfactants described above can coexist with peracids because the generated peracids are stored for only a very limited time, typically at most a few hours, and the reaction between the surfactant and the peracid is insignificant.

[0127] In some embodiments, the composition comprises about 1% to about 80% by weight of a surfactant. In other embodiments, the composition comprises about 1% to about 50% by weight of a surfactant, or about 1% to about 10% by weight of a surfactant. In yet another embodiment, the composition or a solution of the composition comprises about 10 ppm to about 10,000 ppm of a surfactant. In yet another embodiment, the composition or a solution of the composition comprises about 10 ppm to about 100 ppm of a surfactant. It should be understood that the present invention covers all ranges and values ​​between these ranges and values.

[0128] Nonionic surfactants

[0129] Suitable nonionic surfactants for use with the composition include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, terminated EO / PO copolymers, alcohol alkoxylates, terminated alcohol alkoxylates, mixtures thereof, etc. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers, such as Pluronic and reverse Pluronic surfactants; alcohol alkoxylates; and terminated alcohol alkoxylates, such as Plurafac LF221; mixtures thereof, etc.

[0130] Semi-polar nonionic surfactants

[0131] Semi-polar nonionic surfactants are another class of nonionic surfactants suitable for use in compositions. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides, and their alkoxylated derivatives.

[0132] Amine oxides are tertiary amine oxides corresponding to the following general formula:

[0133]

[0134] The arrows represent the conventional representation of semi-polar bonds; and R 1 R 2 and R 3 It can be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. Generally, for detergents, the focus is on amine oxides, R... 1 It is an alkyl group having about 8 to about 24 carbon atoms; R 2 and R 3 It is an alkyl or hydroxyalkyl group with one to three carbon atoms, or a mixture thereof; R 2 and R 3 They can be interconnected, for example, through oxygen or nitrogen atoms, to form ring structures; R 4It is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to about 20. Amine oxides can be generated from the corresponding amine and an oxidizing agent (such as hydrogen peroxide).

[0135] The usable water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut, or animal lipid alkyl di-(lower alkyl)amine oxides. Specific examples include octyl dimethylamine oxide, nonyl dimethylamine oxide, decyl dimethylamine oxide, undecyl dimethylamine oxide, dodecyl dimethylamine oxide, isododecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, and heptadecanyl dimethylamine oxide. Amines, octadecyl dimethylamine oxide, dodecyl dipropylamine oxide, tetradecyl dipropylamine oxide, hexadecyl dipropylamine oxide, tetradecyl dibutylamine oxide, octadecyl dibutylamine oxide, bis(2-hydroxyethyl) dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyl dimethylamine oxide, and 3-dodecoxy-2-hydroxypropyl di-(2-hydroxyethyl)amine oxide.

[0136] Anionic surfactants

[0137] The anionic sulfate surfactants suitable for use in the compositions of the present invention comprise 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, and C5-C... 17 Acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) reduced glucosamine sulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides. Also includes 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 oxyethylene groups per molecule).

[0138] 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 with or without substituents. Preferred anionic surfactants include linear alkylbenzene sulfonates (LAS) and sodium lauryl sulfate (SLS).

[0139] Anionic carboxylate surfactants suitable for use in the compositions of the present invention comprise carboxylic acids (and salts), such as alkyl acids (and alkyl esters), carboxylic acid esters (e.g., alkyl succinate esters), ether carboxylic acids, etc. Such carboxylate salts include alkyl ethoxycarboxylates, alkyl aryl ethoxycarboxylates, alkyl polyethoxy polycarboxylates surfactants, and soaps (e.g., alkyl carboxylates). Secondary carboxylate salts suitable for use in the compositions of the present invention include those containing a carboxyl unit linked to a secondary carbon. The secondary carbon may be cyclic, for example, in the form of p-octylbenzoic acid or in the form of an alkyl-substituted cyclohexylcarboxylate ester. 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 carbon soap surfactants typically contain 11 to 13 total carbon atoms, but more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acyl amino acids (and salts), such as acylglutamate, acyl peptides, sarcosine salts (e.g., N-acylsarcosine), tartrates (e.g., fatty acid amides of N-acyl tartrate and methylaminoethanesulfonate), etc.

[0140] Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula: RO-(CH2CH2O) n (CH2) m -CO2X, where R is C8 to C9. 22 alkyl or

[0141]

[0142] Where R1 is C4-C 16 An alkyl group; wherein 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 C8-C. 16 Alkyl group. In some embodiments, R is C 12 -C 14 Alkyl groups, n is 4 and m is 1.

[0143] In other implementations, R is

[0144]

[0145] And R1 is C6-C 12 Alkyl groups. In yet another embodiment, R1 is a C9 alkyl group, n is 10 and m is 1. No such alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically obtained in acidic form that can be readily converted into anionic or salt forms.

[0146] Amphoteric surfactants

[0147] Amphoteric surfactants contain both basic and acidic hydrophilic groups, as well as organic hydrophobic groups. These ionic entities can be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In several surfactants, sulfonate, sulfate, phosphonate, or phosphate groups provide a negative charge.

[0148] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group can be linear or branched, and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms, and one of the aliphatic substituents contains an anionic water-soluble group, such as a carboxyl, sulfonic acid, sulfate, phosphate, or phosphonoyl group. Amphoteric surfactants are subdivided into two main categories, which are known to those skilled in the art and described in "Surfactant Encyclopedia," Cosmetics & Toiletries, Vol. 104(2)69-71 (1989), which is incorporated herein by reference in its entirety. The first category includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second category includes N-alkyl amino acids and their salts. Some amphoteric surfactants may be considered to fall into both categories.

[0149] Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethyl imidazoline can be synthesized by condensation and ring-closure of a long-chain carboxylic acid (or derivative) with dialkylethylenediamine. Commercially available amphoteric surfactants are derivatized by alkylation, for example, using chloroacetic acid or ethyl acetate, which sequentially hydrolyzes and ring-opens the imidazoline ring. During alkylation, one or both carboxyl groups react to form a tertiary amine and an ether bond, wherein different alkylating agents produce different tertiary amines.

[0150] Exemplary suitable amphoteric surfactants comprise long-chain imidazole derivatives, including carboxymethylated compounds (glycine salts) often referred to as betaine. Betaine is a particular class of amphoteric surfactants discussed below in the section entitled Amphoteric Surfactants. These and other amphoteric surfactants are further described in U.S. Patent Application Serial No. 12 / 568,493 entitled "Sulfoperoxycarboxylic Acids, Their Preparation and Methods of Use as Bleaching and Antimicrobial Agents," which is expressly incorporated herein by reference in its entirety.

[0151] The long-chain imidazole derivatives used in this invention generally have the following general formula:

[0152]

[0153] Wherein R is a noncyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation used to neutralize the charge of the anion, typically sodium. Commercially known imidazoline-derived amphoteric surfactants that can be used in this composition include, for example: cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropylsulfonate, and cocoamphocarboxypropionic acid. The amphoteric carboxylic acid can be generated from aliphatic imidazolines, wherein the dicarboxylic acid functional group of the amphoteric dicarboxylic acid is diacetic acid and / or dipropionic acid.

[0154] The carboxymethylated compounds (glycine salts) described above in this article are often referred to as betaine. Betaine is a special class of amphoteric surfactants discussed below in the section entitled "Amphoteric Surfactants".

[0155] Additionally, suitable amphoteric surfactants contain components that readily pass through RNH2 (where R = C8-C). 18 Long-chain N-alkyl amino acids are prepared by reacting straight-chain or branched alkyl groups, aliphatic amines, and halocarboxylic acids. Alkylation of the primary amino group of the amino acid yields secondary and tertiary amines. The alkyl substituent may have additional amino groups providing more than one reactive nitrogen center. Most commercially available N-alkylamino acids are alkyl derivatives of β-alanine or β-N(2-carboxyethyl)alanine. Examples of commercially available N-alkyl amino acid amphoteric electrolytes used in this invention include alkyl β-aminodipropionates, RN(C2H4COOM)2, and RNHC2H4COOM. In one embodiment, R may be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation used to neutralize the charge of the anion.

[0156] Suitable amphoteric surfactants include those derived from coconut products (such as coconut oil or coconut fatty acids). Other suitable coconut-derived surfactants include an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety (e.g., glycine), or a combination thereof as part of their structure; and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants can also be considered alkyl amphoteric dicarboxylic acids. These amphoteric surfactants can contain chemical structures represented as follows: C 12 -alkyl-C(O)-NH-CH2-CH2-N + (CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -alkyl-C(O)-N(H)-CH2-CH2-N + (CH2-CO2Na)2-CH2-CH2-OH. Disodium coconut oil dipropionate is a suitable amphoteric surfactant and can be marketed under the brand name MIRANOL. TM FBS was purchased from Rhodia Inc. (Cranbury, NJ). Another suitable coconut-derived amphoteric surfactant with the chemical name disodium cocoate amphoteric diacetate is marketed under the trade name MIRATAINE. TM JCHA sales also come from Rhodia Inc.

[0157] A typical list of these amphoteric classes and substances of surfactants is given in U.S. Patent No. 3,929,678 to Laughlin and Heuring, December 30, 1975, and further examples are given in “Surface Active Agents and Detergents” (Volumes I and II, by Schwartz, Perry, and Berch), each of which is expressly incorporated herein by reference in its entirety.

[0158] zwitterionic surfactants

[0159] Amphoteric surfactants can be considered a subgroup of amphoteric surfactants and may include anionic charges. Broadly speaking, amphoteric surfactants can be described as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium compounds. Or derivatives of tertiary sulfonium compounds. Typically, zwitterionic surfactants include positively charged quaternary ammonium ions, or in some cases, sulfonium ions or... Ions; negatively charged carboxyl groups; and alkyl groups. Zwitterionic surfactants typically contain cationic and anionic groups that are ionized to almost the same degree in the isoelectric region of the molecule, and they can form a strong "internal salt" attraction between the positive and negative charge centers. Examples of such synthesized zwitterionic surfactants include aliphatic quaternary ammonium groups, Derivatives of sulfonium compounds, wherein the aliphatic group may be straight-chain or branched and wherein one of the aliphatic substituents contains 8 to 18 carbon atoms, and one of the aliphatic substituents contains an anionic water-soluble group, such as a carboxyl group, sulfonate group, sulfate group, phosphate group, or phosphonate group. Betaine surfactants and sulfobetaine surfactants are exemplary zwitterionic surfactants used herein.

[0160] The general formula for these compounds is:

[0161]

[0162] Where R 1 Contains an alkyl, alkenyl, or hydroxyalkyl group with 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moieties; Y is selected from nitrogen, phosphorus, and sulfur atoms; R 2 It is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; when Y is a sulfur atom, x is 1, and when Y is a nitrogen or phosphorus atom, x is 2, R 3 It is an alkylene group or a hydroxyalkylene group or a hydroxyalkylene group having 1 to 4 carbon atoms, and Z is a group selected from carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.

[0163] Examples of zwitterionic surfactants having the structures listed above include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonium]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonyl]-3-hydroxypentane-1-sulfate; 3-[P,p-diethyl-P-3,6,9-trioxatetracosylphosphine] [N,N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonium]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonium)-2-hydroxy-propane-1-sulfonate; 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonium]-butane-1-carboxylate; 3-[S-ethyl-S-(3-dodecyloxy-2-hydroxypropyl)sulfonyl]-propane-1-phosphate; 3-[P,P-dimethyl-P-dodecylphosphonate] [N,N-bis(3-hydroxypropyl)-N-hexadecylammonium]-2-hydroxy-pentane-1-sulfate; and S[N,N-bis(3-hydroxypropyl)-N-hexadecylammonium]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in the detergent surfactant may be straight-chain or branched and may be saturated or unsaturated.

[0164] Suitable zwitterionic surfactants for use in this composition include betaine having the following general formula:

[0165]

[0166] These surfactants, betaines, typically do not exhibit strong cationic or anionic properties at extreme pH values, nor do they show a decrease in water solubility over their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic surfactants. Examples of suitable betaines include cocoylaminopropyl dimethyl betaine; hexadecyl dimethyl betaine; C 12-14 Acylamidopropyl betaine; C 8-14 Acylamidohexyldiethylbetaine; 4-C 14-16 Acylmethylamidodiethylammonium-1-carboxybutane; C 16-18 Acylamidodimethylbetaine; C 12-16 Acylaminopentanediethyl betaine; and C 12-16 Acylmethylamidodimethylbetaine.

[0167] The sulfobetaines that can be used in this invention include those having the formula R(R) 1 )2N + R 2 SO 3- Those compounds in which R is C6-C 18 Hydrocarbon group, each R 1 Typically C1-C3 alkyl, for example, methyl, and R 2 It is a C1-C6 hydrocarbon group, such as a C1-C3 alkylene group or a hydroxyalkylene group.

[0168] A typical list of zwitterionic classes and substances of these surfactants is given in U.S. Patent No. 3,929,678, granted to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Volumes I and II, by Schwartz, Perry, and Berch). These references are each incorporated herein in full.

[0169] Method of treating targets with peroxyhydroxycarboxylic acid

[0170] In one aspect, the method for forming a peroxyhydroxycarboxylic acid is suitable for treating a surface or target, the method comprising contacting the surface or target with an effective amount of the peroxyhydroxycarboxylic acid formed using the above method to form a treated surface or target composition, wherein the treated surface or target composition comprises about 0.1 ppm to about 10,000 ppm of the peroxyhydroxycarboxylic acid, and the contact step lasts for a sufficient time to stabilize or reduce the microbial community on the surface or target or the treated surface of the target composition.

[0171] Advantageously, according to various embodiments, the method using the peroxyhydroxycarboxylic acid composition does not require a stabilizer for the composition. In some embodiments, the composition used comprises a peroxyalpha-hydroxycarboxylic acid (e.g., peroxylactic acid), hydrogen peroxide, lactic acid, and a solvent (e.g., water). In some embodiments, the composition used in the method of the present invention does not contain inorganic acids, such as those disclosed in WO 91 / 07375.

[0172] The peroxyhydroxycarboxylic acid and the surface or target can contact to form a peroxyhydroxycarboxylic acid containing any suitable concentration, for example, about 0.1 ppm to 1 ppm, 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm, 300 ppm to 350 ppm, 350 ppm to 400 ppm, 400 ppm to 450 ppm, 450 ppm Up to 500ppm, 500ppm to 550ppm, 550ppm to 600ppm, 600ppm to 650ppm, 650ppm to 700ppm, 700ppm to 750ppm, 750ppm to 800ppm, 800ppm to 850ppm, 850ppm to 900ppm, 900ppm to 950ppm, 950ppm to 1,000ppm, 1,000ppm to 1,500ppm, 1,500ppm to 2,000ppm, 2,000ppm to 2,500ppm, 2,500ppm to 3,000ppm, 3,000ppm to 3,500ppm, 3,500ppm to 4,000ppm, 4,000ppm to 4,500ppm, or Treated target compositions of peroxyhydroxycarboxylic acids in amounts of 4,500 ppm to 5,000 ppm, 5,000 ppm to 5,500 ppm, 5,500 ppm to 6,000 ppm, 6,000 ppm to 6,500 ppm, 6,500 ppm to 7,000 ppm, 7,000 ppm to 7,500 ppm, 7,500 ppm to 8,000 ppm, 8,000 ppm to 8,500 ppm, 8,500 ppm to 9,000 ppm, 9,000 ppm to 9,500 ppm, or 9,500 ppm to 10,000 ppm. In a preferred embodiment, the peroxyhydroxycarboxylic acid and the surface or target can contact to form a treated target composition comprising about 0.1 ppm to 2,000 ppm, about 1 ppm to 2,000 ppm, about 10 ppm to 2,000 ppm, about 10 ppm to 1,000 ppm, or about 100 ppm to 1,000 ppm of the peroxyhydroxycarboxylic acid.

[0173] In some embodiments, the target to be treated by the method of the present invention may be at least a portion of a food article or plant article and / or a medium, container, device, system, or facility used for growing, maintaining, processing, packaging, storing, transporting, preparing, cooking, or serving the food article or plant article. In some embodiments, the food article or plant article is a consumer product and / or is in a consumer's home. Any suitable concentration of peroxyhydroxycarboxylic acid may be used in the method of the present invention. For example, peroxyhydroxycarboxylic acids can be used at concentrations from about 1 ppm to about 100 ppm, such as about 1 ppm to 2 ppm, 2 ppm to 3 ppm, 3 ppm to 4 ppm, 4 ppm to 5 ppm, 5 ppm to 6 ppm, 6 ppm to 7 ppm, 7 ppm to 8 ppm, 8 ppm to 9 ppm, 9 ppm to 10 ppm, 10 ppm to 15 ppm, 15 ppm to 20 ppm, 20 ppm to 25 ppm, or 25 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, or 90 ppm to 100 ppm. In some embodiments, the target is a food article or a plant article, and the contact step minimizes or eliminates sensory effects in and / or on the food article and / or plant article.

[0174] The method of the present invention can be used to treat any suitable plant article. In some embodiments, the plant article is a cereal, fruit, vegetable, or flowering plant article. In other embodiments, the plant article is a living plant article or a harvested plant article. In still other embodiments, the plant article includes seeds, tubers, growing plants, cuttings, or rhizomes. In still other embodiments, the method of the present invention is used to treat living plant tissue, including treating the plant tissue with a diluted concentration of the composition described above to stabilize or reduce the microbial community in and / or on the plant tissue. In still other embodiments, the method of the present invention is used to cultivate plants on a hydroponic substrate in a hydroponic liquid supply medium, including: (a) establishing living plant tissue in the hydroponic substrate; (b) contacting the living plant tissue, the hydroponic substrate, and the hydroponic liquid with the composition of the present invention to stabilize or reduce the microbial community in and / or on the living plant tissue; and (c) harvesting a usable plant product with reduced microbial contamination.

[0175] The method of this invention can be used to process any suitable food article. For example, the food article can be animal product, such as animal carcasses or eggs, fruit articles, vegetable articles, or grain articles. In some embodiments, the animal carcass can be a cow, pig, calf, buffalo, sheep, fish, seafood, or poultry carcass. In other embodiments, the seafood carcass can be scallops, shrimp, crab, octopus, mussels, squid, or lobster. In still other embodiments, the fruit article can be a plant fruit, culinary fruit, monocarp, aggregate fruit, berry, appendage fruit, or seedless fruit. In still other embodiments, the vegetable article can be a flower bud, seed, leaf, leaf sheath, bud, stem, leaf stem, stem bud, tuber, whole plant bud, root, or bulb. In still other embodiments, the grain article can be corn, rice, wheat, barley, sorghum, millet, oats, black wheat, rye, buckwheat, forniamidum, or quinoa.

[0176] In some embodiments, the target to be treated by the method of the present invention may be a medical care facility, such as a medium, surface, container, device, or system in a physical office or hospital. Any suitable concentration of peroxyhydroxycarboxylic acid can be used in the method of the present invention. For example, peroxyhydroxycarboxylic acid can be used at concentrations from about 10 ppm to about 300 ppm, such as 10 ppm to 15 ppm, 15 ppm to 20 ppm, 20 ppm to 25 ppm, or 25 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, or 250 ppm to 300 ppm.

[0177] The method of the present invention can be used to process targets that are at least a portion of containers, equipment, systems, or facilities used for holding, processing, packaging, storing, conveying, preparing, cooking, or serving food articles or plant articles. In some embodiments, the target is at least a portion of a container, equipment, system, or facility used for holding, processing, packaging, storing, conveying, preparing, cooking, or serving meat articles, fruit articles, vegetable articles, or grain articles. In other embodiments, the target is at least a portion of a container, equipment, system, or facility used for holding, processing, packaging, storing, or conveying animal carcasses. In still other embodiments, the target is at least a portion of a container, equipment, system, or facility used in the food processing, food service, or medical industries. In still other embodiments, the target is at least a portion of a stationary process facility. Exemplary stationary process facilities may include dairy milk lines, continuous brewing systems, pumpable food systems, or beverage processing lines.

[0178] The method of the present invention can be used to treat a target that is at least a portion of a solid surface or a liquid medium. In some embodiments, the solid surface is a non-living solid surface. Non-living solid surfaces can be contaminated by biological fluids (e.g., biological fluids containing blood, other harmful fluids, or mixtures thereof). In other embodiments, the solid surface can be a contaminated surface. Exemplary contaminated surfaces may include the surface of food service utensils or equipment, or the surface of fabrics.

[0179] Peroxyhydroxycarboxylic acids can be applied in any suitable manner. In some embodiments, the peroxyhydroxycarboxylic acid can be applied to the target by means of spraying, atomizing, or foaming, or by immersing all or part of the target in a composition containing the peroxyhydroxycarboxylic acid. In some embodiments, the peroxyhydroxycarboxylic acid composition is applied to the target by means of spraying, atomizing, or foaming. In other embodiments, the diluted peroxyhydroxycarboxylic acid is applied to the target in the form of a thickening or gelling solution. In still other embodiments, all or part of the target is immersed in the peroxyhydroxycarboxylic acid composition. The target and / or the peroxyhydroxycarboxylic acid composition can be subjected to any suitable movement to aid or promote contact between the target and the peroxyhydroxycarboxylic acid composition. In some embodiments, the peroxyhydroxycarboxylic acid composition can be agitated. In other embodiments, the peroxyhydroxycarboxylic acid composition can be sprayed onto a target, such as an animal carcass, at a suitable pressure and a suitable temperature. For example, the peroxyhydroxycarboxylic acid composition can be sprayed onto an animal carcass at a pressure of at least 50 psi and a temperature of up to about 60°C, thereby creating a contact time of at least 30 seconds.

[0180] The method of the present invention may include any suitable additional steps. In some embodiments, the method of the present invention may include a vacuum processing step. In other embodiments, the method of the present invention may include the step of applying an activated light source to a target, such as an animal carcass.

[0181] The contact step in the method of the present invention can last for any suitable amount of time. In some embodiments, the contact step can last for at least about 1 second or at least about 10 seconds. For example, the contact step can last for at least about 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 1-2 minutes, 2-3 minutes, 3-4 minutes, 4-5 minutes, 5-6 minutes, 6-7 minutes, 7-8 minutes, 8-9 minutes or 9-10 minutes, 10-15 minutes, 15-20 minutes, 20-25 minutes, 25-30 minutes, 30-40 minutes, 40-50 minutes, 50-65 minutes, 1-2 hours, 2-3 hours, 3-4 hours, 4-5 hours, 5-6 hours, 6-7 hours, 7-8 hours, 8-9 hours or 9-10 hours, 16 hours, 1 day, 3 days, 1 week or longer. In one aspect, the contact occurs for a period of time before the peroxyhydroxycarboxylic acid composition degrades.

[0182] The method of the present invention can be used to reduce the microbial community in and / or on a target or treated target composition by any suitable order of magnitude. In some embodiments, the method of the present invention can be used to reduce the microbial community in and / or on a target or treated target composition by at least log 10 Two logs 10 Three logs 10 Four logs 10 Five logs 10 Or more. In other embodiments, if present in and / or on the target or treated target composition, the level of microorganisms can be stabilized or reduced by the method of the present invention. For example, if present in and / or on the target or treated target composition, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or more of microorganisms can be killed, destroyed, removed, and / or inactivated by the method of the present invention.

[0183] The method of the present invention can be used to reduce a population of any one or more suitable microorganisms in and / or on a target or treated target composition by any suitable order of magnitude. In some embodiments, the method of the present invention can be used to reduce a population of prokaryotic microorganisms, such as bacteria or archaea. In other embodiments, the method of the present invention can be used to reduce a population of eukaryotic microorganisms, such as protozoa or fungi. In still other embodiments, the method of the present invention can be used to reduce a population of viruses. Exemplary viral populations may include populations of DNA viruses, RNA viruses, and retroviruses.

[0184] The method of the present invention can be used to stabilize or reduce microbial communities in and / or on a target or treated target composition, wherein the target is a food article or plant article, and the contact step minimizes or eliminates sensory effects in and / or on the food article and / or plant article. Typical sensory characteristics include, for example, aspects experienced by the senses of a food or other substance, taking into account dryness, moisture, and staleness-freshness factors, including taste, sight, smell, and touch. See, for example, Jasper Womach, the Congressional Research Service document "Report for Congress: Agriculture: A Glossary of Term, Programs, and Laws, 2005". In some embodiments, sensory procedures are performed as part of meat and poultry inspections to detect signs of disease or contamination. In other embodiments, sensory testing is performed to determine whether packaging materials and components can transfer taste and odor to the food or pharmaceutical product they package. Shelf life studies typically use taste, sight, and smell (in addition to food chemistry and toxicology testing) to determine whether a food is fit for consumption. In other implementations, sensory testing is performed as part of the Hurdle technique. Typically, the Hurdle technique refers to a smart combination of barriers that ensures the microbiological safety and stability of food products, as well as their sensory and nutritional quality and economic viability. See also Leistner L (1995) "In Gould GW (ed.) New Methods of Food Preservation, Springer, pp. 1-21; and Leistner I (2000) "International Journal of Food Microbiology, 55: 181-186."

[0185] The method of the present invention can be performed within any suitable temperature range. In some embodiments, the method of the present invention can be performed at temperatures ranging from about 0°C to about 70°C, for example, in the range of about 0°C to 1°C, 1°C to 2°C, 2°C to 3°C, 3°C to 4°C, 4°C to 5°C, 5°C to 10°C, 10°C to 15°C, 15°C to 20°C, 20°C to 25°C, 25°C to 30°C, 30°C to 35°C, 35°C to 40°C, 40°C to 45°C, 45°C to 50°C, 50°C to 55°C, 55°C to 60°C, 60°C to 65°C, or 65°C to 70°C. In other embodiments, the method of the present invention can be performed at temperatures equal to or below 0°C.

[0186] In some embodiments, the method of the present invention may include adding a peroxidase or catalase to further reduce the level of hydrogen peroxide in and / or on the target or treated target composition. The peroxidase or catalase may be added in any suitable manner. In some embodiments, the peroxidase or catalase may be added to the target or treated target composition before the composition used in the method of the present invention is provided to the target. In other embodiments, the composition of the present invention may be diluted to a suitable intermediate amount, and the peroxidase or catalase may be added to the diluted intermediate amount. Thereafter, the diluted intermediate amount containing the peroxidase or catalase may be added to the target. Any suitable peroxidase or catalase, including the peroxidases or catalases described below, may be used in the method of the present invention.

[0187] Used in water treatment

[0188] The method of the present invention can be used to treat any suitable surface or target. In some embodiments, the target is water, and the method of the present invention may include providing an effective amount of peroxyhydroxycarboxylic acid formed using the above method to a water source to be treated to form a treated water source, wherein the treated water source contains about 1 ppm to about 10,000 ppm of the peroxyhydroxycarboxylic acid, for example, about 1 ppm to 10 ppm, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm... Peroxyhydroxycarboxylic acids ranging from 1 pm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm, 300 ppm to 350 ppm, 350 ppm to 400 ppm, 400 ppm to 450 ppm, 450 ppm to 500 ppm, 500 ppm to 550 ppm, 550 ppm to 600 ppm, 600 ppm to 650 ppm, 650 ppm to 700 ppm, 700 ppm to 750 ppm, 750 ppm to 800 ppm, 800 ppm to 850 ppm, 850 ppm to 900 ppm, 900 ppm to 950 ppm, and 950 ppm to 1,000 ppm.

[0189] The method of this invention can be used to treat any suitable water source. For example, the water source to be treated can be fresh water, pond water, seawater, produced water, papermaking water, tower water, or a combination thereof.

[0190] In some embodiments, the tower water is cooling water and the treated water source contains about 1 ppm to about 10 ppm of peroxyhydroxycarboxylic acid, for example, about 1 ppm to 2 ppm, 2 ppm to 3 ppm, 3 ppm to 4 ppm, 4 ppm to 5 ppm, 5 ppm to 6 ppm, 6 ppm to 7 ppm, 7 ppm to 8 ppm, 8 ppm to 9 ppm, or 9 ppm to 10 ppm of peroxyhydroxycarboxylic acid. The contact step can last for any suitable amount of time, for example, about 1 minute to 2 minutes, 2 minutes to 3 minutes, 3 minutes to 4 minutes, 4 minutes to 5 minutes, 5 minutes to 6 minutes, 6 minutes to 7 minutes, 7 minutes to 8 minutes, 8 minutes to 9 minutes, or 9 minutes to 10 minutes. The contact step can be carried out within any suitable temperature range. For example, the contact step can be carried out at temperatures ranging from about 0°C to about 60°C, such as from about 0°C to 1°C, 1°C to 2°C, 2°C to 3°C, 3°C to 4°C, 4°C to 5°C, 5°C to 10°C, 10°C to 15°C, 15°C to 20°C, 20°C to 25°C, 25°C to 30°C, 30°C to 35°C, 35°C to 40°C, 40°C to 45°C, 45°C to 50°C, 50°C to 55°C, or 55°C to 60°C.

[0191] In some embodiments, the method of the present invention can be used to treat water sources used in oil or gas drilling operations. For example, the method of the present invention can be used to treat water sources used in induced hydraulic fracturing (hydraulic fracturing or fracturing) operations. The water source may contain friction reducers or viscosity enhancers. The method of the present invention can be used to treat the water source to form a treated water source containing about 1 ppm to about 10 ppm of peroxyhydroxycarboxylic acid, such as about 1 ppm to 2 ppm, 2 ppm to 3 ppm, 3 ppm to 4 ppm, 4 ppm to 5 ppm, 5 ppm to 6 ppm, 6 ppm to 7 ppm, 7 ppm to 8 ppm, 8 ppm to 9 ppm, or 9 ppm to 10 ppm of peroxyhydroxycarboxylic acid. The method of the present invention may also include disposing of the treated water source. The method of the present invention may also include directing the treated water source to a subsurface environment, such as the subsurface environment of a well comprising natural gas and / or oil. In some embodiments, the target water to be treated contains iron sulfide and / or H2S, and the method of the present invention can be used to oxidize the iron sulfide in the target water and / or reduce or eliminate the H2S in the target water. In other embodiments, the target water to be treated needs to be clarified, for example, containing particles, and the method of the present invention can be used to clarify the target water.

[0192] In some embodiments, the target to be treated by the method of the present invention may be water and / or at least a portion of a medium, container, device, system, or facility used for the production, holding, processing, packaging, storage, or transport of pulp. The method of the present invention can be used to treat water and / or other targets for any suitable purpose. For example, the method of the present invention can be used in the paper, textile, food, or pharmaceutical industries. The method of the present invention can be used to treat water sources alone or in combination with other targets to form a treated water source containing any suitable concentration of peroxyhydroxycarboxylic acid, for example, about 1 ppm to 2 ppm, 2 ppm to 3 ppm, 3 ppm to 4 ppm, 4 ppm to 5 ppm, 5 ppm to 6 ppm, 6 ppm to 7 ppm, 7 ppm to 8 ppm, 8 ppm to 9 ppm, 9 ppm to 10 ppm, 10 ppm to 15 ppm, 15 ppm to 20 ppm, 20 ppm to 25 ppm, or 25 ppm to 30 ppm of peroxyhydroxycarboxylic acid.

[0193] Peroxyhydroxycarboxylic acid compositions can be used in a variety of industrial applications, for example, to reduce microbial or viral populations on or within surfaces or objects or water streams. In some aspects, the invention includes methods of using peroxyhydroxycarboxylic acid compositions to prevent biofouling in various industrial processes and industries (including oil and gas operations), control microbial growth, eliminate microbial contamination, and limit or prevent biofouling on the surfaces of liquid systems, process water, or equipment in contact with such liquid systems. As described herein, microbial contamination can occur in a variety of industrial liquid systems, including but not limited to airborne contamination, makeup water, process leaks, and improperly cleaned equipment. In another aspect, peroxyhydroxycarboxylic acid and catalase compositions are used to control microbial growth in water used in various oil and gas operations. In yet another aspect, the compositions are suitable for incorporation into fracturing fluids to control or eliminate microorganisms.

[0194] As used herein with respect to the method of the invention, the peroxyhydroxycarboxylic acid composition can be a variety of peroxyhydroxycarboxylic acid compositions having low or even substantially no hydrogen peroxide concentration. These peroxyhydroxycarboxylic acid compositions include those containing catalase or peroxidase and / or other peroxyhydroxycarboxylic acid compositions disclosed herein that have reduced hydrogen peroxide, said catalase or peroxidase lowering the ratio of hydrogen peroxide to peracid. In a preferred embodiment, a peroxyhydroxycarboxylic acid composition having reduced or substantially no hydrogen peroxide and catalase are introduced into the water source to be treated using a solution.

[0195] The method of introducing the peroxyhydroxycarboxylic acid solution into the aqueous fluid according to the invention is not important. The introduction of the peroxyhydroxycarboxylic acid composition can be carried out continuously or intermittently and will depend on the type of water being treated. In some embodiments, the peroxyhydroxycarboxylic acid composition is introduced into the aqueous fluid according to the method disclosed in U.S. Patent Application Serial No. 13 / 645,671 entitled "New Method and Arrangement for Feeding Chemicals into a Hydrofracturing Process and Oil and Gas Applications", which is incorporated herein by reference in its entirety.

[0196] In some embodiments, the water source treated by the method of the present invention does not contain reused water, the treated water source contains about 10 ppm to about 20 ppm of in-situ formed peroxyhydroxycarboxylic acid and about 1 ppm to about 2 ppm of hydrogen peroxide, and the treated water source does not contain friction modifiers and / or rheology modifiers.

[0197] In some aspects, the disclosed methods for water treatment in oil and gas recovery provide effective antimicrobial efficacy without harmful interactions with functional agents, including, for example, friction modifiers. In another aspect, the methods for water treatment provide increased antimicrobial efficacy compared to the use of antimicrobial peracids alone. In yet another aspect, the methods allow for the treatment of cleaner water with low microbial concentrations. In yet another aspect, the reduction and / or elimination of H2O2 from the peracid composition minimizes the negative impact of the oxidant H2O2. Furthermore, due to the reduction and / or elimination of H2O2 from the system, the methods of the present invention reduce volume expansion within the sealing systems used in oil and gas recovery methods.

[0198] In one aspect, a peroxyhydroxycarboxylic acid solution is added to the water to be treated prior to drilling and fracturing steps to limit the introduction of microorganisms into the reservoir and prevent microorganisms from negatively impacting the integrity of the fluid. Source water (e.g., ponds, lakes, municipal water, etc.) and / or produced water treatment are particularly suitable for use according to the invention.

[0199] The treated water according to the invention can be used for slickwater fracturing (i.e., using friction modifiers) and / or gel fracturing (i.e., using viscosity enhancers), depending on the type of fracturing formation and the type of hydrocarbons expected to be generated. The use of peroxyhydroxycarboxylic acid solutions (including catalase-treated peroxyhydroxycarboxylic acid compositions with low or even essentially no hydrogen peroxide) is suitable for both slickwater fracturing and gel fracturing. On one hand, pretreatment of the peroxyhydroxycarboxylic acid composition with catalase substantially removes hydrogen peroxide with minimal or no effect on the fracturing fluid and the well itself. On the other hand, catalase-pretreated peroxyhydroxycarboxylic acid compositions allow for the formation of gels suitable for gel fracturing, as opposed to untreated peroxyhydroxycarboxylic acid composition solutions that, under certain conditions, do not allow gel formation. On the other hand, peroxyhydroxycarboxylic acid composition solutions are added to the water requiring treatment in the subsurface well formation (e.g., introduced through boreholes in the subsurface formation). These methods provide additional control within the well formation, suitable for reducing the microbial community already present in the downhole conduit or within the reservoir itself.

[0200] In another aspect, a peroxyhydroxycarboxylic acid composition solution is added to the water requiring treatment prior to disposal. In this regard, the return water (e.g., after fracturing) is treated to minimize microbial contamination and remove solids before being discharged into underground wells, reused in subsequent fracturing applications, or returned to local environmental water sources.

[0201] On one hand, the water sources that need to be treated can vary greatly. For example, the water source can be freshwater (e.g., pond water), brackish or saline water, slightly brackish water, recirculating water, etc. In one aspect involving offshore drilling operations, seawater sources (e.g., brackish or non-brackish water) are often used. Advantageously, the peroxyhydroxycarboxylic acid composition of the present invention is suitable for use with any type of water, regardless of the presence or absence of catalase, and provides effective antimicrobial efficiency for any of such water sources.

[0202] According to the invention, a large amount of water is used to meet the needs of well fluid operations. Therefore, in one aspect of the invention, a circulating water source (e.g., produced water) is typically used to reduce the amount of freshwater, pond water, or seawater required. Circulating water or produced water is understood to include non-potable water sources. Using such produced water (in combination with freshwater, pond water, or seawater) reduces certain economic and / or environmental limitations. In one aspect, thousands to millions of gallons of water can be used, and the combination of produced water with freshwater sources provides significant economic and environmental advantages. In one aspect, as much produced water as possible is used. In one embodiment, at least 1% of the produced water is used, preferably at least 5%, preferably at least 10%, preferably at least 20%, or more preferably more than 20%.

[0203] According to embodiments of the invention, a sufficient amount of a peroxyhydroxycarboxylic acid composition, with or without catalase, is added to the aqueous water source to be treated to provide the concentration of peroxyhydroxycarboxylic acid required for antimicrobial efficacy. For example, a certain amount of a peroxyhydroxycarboxylic acid and catalase solution composition is added to the water source until the concentration of peroxyhydroxycarboxylic acid in the water source is detected to be within a preferred concentration range (e.g., about 1 ppm to about 100 ppm peracid). In one aspect, the microbial count is preferably less than about 100,000 microorganisms / mL, more preferably less than about 10,000 microorganisms / mL, or even more preferably less than about 1,000 microorganisms / mL.

[0204] The methods of use described herein can vary in terms of temperature and pH conditions associated with the use of the aqueous treatment fluid. For example, according to the applications disclosed herein, the aqueous treatment fluid can withstand different ambient temperatures, including a range from about 0°C to about 130°C during treatment operations. Preferably, the temperature range is between about 5°C and about 100°C, more preferably between about 10°C and about 80°C. However, since most of the antimicrobial activity of the compositions of the present invention occurs over a short period of time, exposure of the compositions to relatively high temperatures is not a major problem. Additionally, the overly acidic aqueous treatment fluid compositions (i.e., the solution used) can withstand different pH ranges, such as from 1 to about 10.5.

[0205] The antimicrobial composition of the present invention is fast-acting. However, for sufficient antimicrobial activity to occur, the method of this disclosure requires a minimum contact time between the composition and the water to be treated. The contact time can vary depending on the concentration of the composition used, the method of application of the composition, the temperature at which the composition is used, the pH of the composition used, the volume of water to be treated, the amount of dirt or matrix in the water to be treated, etc. The contact or exposure time can be at least about 15 seconds. In some embodiments, the exposure time is about 1 to 5 minutes. In other embodiments, the exposure time is at least about 10 minutes, 30 minutes, or 60 minutes. In other embodiments, the exposure time is from several minutes to several hours. The contact time will further vary based on the concentration of superacidity in the solution used.

[0206] Beneficial effects of water treatment methods

[0207] On one hand, the method of use provides an antimicrobial agent that will not have a negative impact on the environment. Advantageously, the degradation of the compositions of the present invention provides a "green" alternative.

[0208] On the other hand, the method of application provides an antimicrobial agent that does not negatively interfere with the use of friction reducers, viscosity enhancers, and / or other functional ingredients. On the other hand, the method of application does not negatively interfere with any additional functional agents used in water treatment methods, including, for example, corrosion inhibitors, descaling agents, etc. The composition applied according to the invention provides extremely effective control of microorganisms without adversely affecting the functional properties of any added polymers in the aqueous system. Furthermore, the peroxyhydroxycarboxylic acid composition provides additional benefits to the system, including, for example, reduced corrosion within the system due to the reduction or substantial elimination of hydrogen peroxide from the treated composition. Advantageously, the peroxyhydroxycarboxylic acid composition (with or without catalase) achieves a harmless effect on various functional ingredients used in water treatment methods, regardless of the composition of the water source to be treated.

[0209] On the other hand, methods are used to prevent system contamination, such as well or reservoir acidification. In other aspects, methods are used to prevent corrosion caused by microbial influences on the systems in which they are applied.

[0210] In other respects, the methods of use utilize the antimicrobial and / or bleaching activity of the peroxyhydroxycarboxylic acid composition. For example, the present invention includes methods for reducing microbial communities and / or bleaching methods. These methods can be carried out on the article, on a surface, in the body, or in the like, or in a stream of water or gas, by contacting the composition with the article, surface, body, or stream. Contact can include any of a variety of methods for applying the composition, including but not limited to providing the antimicrobial peroxyhydroxycarboxylic acid composition in an aqueous solution of use and immersing any article, and / or providing it to a water source requiring treatment.

[0211] The compositions are suitable for antimicrobial efficacy against a broad spectrum of microorganisms, thereby providing broad-spectrum bactericidal and bacteriostatic activity. For example, the peracidic biocides of the present invention provide broad-spectrum activity against a variety of different types of microorganisms (including both aerobic and anaerobic microorganisms), including bacteria, yeasts, molds, fungi, algae, and other problematic microorganisms associated with oilfield and gas field operations.

[0212] Exemplary microorganisms sensitive to the peroxyhydroxycarboxylic acid compositions of the present invention include Gram-positive bacteria (e.g., Staphylococcus aureus, Bacillus species such as Bacillus subtilis, Clostridia), Gram-negative bacteria (e.g., Escherichia coli, Pseudomonas, Klebsiella pneumoniae, Legionella pneumophila, Enterobacter, Serratia, Desulfovibrio, and Desulfotomaculum), yeasts (e.g., Saccharomyces cerevisiae and Candida albicans), and molds (e.g., Aspergillus niger). The fungi include *Aspergillus niger*, *Cephalosporium acremonium*, *Penicillium notatum*, and *Aureobasidium pullulans*, filamentous fungi (e.g., *Aspergillus niger* and *Cladosporium resinae*), algae (e.g., *Chlorella vulgaris*, *Euglena gracilis*, and *Selenastrum capricornutum*), and other similar microorganisms and single-celled organisms (e.g., phytoplankton and protozoa). Other exemplary microorganisms sensitive to the peracid compositions of the present invention include those disclosed in U.S. Patent Application US 2010 / 0160449 A1, such as sulfur or sulfate-reducing bacteria, such as *Desulfovibrio* and *Desulfuric Enterobacteriaceae*.

[0213] Used in other processes

[0214] Other implementations include water treatment for various industrial processes involving the treatment of liquid systems. As used herein, a “liquid system” means an environment containing water or at least one artifact that contains a significant amount of liquid capable of undergoing biofouling. Liquid systems include, but are not limited to, industrial liquid systems, industrial water systems, liquid process flows, industrial liquid process flows, industrial process water systems, process water applications, process water, utility water, water used in manufacturing, water used in industrial services, aqueous liquid flows, liquid flows containing two or more liquid phases, and any combination thereof.

[0215] On the other hand, the method of the present invention can also be used to treat other liquid systems in which the antimicrobial properties and oxidizing properties of the composition can be utilized. In addition to microbial problems surrounding wastewater, wastewater is often rich in odorous compounds containing reduced sulfur, nitrogen, or phosphorus. Strong oxidants such as the compositions disclosed herein effectively convert these compounds into their odorless derivatives, such as sulfates, phosphates, and amine oxides. These same properties are very useful in the pulp and paper industry, where bleaching properties are also helpful.

[0216] The method of the present invention can be carried out at any suitable temperature. In some embodiments, the method of the present invention is carried out in the range of about -2°C to about 70°C, for example about 0°C to about 4°C or 5°C, about 5°C to about 10°C, about 11°C to about 20°C, about 21°C to about 30°C, about 31°C to about 40°C, including temperatures at about 37°C, about 41°C to about 50°C, about 51°C to about 60°C, or about 61°C to about 70°C.

[0217] The method of the present invention can be used in the methods, processes, or procedures described and / or claimed in U.S. Patent Nos. 5,200,189, 5,314,687, and 5,718,910. In some embodiments, the method of the present invention can be used to sterilize a facility or equipment, comprising the step of contacting the facility or equipment with the composition of the present invention at a temperature ranging from about 4°C to about 60°C. The peroxyhydroxycarboxylic acid composition is then circulated or contacted with the facility or equipment for a sufficient sterilization time (typically at least 30 seconds), and then the treated target composition is discharged or removed from the facility or equipment.

[0218] As described above, the method of the present invention can be used for cleaning or disinfecting processing facilities or equipment in the food service, food processing, or health care industries. Examples of processing facilities to which the method of the present invention can be used include dairy production lines, continuous brewing systems, food processing lines such as pumpable food systems, and beverage production lines. Food serving dishes can also be sterilized using the method of the present invention. The method of the present invention can also be used for disinfection or sterilization of solid surfaces present in the medical industry, such as floors, counters, furniture, medical tools, and equipment. Such surfaces are often contaminated with liquid bodily spills such as blood, other hazardous bodily fluids, or mixtures thereof.

[0219] Generally, the actual cleaning of the system or other surfaces (i.e., removing unwanted residues) can be accomplished using various materials, such as formulated detergents with hot water. Following this cleaning step, the peroxyhydroxycarboxylic acid composition can be applied to or introduced into the system at a concentration suitable for use in unheated ambient water. In some embodiments, the peroxyhydroxycarboxylic acid composition has been found to remain soluble in both cold (e.g., 40°F / 4°C) and hot (e.g., 140°F / 60°C) water. While heating the aqueous solution of the peroxyhydroxycarboxylic acid composition is generally not required, heating may be necessary in some environments to further enhance its antimicrobial activity.

[0220] In some embodiments, a method for sterilizing a substantially in-situ process facility includes the following steps: The peroxyhydroxycarboxylic acid composition of the present invention is introduced into the processing facility at a temperature ranging from about 4°C to about 60°C. After the introduction of the working solution, the solution is circulated throughout the system for a sufficient time to sterilize the process facility (i.e., kill unwanted microorganisms). After sterilization of the system using the composition of the present invention, the working composition or solution is drained from the system. After the sterilization step is completed, the system may optionally be rinsed with other materials such as drinking water. The composition of the present invention is preferably circulated through the processing facility for 10 minutes or less.

[0221] In other embodiments, the peroxyhydroxycarboxylic acid composition of the present invention can also be used by the following steps: immersing food processing equipment in the diluted (or used) composition or solution of the present invention for a sufficient time to sterilize the equipment, and wiping or draining excess solution from the equipment. The composition can be further used by the following steps: spraying or wiping the food processing surface with the solution, keeping the surface moist for a sufficient time to sterilize the surface, and removing excess composition or solution by wiping, vertical draining, vacuum treatment, etc.

[0222] In other embodiments, the peroxyhydroxycarboxylic acid composition of the present invention can also be used in methods for disinfecting hard surfaces (such as machine-type equipment, utensils, tableware, healthcare equipment or tools, and other hard surfaces). The peroxyhydroxycarboxylic acid composition can also be used to disinfect contaminated clothing or fabrics. The peroxyhydroxycarboxylic acid composition is brought into contact with any of the aforementioned contaminated surfaces or articles at a usage temperature ranging from about 4°C to about 60°C for a sustained and effective period of time to disinfect, sterilize, or sterilize the surface or article.

[0223] The methods of this invention can be used in the methods, processes, or procedures described and / or claimed in U.S. Patent Nos. 6,165,483 and 6,238,685B1 to treat plant tissues, seeds, fruits, and growing media, as well as containers, grown in the field or in a greenhouse. The peroxyhydroxycarboxylic acid compositions of this invention can reduce the load of natural, plant pathogens, and human pathogenic microorganisms, thereby reducing waste due to molding, spoilage, and destruction caused by pathogenic toxins.

[0224] In some embodiments, the peroxyhydroxycarboxylic acid compositions of the present invention can be used to protect cultivated plant tissues from the adverse effects of microbial invasion. The peroxyhydroxycarboxylic acid compositions can be applied to cultivated plant tissues and can provide residual antimicrobial effects after the plant has completed its growth cycle and the fruit or vegetable material has been harvested and sent to market. The compositions of the present invention can effectively treat living or cultivated plant tissues, including seeds, roots, tubers, seedlings, cuttings, rhizomes, cultivated plants, agricultural products, fruits, and vegetables. In some cases, a single peroxyacid material can be effective; however, in other cases, a mixture of peroxyacids has significantly improved and unexpected properties.

[0225] Animal handling / Egg Methods of white matter carcasses

[0226] The method of the present invention can be used in the methods, processes, or procedures described and / or claimed in U.S. Patent Nos. 6,010,729, 6,103,286, 6,545,047, and 8,030,351 for disinfecting animal carcasses. In some embodiments, the composition of the present invention can be used in a method of treating animal carcasses to achieve a reduction of at least 50%, 90%, 99%, or 99.9% or more of the surface microbial community, said method comprising the step of treating said carcass with the composition of the present invention to reduce the microbial community, said composition comprising an effective antimicrobial amount, i.e., at least 1 part per million parts (ppm, parts per million by weight) of one or more peroxy-α-hydroxycarboxylic acids.

[0227] In other embodiments, the present invention relates to a method for treating animal carcasses to reduce the microbial community in the resulting cut meat, the method comprising the steps of: spraying an aqueous antimicrobial treatment composition onto the carcass at a temperature up to about 60°C and a pressure of at least 50 psi, maintaining a contact time of at least 5 seconds, the antimicrobial composition comprising an effective antimicrobial amount, i.e., at least 1 ppm of one or more carboxylic acids, percarboxylic acids, or mixtures thereof, and the first and second stabilizers described above; and achieving at least one log 10 The microbial community is reduced. High-temperature and low-temperature treatment methods can be used for the use of animal carcasses.

[0228] In other embodiments, the present invention relates to a method for treating animal carcasses to reduce the microbial community in the resulting cut meat, the method comprising the steps of: placing the animal carcass in a chamber at atmospheric pressure; filling the chamber with condensed steam containing an antimicrobial composition, for example, a diluted composition of the present invention, for a short period of time; and rapidly venting and cooling the chamber to prevent browning of the meat; wherein the duration of the steam heat treatment may be from about 5 seconds to about 30 seconds, and the chamber temperature may reach from about 50°C to about 93°C.

[0229] Antimicrobial compositions can be applied in various ways to achieve close contact with each potential microbial contaminant placement. For example, they can be sprayed onto carcasses or the carcasses can be immersed in the composition. Other methods include applying foaming compositions and thickening or gelling compositions. Methods of application for treating microbial contamination on carcasses can be applied at both high and low temperatures. If desired, vacuum and / or light treatment can be included during the application of the antimicrobial composition. Heat treatment can also be applied before, during, or after the application of the antimicrobial composition.

[0230] A preferred spraying method for treating carcasses with the diluted composition of the present invention includes spraying the carcass with an aqueous sprayer at a pressure of about 50 psi to 500 psi gauge pressure and a temperature below about 60°C, wherein the sprayer contains an effective antimicrobial amount of carboxylic acid, an effective antimicrobial amount of peroxycarboxylic acid, or a mixture thereof, and the first and second stabilizers described above. These sprayers may also contain an effective portion of a peroxide compound (such as hydrogen peroxide) and other components (such as multivalent chelating agents). The high-pressure spraying action of the water treatment can further reduce such populations on the carcass surface by removing microbial communities through a combination of the mechanical action of the sprayer and the chemical action of the antimicrobial material.

[0231] All pressures are in psig (or psi gauge pressure). In some embodiments, the distinction between the “biocidal” and “bioinhibitory” activities of the antimicrobial agent, the definition describing the degree of efficacy, and the official laboratory protocol used to measure this efficacy are important considerations for understanding the relevance of the antimicrobial agent in the composition. Antimicrobial compositions can affect two types of microbial cell damage. The first is a truly lethal, irreversible effect, resulting in the complete destruction or incapacitation of the microbial cell. The second type of cell damage is reversible, so that the organism can reproduce again if the agent is not present. The former is called bactericidal, and the latter is called bacteriostatic. By definition, disinfectants and bactericides are agents that provide antimicrobial or bactericidal activity and can achieve a reduction of at least five times (i.e., five log10 reductions) in the microbial population after a 30-second contact time (see AOAC Method 960.09).

[0232] Industry application methods

[0233] The methods of this invention can be used in the methods, processes, or procedures described and / or claimed in U.S. Patent Nos. 8,017,409 and 8,236,573. In some embodiments, the methods of this invention can be used in a variety of domestic or industrial applications, for example, to reduce populations of microorganisms or viruses on or in objects or in water. The peroxyhydroxycarboxylic acid compositions of this invention can be applied in 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 having smooth, irregular, or porous morphologies. Suitable hard surfaces include, for example, architectural surfaces (e.g., floors, walls, windows, sinks, tables, counters, and signs); tableware; 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 operating room linens and clothing; soft-surface medical or surgical instruments and devices; and soft-surface packaging. These soft surfaces can be made from a variety of materials, including, for example, paper, fibers, woven or nonwoven fabrics, soft plastics, and elastomers. Diluted (or used) compositions can also be applied to soft surfaces such as food and skin (e.g., hands). Diluted (or used) compositions can be used as foaming or non-foaming environmental disinfectants or bactericides.

[0234] In other embodiments, the peroxyhydroxycarboxylic acid composition of the present invention may be included in products such as sterilizing agents, disinfectants, disinfectants, preservatives, deodorants, antiseptics, fungicides, bactericides, yeast killers, sporicides, viricides, detergents, bleach, hard surface cleaners, hand soaps, anhydrous hand sanitizers, and pre- or post-operative disinfection solutions.

[0235] In other embodiments, the peroxyhydroxycarboxylic acid composition of the present invention can also be used in veterinary products such as mammalian skin treatments, or in products for disinfecting or sterilizing animal enclosures, pendants, watering stations, and veterinary treatment areas (such as examination tables and operating rooms). The peroxyhydroxycarboxylic acid composition can also be used in antimicrobial foot baths for livestock or humans.

[0236] In other embodiments, the method of the present invention can be used to reduce populations of pathogenic microorganisms, such as pathogens of humans, animals, etc. Exemplary pathogenic microorganisms include fungi, molds, bacteria, spores, and viruses, such as Staphylococcus aureus, Escherichia coli, Streptococcus spp., Legionella spp., Pseudomonas aeruginosa, Mycobacterium spp., tuberculosis, bacteriophages, etc. Such pathogens can cause a variety of diseases and symptoms, including mastitis or milking disorders in other mammals, tuberculosis, etc. The method of the present invention can be used to reduce microbial populations on the skin or other external or mucous membrane surfaces of animals. Additionally, the method of the present invention can be used to kill pathogenic microorganisms that are spread by means of water, air, or surface substrate transfer. In some applications, the compositions of the present invention only need to be applied to the skin, other external or mucous membrane surfaces, water, air, or surfaces of animals.

[0237] In other embodiments, the method of the present invention can also be used for food and plant species to reduce surface microbial communities; for processing sites of such food and plant species; or for treating process water around such sites. For example, the method of the present invention can be used in food transport lines (e.g., belt sprayers); feed hoppers and handwashing trays; food storage facilities; anti-corrosion air circulation systems; refrigeration and cooling equipment; beverage coolers and heaters, scalding machines, cutting boards, third-tank areas, and meat coolers or scalding devices. The method of the present invention can be used to treat transport water, such as that found in water tanks, pipeline transport, cutters, slicers, scalding devices, distillation systems, washing machines, etc. Specific foods that can be treated by the method of the present invention include eggs, meat, seeds, leaves, fruits, and vegetables. Specific plant surfaces include harvested and growing leaves, roots, seeds, peels or shells, stems, stalks, tubers, bulbs, fruits, etc. The method of the present invention can also be used to treat animal carcasses to reduce levels of pathogenic and non-pathogenic microorganisms.

[0238] In other embodiments, the method of the present invention can be used to clean or disinfect containers, processing facilities, or equipment in the food service or food processing industry. The method of the present invention can be used for food packaging materials and equipment, including cold or hot aseptic packaging. Examples of processing facilities where the method of the present invention can be employed include dairy production lines, continuous brewing systems, food processing lines such as pumpable food systems, and beverage production lines. Food serving dishes can be sterilized using the method of the present invention. For example, the method of the present invention can also be used on or within dishwashing machines, tableware, bottle washers, bottle coolers, heaters, third-tank washers, cutting areas (e.g., water jets, slicers, cutters, and saws), and egg washers. Particularly treatable surfaces include packaging such as cartons, bottles, films, and resins; tableware such as glasses, plates, utensils, pots, and pans; dishwashers; 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 dairy products such as milk, cheese, and ice cream); and transport 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.

[0239] In other embodiments, the method of the present invention can also be used on or in other industrial equipment and other industrial process flows, such as heaters, cooling towers, boilers, distilled water, rinsing water, aseptic packaging washing water, etc. The method of the present invention can also be used to treat microorganisms and odors in recreational water, such as swimming pools, hot springs, recreational water tanks, water slides, fountains, etc.

[0240] In other embodiments, filters containing the peroxyhydroxycarboxylic acid composition of the present invention can be used to reduce microbial communities in air and liquids. Such filters can be used to remove waterborne and airborne pathogens, such as Legionella.

[0241] In other embodiments, the method of the present invention can be used to reduce populations of microorganisms, fruit flies, or other insect larvae on drains or other surfaces.

[0242] In other embodiments, the method of the present invention may also be employed by the following steps: immersing the food processing equipment in the peroxyhydroxycarboxylic acid composition or solution of the present invention for a sufficient time to sterilize the equipment, and wiping or draining excess composition or solution from the equipment. The method of the present invention may also be further employed by the following steps: spraying or wiping the food processing surface with the peroxyhydroxycarboxylic acid composition or solution, keeping the surface moist for a sufficient time to sterilize the surface, and removing excess composition or solution by wiping, vertical draining, vacuum treatment, etc.

[0243] In other embodiments, the method of the present invention can also be used to disinfect hard surfaces, such as machine-type equipment, utensils, tableware, healthcare equipment or tools, and other hard surfaces. The method of the present invention can also be used to disinfect contaminated clothing or fabrics. The peroxyhydroxycarboxylic acid composition can be brought into contact with any contaminated surface or article at a usage temperature in the range of about 4°C to 60°C, effectively disinfecting, sterilizing, or sterilizing the surface or article for a period of time. For example, the peroxyhydroxycarboxylic acid composition can be added to the wash water or rinse water of a washing machine and brought into contact with the contaminated fabric for a sufficient time to disinfect the fabric. Excess composition can be removed by rinsing or centrifuging the fabric.

[0244] In other embodiments, the peroxyhydroxycarboxylic acid composition of the present invention can be applied to microorganisms or to soiled or clean surfaces using various methods. These methods can be operated on an object, on a surface, inside a body, or in a stream of water or gas by contacting an object, surface, body, or flow with the diluted (or used) composition. Contact can include any of a variety of methods for applying the composition, such as spraying the composition, immersing an object in the composition, foaming or gelling the object with the composition, or combinations thereof.

[0245] In other embodiments, the peroxyhydroxycarboxylic acid composition of the present invention can be used for bleaching.

[0246] In other embodiments, further hard surface cleaning applications of the peroxyhydroxycarboxylic acid compositions of the present invention include cleaning-in-place (CIP) systems, cleaning-out-of-place (COP) systems, washer-stain removers, sterilizers, textile washing machines, ultrafiltration and nanofiltration systems, and indoor air filters. COP systems may include easily accessible systems such as wash tubs, soaking containers, mop buckets, water tanks, washing basins, automotive parts washers, non-continuous intermittent washing machines and systems, etc.

[0247] The concentration of peroxyhydroxycarboxylic acid and / or hydrogen peroxide in the peroxyhydroxycarboxylic acid compositions of the present invention can be monitored in any suitable manner. In some embodiments, the concentration of peroxyhydroxycarboxylic acid and / or hydrogen peroxide in the peroxyhydroxycarboxylic acid and / or hydrogen peroxide compositions can be monitored using kinetic assay procedures, such as the exemplary procedures disclosed in U.S. Patent Nos. 8,017,409 and 8,236,573. When using, for example, buffered iodide reagents to distinguish the concentrations of the two analyte compounds in the presence of both peroxyhydroxycarboxylic acid and hydrogen peroxide in the composition used, this can be achieved by utilizing the difference in reaction rates between peroxyhydroxycarboxylic acid and hydrogen peroxide. The monitor can also determine the concentration of peroxyhydroxycarboxylic acid and / or hydrogen peroxide in the presence of other additional components, such as acidifiers, one or more stabilizers, nonionic surfactants, semi-polar nonionic surfactants, anionic surfactants, amphoteric / ampholytic surfactants, adjuvants, solvents, additional antimicrobial agents, or other components that may be present in the composition used.

[0248] Methods for treating biofilms

[0249] In another aspect, the present invention relates to a method for treating biofilms, the method comprising contacting a biofilm on a surface with an effective amount of peroxyhydroxycarboxylic acid for a sufficient duration to stabilize, reduce and / or remove the microbial community in and / or on the treated biofilm, or to stabilize, reduce and / or remove the biofilm on the surface.

[0250] The method of the present invention can be used to treat biofilms in any suitable location or environment. In some embodiments, the method of the present invention can be used to treat biofilms located on or within human environments, such as those located in or within shower rooms or spaces, water pipes, sewage pipes, floors, counters, or parts of the human body. For example, the method of the present invention can be used to treat biofilms located on or within dental plaque, a part of the urinary tract, a part of the middle ear, or a part of the gums. In other embodiments, the method of the present invention can be used to treat biofilms located on or within cooling or heating water systems. In still other embodiments, the method of the present invention can be used to treat biofilms located on or within engineering systems, such as pipelines in the oil and gas industry. In still other embodiments, the method of the present invention can be used to treat biofilms located on or within vehicles, such as automobiles, boats, or ships. In still other embodiments, the method of the present invention can be used to treat biofilms located on or within plants. In still other embodiments, the method of the present invention can be used to treat biofilms located on or within consumer products, such as contact lenses or a pair of eyeglasses. In still other embodiments, the method of the present invention can be used to treat biofilms located on or within medical devices, such as implantable medical devices. Exemplary implantable medical devices include catheters, artificial heart valves, or intrauterine devices. In other embodiments, the method of the present invention can be used to treat biomembranes located on or within a membrane, such as an ultrafiltration (UF) membrane.

[0251] The method of the present invention can use any suitable concentration of peroxyhydroxycarboxylic acid. In some embodiments, the method of the present invention may include reacting a biofilm on a surface with about 10 ppm to about 1,000 ppm of peroxyhydroxycarboxylic acid, for example, 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm, or 2,000 ppm to 300 ppm. Peroxyhydroxycarboxylic acid contact at 00 ppm, 300 ppm to 350 ppm, 350 ppm to 400 ppm, 400 ppm to 450 ppm, 450 ppm to 500 ppm, 500 ppm to 550 ppm, 550 ppm to 600 ppm, 600 ppm to 650 ppm, 650 ppm to 700 ppm, 700 ppm to 750 ppm, 750 ppm to 800 ppm, 800 ppm to 850 ppm, 850 ppm to 900 ppm, 900 ppm to 950 ppm or 950 ppm to 1,000 ppm.

[0252] The method of the present invention may include contacting a biofilm on a surface with an effective amount of peroxyhydroxycarboxylic acid for any suitable duration. In some embodiments, the method of the present invention may include contacting a biofilm on a surface with an effective amount of peroxyhydroxycarboxylic acid for about 1 minute to about 10 hours, for example, about 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours. In one aspect, the contact occurs for a period of time prior to the degradation of the peroxyhydroxycarboxylic acid composition.

[0253] The method of the present invention can be used to treat biofilms made from or derived from any suitable microbial community. In some embodiments, the method of the present invention can be used to treat biofilms made from or derived from prokaryotic microbial communities, such as bacterial or archaea communities. Exemplary bacterial communities include *Pseudomonas aeruginosa*, *Streptococcus mutans*, *Streptococcus pneumoniae*, *Legionella*, or *Bacillus* communities, such as *Bacillus subtilis* sp. spores. In other embodiments, the method of the present invention can be used to treat biofilms made from or derived from eukaryotic microbial communities, such as protozoan or fungal communities. In still other embodiments, the method of the present invention can be used to treat biofilms made from or derived from viral communities.

[0254] High-level sterilization methods, such as reprocessing of endoscopes and other instruments.

[0255] In another aspect, various methods of treatment using peroxyhydroxycarboxylic acids generated according to the method of the invention can be used for high-level disinfectant applications, including the sterilization of medical devices. The in-situ formation rate of the peroxyhydroxycarboxylic acid is particularly advantageous for applications used for high-level disinfection. The disinfectant is generated in situ and supplied on demand. Advantageously, the method of using high-level disinfectants does not require the high pressure and high temperature required to achieve sterility. In one embodiment, the surface to be treated (such as an instrument) is contacted with an effective amount of peroxyhydroxycarboxylic acid for a sufficient time to stabilize, reduce, and / or remove the microbial community in and / or on the treated surface, or to stabilize, reduce, and / or remove dirt and microorganisms on the surface.

[0256] In one aspect, the method allows for the reuse or reuse of surfaces (such as instruments) by sterilizing and / or disinfecting them. Exemplary surfaces (including instruments) suitable for reprocessing according to the invention include any instruments that can benefit from cleaning with the compositions according to the invention, including medical or dental instruments or devices. Particularly suitable instruments include, but are not limited to, diagnostic instruments, endoscopes (e.g., endoscopes, stethoscopes, and arthroscopy) and related equipment, or combinations thereof.

[0257] The method of the present invention can use any suitable concentration of peroxyhydroxycarboxylic acid. In some embodiments, the method of the present invention may include subjecting the surface to a concentration of peroxyhydroxycarboxylic acid of about 10 ppm to about 1,000 ppm, such as 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm. Contact with peroxyhydroxycarboxylic acids at concentrations of 300 ppm to 350 ppm, 350 ppm to 400 ppm, 400 ppm to 450 ppm, 450 ppm to 500 ppm, 500 ppm to 550 ppm, 550 ppm to 600 ppm, 600 ppm to 650 ppm, 650 ppm to 700 ppm, 700 ppm to 750 ppm, 750 ppm to 800 ppm, 800 ppm to 850 ppm, 850 ppm to 900 ppm, 900 ppm to 950 ppm, or 950 ppm to 1,000 ppm. In a preferred aspect, the contact method provides about 10 ppm to about 500 ppm of peroxyhydroxycarboxylic acids to the in-situ generated high level of bactericide within minutes.

[0258] The method of the present invention may include contacting a surface with an effective amount of peroxyhydroxycarboxylic acid for any suitable duration. In some embodiments, the method of the present invention may include contacting a surface with an effective amount of peroxyhydroxycarboxylic acid for about 1 minute to about 1 hour, for example, about 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes or longer. In one aspect, the contact time is preferably less than 10 minutes, more preferably less than 5 minutes. In another aspect, the contact occurs for a period of time before the peroxyhydroxycarboxylic acid composition degrades.

[0259] The method of the present invention can be used to treat instrument reprocessing surfaces contaminated with any suitable microbial community. In some embodiments, the method of the present invention can be used to treat surfaces made of or derived from prokaryotic microbial communities, such as bacterial or archaea communities. Exemplary bacterial communities include Pseudomonas aeruginosa, Streptococcus mutans, Streptococcus pneumoniae, Legionella, or Bacillus communities, such as Bacillus sp. spores. In other embodiments, the method of the present invention can be used to treat surfaces made of or derived from eukaryotic microbial communities, such as protozoan or fungal communities. In still other embodiments, the method of the present invention can be used to treat surfaces made of or derived from viral communities.

[0260] The method of the present invention can be performed within any suitable temperature range. In some embodiments, the method of the present invention can be performed at temperatures or under ambient conditions ranging from about 20°C to about 40°C, for example, from about 20°C to 25°C, 25°C to 30°C, 30°C to 35°C, or 35°C to 40°C. The method of the present invention is preferably performed at a near-neutral pH of the peroxyhydroxycarboxylic acid composition to avoid corrosion of the treated surface. In some embodiments, the pH is about 4 to 9, 4.5 to 5.5, and preferably 5.5 to 6.5. In a preferred aspect, the method is performed at a near-neutral pH, thereby reducing and / or eliminating the risk of corrosion to the treated surface.

[0261] Advantageously, high-level sterilization methods are suitable for the in-situ generation of peroxyhydroxycarboxylic acids under conditions suitable for sterilization. In one aspect, the peroxyhydroxycarboxylic acid is generated and used within minutes of application.

[0262] Methods of treating targets or surfaces using saturated wiping agents

[0263] In another aspect, various methods of treatment using the peroxyhydroxycarboxylic acid generated according to the method of the invention can be delivered using saturated wipes. Disposable substrates are commonly used for cleaning applications. Suitable substrates include woven fabrics and nonwoven fabrics, and various combinations thereof. Such substrates can be impregnated with compositions that generate peroxyhydroxycarboxylic acids according to the invention, or impregnated with the generated peroxyhydroxycarboxylic acid when the substrate is used for application. The resulting disinfectant products made from such impregnated substrates are considered a convenient and practical means of cleaning surfaces, as disclosed in, for example, U.S. Patent Publication No. 2014 / 0271762, which is incorporated herein by reference in its entirety.

[0264] In one embodiment, the microfiber product herein is used to deliver peroxyhydroxycarboxylic acids for consumer cleaning, such as those constructed from split conjugated fibers of polyester and polyamide, or optionally in a polyamide-free form. In one aspect, the peroxyhydroxycarboxylic acid generated according to the method of the invention is used to coat a substrate of a contact surface. In another aspect, a portion of the reagent for generating the peroxyhydroxycarboxylic acid composition is impregnated into the substrate, and then the substrate is brought into contact with the remaining reagent to generate the peroxyhydroxycarboxylic acid composition upon user use.

[0265] The peroxyhydroxycarboxylic acid (or reagent) coated on the substrate may optionally contain one or more additives, such as fragrances, dyes, pigments, emollients, bleaching agents, antistatic agents, antiwrinkle agents, deodorants / odor removers, UV protectants, insect repellents, acidifiers, mildew removers, antiallergens, and mixtures thereof.

[0266] In one embodiment, the disinfectant is applied to a substrate for a duration of approximately 20 seconds, 30 seconds, 45 seconds, 1 minute, 2 minutes, 5 minutes, 10 minutes up to approximately 7 days. The pre-coated wipes can be sold in sealed containers. These pre-coated wipes can be exposed to the disinfectant along with the peroxyhydroxycarboxylic acid according to the invention for seconds, hours, to days, and preferably up to a week.

[0267] Methods for disinfection and sterilization of skin and surfaces

[0268] In another aspect, various methods can be employed for treatment with peroxyhydroxycarboxylic acids generated according to the method of the present invention to create skin disinfectants and bactericides, including methods for, for example, mastitis control. The in-situ formation rate of the peroxyhydroxycarboxylic acid is particularly advantageous for applications intended for skin disinfection. In one embodiment, the surface requiring the bactericide, including animal skin or other external surfaces or mucous membranes, is brought into contact with an effective amount of peroxyhydroxycarboxylic acid for a sufficient time to reduce and / or remove the microbial community on the treated surface.

[0269] The method of the present invention can disinfect the skin by applying a liquid, i.e., a solution, to the skin surface using any suitable concentration of peroxyhydroxycarboxylic acid. In some embodiments, the method of the present invention may include subjecting the surface to peroxyhydroxycarboxylic acid at concentrations from about 10 ppm to about 1,000 ppm, such as 10 ppm to 20 ppm, 20 ppm to 30 ppm, 30 ppm to 40 ppm, 40 ppm to 50 ppm, 50 ppm to 60 ppm, 60 ppm to 70 ppm, 70 ppm to 80 ppm, 80 ppm to 90 ppm, 90 ppm to 100 ppm, 100 ppm to 150 ppm, 150 ppm to 200 ppm, 200 ppm to 250 ppm, 250 ppm to 300 ppm. Contact with peroxyhydroxycarboxylic acids at concentrations of 300 ppm to 350 ppm, 350 ppm to 400 ppm, 400 ppm to 450 ppm, 450 ppm to 500 ppm, 500 ppm to 550 ppm, 550 ppm to 600 ppm, 600 ppm to 650 ppm, 650 ppm to 700 ppm, 700 ppm to 750 ppm, 750 ppm to 800 ppm, 800 ppm to 850 ppm, 850 ppm to 900 ppm, 900 ppm to 950 ppm, or 950 ppm to 1,000 ppm. In a preferred aspect, the contact method provides about 10 ppm to about 500 ppm of peroxyhydroxycarboxylic acids to the in-situ generated bactericide within minutes.

[0270] The method of the present invention may include contacting a surface with an effective amount of peroxyhydroxycarboxylic acid for any suitable duration. In some embodiments, the method of the present invention may include contacting a surface with an effective amount of peroxyhydroxycarboxylic acid for about 1 minute to about 1 hour, for example, about 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes or longer. In one aspect, the contact time is preferably less than 10 minutes, more preferably less than 5 minutes. In another aspect, the contact occurs for a period of time before the peroxyhydroxycarboxylic acid composition degrades.

[0271] The method of the present invention can be used to treat surfaces contaminated with any suitable microbial community, including skin. In some embodiments, the method of the present invention can be used to treat surfaces made of or derived from prokaryotic microbial communities, such as bacterial or archaea communities. Exemplary bacterial communities include communities of Staphylococcus aureus, Streptococcus agalactiae, Streptococcus isomalaciae, and Streptococcus lactis. The method is suitable for disinfecting common pathogens causing mastitis, including infectious and environmental pathogens. Infectious bacteria, such as Streptococcus agalactiae and Staphylococcus aureus, primarily colonize host tissue sites (such as mammary glands, teat canals, teat skin lesions, etc.) and are transmitted from one infected cow to another during milking. Environmental bacteria, typically streptococci, enterococci, and Escherichia coli, are usually present in the environment surrounding the cow from sources such as cow dung, soil, plant material, bedding, or water and are acquired through accidental contact with the animal during milking.

[0272] Methods for disinfecting skin surfaces can involve contacting the surface with an effective amount of a disinfectant composition through various application routes. In one aspect, the disinfectant composition can contact the surface by immersing the skin surface (e.g., a nipple) in a solution, spraying the solution onto the surface, or immersing it in foam generated by the solution. In a preferred aspect, methods for treating lactating animal nipples include applying an effective amount of the composition by immersing the nipple in a solution, spraying the solution onto the nipple, or immersing it in foam generated by the solution.

[0273] In a preferred aspect, the polyol includes glycerol, propylene glycol, sorbitol, polyglycerol, and mixtures thereof, which can be combined with the peroxyhydroxycarboxylic acid composition. In a preferred aspect, the surface is in contact with a disinfectant comprising a solution of a peroxyhydroxycarboxylic acid and a polyol comprising about 0.5% to about 50% by weight of the disinfectant. In a preferred aspect, the surface is in contact with a disinfectant comprising a solution of a peroxyhydroxycarboxylic acid and a polyol comprising about 1% to about 10% by weight of the disinfectant.

[0274] In some embodiments, the method of the present invention may further include contacting the surface with a peroxyhydroxycarboxylic acid composition further comprising a surface wetting agent. The surfactant or surfactant blend of the present invention may be selected from compatible water-soluble or water-dispersible nonionic surfactants or anionic surfactants; or mixtures of each or both types. Nonionic and anionic surfactants offer a wide range of commercial options at low cost; most importantly, they have excellent detergency—i.e., surface wetting. The surfactant or “wetting agent” is used to increase the penetrating activity of the penetrant of the present invention into tissue surfaces at risk of pathogens causing mastitis. Nonionic surfactants that can be used in the present invention are generally characterized by the presence of organic hydrophobic and organic hydrophilic groups, and are typically generated by the condensation of an organic aliphatic, alkyl aromatic, or polyoxyolefin hydrophobic compound with, conventionally, ethylene oxide or its polyhydrated form, or the hydrophilic basic oxidized portion of polyethylene glycol. In fact, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can be condensed with ethylene oxide or its polyhydrated adduct or a mixture thereof with an alkyl oxide (such as propylene oxide) to form a nonionic surfactant. The length of the hydrophilic polyoxyethylene moiety condensed with any particular hydrophobic compound can be easily adjusted to produce a water-dispersible or water-soluble compound with a desired balance between hydrophilic and hydrophobic properties.

[0275] Also useful are surfactants classified as anionic because the hydrophobic component has a negative charge; or surfactants in which the hydrophobic portion of the molecule is uncharged unless the pH is raised to neutral or higher (e.g., carboxylic acids). Carboxylates, sulfonates, sulfates, and phosphates are polar (hydrophilic) dissolving groups present in anionic surfactants. Among the cations (counterions) associated with these polar groups, sodium, lithium, and potassium are water-soluble and are most preferred in the compositions of the present invention. Examples of suitable synthetic water-soluble anionic compounds are alkali metal (such as sodium, lithium, and potassium) salts or alkyl mononuclear aromatic sulfonates, such as alkylbenzene sulfonates containing about 5 to about 18 carbon atoms in a straight or branched alkyl group, such as alkylbenzene sulfonates or alkylnaphthalene sulfonates, dialkylnaphthalene sulfonates, and salts of alkoxylated derivatives. Other anionic detergents are olefin sulfonates, comprising long-chain olefin sulfonates, long-chain hydroxyalkane sulfonates, or mixtures of olefin sulfonates and hydroxyalkane sulfonates, as well as alkyl poly(ethylene oxy) ether sulfonates. It also includes alkyl sulfates, alkyl poly(ethylene oxy) ether sulfates, and aromatic poly(ethylene oxy) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 oxyethylene atoms per molecule).

[0276] On one hand, oxidation-sensitive or acid-hydrolysis-sensitive surfactants are used as wetting agents. Exemplary oxidation-sensitive surfactants include polyethylene glycol-based surfactants, polyglycerol, polyol sugar-based surfactants, and mixtures thereof. Exemplary surfactants include alcohol ethoxylates, EO / PO copolymers exemplified by poloxamer, glycerol and polyglycerol ester surfactants, and surfactants derived from... Examples of surfactants include polysorbate surfactants and glycosyl surfactants, such as those exemplified by alkyl polyglucosides. Surfactants. Further disclosures of suitable wetting agents are set forth in U.S. Patent No. 6,749,869 and Reissue Patent No. RE41279E, each of which is incorporated herein by reference in its entirety. Advantageously, the bactericidal composition is stable with the in-situ generated peroxyhydroxycarboxylic acid composition, unlike conventional food- or skin-friendly surfactants, which are unstable in conventionally balanced or concentrated environments with high oxidizing properties or very low pH.

[0277] In some embodiments, the method of the invention may further include contacting the surface with a peroxyhydroxycarboxylic acid composition further comprising a dye or colorant. In one aspect, the peroxyhydroxycarboxylic acid of the bactericide composition provides a dye or colorant to provide a mechanism for color marking the bactericide composition. Advantageously, the in-situ generated peroxyhydroxycarboxylic acid does not exhibit the storage stability and incompatibility with conventional colorant formulations experienced by conventional equilibrium and concentrate peracid systems. In one aspect, the dye or colorant is a food and / or pharmaceutical additive dye. In one aspect, the dye or colorant is not a color-changing or indicator system. In one aspect, the complexed iodine provides the advantage of color development, i.e., easy visibility when applied to the skin. Other antimicrobial agents do not possess this characteristic; therefore, the composition may contain a water-soluble or dispersible colorant (dye or pigment or mixture) that causes the composition to develop color, thereby creating a sharp contrast with the teat skin and allowing herd managers to visually identify treated teats.

[0278] In another aspect, the bactericidal composition may contain any number of optional ingredients. Typically, according to the invention, this composition may contain a formulation adjuvant that contributes to the application of the invention in terms of physical and chemical stability, barrier film formation, maintenance of skin or nipple health, performance, physical form, and manufacturing process anesthetic. Of course, these functions can be achieved solely by the already described compositional components or admixtures thereof; however, situations may arise where additional effects are required in formulation, application, or performance, which can be achieved by introducing one or more additional inorganic or organic agents and mixtures thereof into the composition.

[0279] The composition may optionally include pharmaceuticals, such as sunscreens (e.g., para-aminobenzoic acid) and healing agents (e.g., allantoin or urea), to provide therapeutic effects and stimulate the formation of new tissue; preservatives, such as methylparaben, propylparaben, sorbic acid, and benzoic acid or their salts, to inhibit bacterial growth and prolong shelf life; antioxidants, such as BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), TBHQ (tert-butylhydroquinone), or propyl gallate, to delay oxidative or hydrolytic degradation; multivalent chelating agents, such as aminopolyacetates, polyphosphonates, aminopolyphosphonates, polycarboxylates, and condensed phosphates; dispersants, disintegrants, or suspending agents with polyelectrolyte properties, such as polyacrylates and similar homopolymer or copolymer polycarboxylates; and manufacturing processing agents, such as defoaming additives for promoting blending and mixing.

[0280] Various ingredients suitable for skin disinfection, including those for the control and treatment of mastitis, may be included in the compositions described herein. This list is not intended to be exhaustive, and other optional ingredients well-known in the art may also be used in the compositions, even if not listed. The examples are not intended to be limiting in any way. In some cases, some adjuvants in a single adjuvant may overlap with other classes. Adjuvants used should be selected to avoid interfering with the antimicrobial activity of the composition and to avoid physical or chemical instability of the product.

[0281] The method of the present invention can be performed within any suitable temperature range as disclosed herein. Typically, the pH for the control and treatment of bovine mastitis can vary from as low as about pH 2.0 to as high as about 11.0, depending primarily on the choice of antimicrobial agent incorporated into the composition, as optimal efficacy usually occurs within a specific narrow pH range. Therefore, buffers or systems are selected accordingly. In some embodiments, the pH is about 2 to 9, 3 to 8, and preferably 4 to 7.

[0282] Methods for treating and / or bleaching clothes

[0283] In one aspect, peroxyhydroxycarboxylic acid compositions are suitable for treating laundry stains and cleaning products, such as textiles, which are soiled. In another aspect, additional functional ingredients, including those listed in U.S. Publication No. 2013 / 0247308 (which is incorporated herein by reference in its entirety), may optionally be combined with the peroxyhydroxycarboxylic acid compositions disclosed herein for laundry applications. The compositions of the present invention can be combined with additional functional ingredients, alone and / or with additional detergents, for removing stains from any conventional fabrics, including but not limited to cotton, cotton-polyester blends, wool, and polyester. The compositions can be used in any article or article made of or including textile materials, woven fabrics, nonwoven fabrics, and knitted fabrics. Textile materials may include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers (such as nylon), acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. The fibers may be treated or untreated.

[0284] Clothes can be processed in a washing machine (such as a washer-spinner or tunnel washing machine). A washer-spinner that can be used includes: a drum having an interior for containing clothes, an electric motor configured and arranged to rotate the drum, a water inlet for introducing water into the drum, a chemical inlet for introducing chemicals into the drum, a drain outlet for allowing fluid to drain from the drum, and a processing unit configured to operate the washer-spinner. The processing unit can be configured to provide a washing cycle for washing clothes with a cleaning and disinfecting composition solution of a first component, a rinsing cycle for removing at least a portion of the detergent solution, and a processing cycle for treating clothes with a bleaching composition of a second component.

[0285] In conventional industrial and / or commercial laundry applications, peroxyhydroxycarboxylic acid compositions can be used to remove dirt from fabrics, both inside and outside the washing machine, when a method for removing dirt is employed in the laundry process. In some respects, when the composition is used outside the washing machine, it is used as a concentrated formulation. In other respects, when the composition is used inside the washing machine, it is used as a diluted (or highly diluted) formulation, such as in the washing liquid of the washing machine, to remove dirt from fabrics.

[0286] In conventional industrial laundry facilities, textile materials may undergo several treatment steps in industrial-scale washing machines to provide cleaning. Exemplary treatment steps include a pre-soaking or pre-washing step, a washing step (e.g., saponification and foaming steps), a rinsing step for removing dirt containing detergent solution, a bleaching step (alone or in combination with the washing step), several optional rinsing steps for removing the bleaching composition, an optional acidification step for adjusting the pH, a softening step, and an extraction step (typically involving rotating the fabric to remove water). The compositions of the present invention can be used in such exemplary conventional pre-washing or pre-soaking steps, washing steps, and / or optionally in washing treatment steps different from such conventional processes. Furthermore, the compositions of the present invention can be used with a variety of washing machines, including industrial, commercial, and / or consumer washing machines (e.g., residential and / or domestic washing machines).

[0287] The method for treating clothing according to the invention can be provided as part of a general method for cleaning clothing according to the invention. That is, as part of a laundry cleaning operation, the compositions of the invention can be used alone to treat articles, such as textiles, or in combination with a conventional detergent suitable for the article to be treated. The clothing cleaning method according to the invention can include removing dirt, removing stains or the appearance of stains, and / or reducing microbial communities. The compositions of the invention can be used with conventional detergents in a variety of ways. Such formulations can include, for example, detergents used for pre-washing or pre-soaking steps and / or saponification / foaming / bleaching steps. In other embodiments, the compositions of the invention can be used as an additive separate from conventional detergents to treat articles. The compositions can be provided in the form of a concentrate, which is diluted with water to provide a working solution. Alternatively, the compositions can be provided in the form of a working solution (diluted with water). When used as a separate additive, the compositions of the invention can contact the article to be treated at any time. For example, the compounds and compositions of the invention can contact the article before, after, or substantially simultaneously with the selected detergent.

[0288] The solution can be used to wash articles. In one aspect, the composition can be applied to a pre-washing step (e.g., heating to about 40°C to 50°C). In some aspects, the heated pre-washing step uses a low water level. Subsequently, excess grease and oil are removed from the surface of the article, and then the article can be thoroughly washed (i.e., the washing step) using detergent, bleach, and / or alkaline builders in a main or conventional foaming step. In these embodiments, the composition contacts the article before it comes into contact with a selected detergent, such as in a pre-soaking or pre-washing case, wherein the article is first contacted with the composition of the present invention to emulsify dirt on the substrate fabric. This step may include a contact time of at least several minutes. This step may optionally include using a builder or component composition to provide an alkalinity source, such as increasing the pH from neutral to alkaline, including, for example, a pH of at least 10, or at least 11 or greater. This step can be carried out over a wide range of temperatures.

[0289] In one embodiment, the composition provides a suitable bleaching step and can be combined with additional bleaching and / or antimicrobial steps. This bleaching and antimicrobial step can occur after or before the steps of washing clothes with the composition of the present invention and draining and / or rinsing the composition solution from the clothes. In other applications, it is desirable that the bleaching and antimicrobial steps be performed simultaneously with the washing step. It is anticipated that combining the washing step using the emulsified composition of the present invention with the bleaching and antimicrobial step may be advantageous in cases of relatively light soiling. That is, the bleaching and antimicrobial step may include a soil removal step and / or this step may be performed before or after the soil removal step.

[0290] In one aspect of the invention, the compositions are particularly suitable for use as additive compositions in conventional washing / laundry processes. For example, as disclosed herein, the compositions can be used as bleaching agents or synergists in conventional foam baths (conventional washing / laundry processes) that already contain a main detergent, alkalinity, and / or possibly a bleaching agent. Such exemplary processes are disclosed in the description of the invention. Further description of suitable laundry washing methods employing the compositions of the invention is set forth, for example, in U.S. Patent Application No. 12 / 726,073, which is incorporated herein by reference in its entirety.

[0291] On one hand, the peroxyhydroxycarboxylic acid composition is used at the pH of the solution, such as in the drum of a washer-spinner or in a tunnel washing machine, at a pH of about 7 to about 14, about 7 to about 13, about 7 to about 12, about 7 to about 11, about 7 to about 10, about 7 to about 9 or about 7 to about 8.

[0292] Example

[0293] The embodiments of the present invention are further limited to 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 illustrated and 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 also intended to fall within the scope of the appended claims.

[0294] Example 1

[0295] Perhydrolysis of lactide from solid peroxy-α-hydroxycarboxylic acid composition. US Publication No. 202I / 0238135 has shown the kinetics of perhydrolysis of lactide to produce peroxylactic acid, wherein the perhydrolysis uses... Figure 1 The reaction is carried out using liquid precursors as depicted in the figure and shown in Table 2, wherein lactide reacts with hydrogen peroxide under weakly alkaline conditions to rapidly generate peroxylactic acid.

[0296] Table 2

[0297]

[0298]

[0299] The formation of peroxylactic acid from the liquid precursor was evaluated, with an initial measurement point of 3 minutes. However, the reaction was almost instantaneous, and peroxylactic acid was generated upon contact with the reagent under the stated conditions. The depicted % PLA illustrates the reaction providing a concentrated chemical solution, which can then be diluted for the desired application. As shown, the rapid and substantial formation of PLA and lactic acid resulted in a decrease in the pH of the concentrated solution.

[0300] Similarly, the kinetics of the perhydrolysis of glycolide to produce peroxyglycolic acid further demonstrate the effectiveness of using liquid precursors. Figure 2 The reaction described in the figure and shown in Table 3 involves lactide reacting with hydrogen peroxide under weakly alkaline conditions to rapidly generate peroxylactic acid.

[0301] Table 3

[0302]

[0303] Advantageously, as shown in Table 3, glycolide reacts with hydrogen peroxide and a caustic base (sodium hydroxide) to rapidly generate perglycolic acid. In this example, the initial measurement point for perglycolic acid formation was 1 minute, which confirmed that the reaction is almost instantaneous and that perglycolic acid is generated upon contact with the reagent.

[0304] Following the successful hydrolysis of lactide and glycolide, according to Figure 1 Using the same reaction protocol, but with the lactide precursor, the solid compositions shown in Table 4 can be used to generate peroxylactic acid (PLA). The lactide precursor was formulated into solid pellets with citric acid and sodium percarbonate, and the solid peroxy-α-hydroxycarboxylic acid-forming composition was added to water for perhydrolysis to generate PLA. Advantageously, citric acid was used as a buffer and dispersant or disintegrant to provide effervescence, thereby dissolving the solid composition in water more quickly and initiating the PLA formation reaction. Reaction kinetics were evaluated by dissolving approximately 2.5 g of pellets (as shown in Table 4) in 500 mL of deionized water to measure PLA formation and pH over time.

[0305] Table 4

[0306] Sodium percarbonate 0.91 37.0 Citric acid 0.75 30.5 lactide 0.80 32.5 2.46 100

[0307] PLA formation was measured twice. Table 5 shows the first PLA formation kinetics, and Table 6 shows the second PLA formation kinetics using the same batch of tablets stored under ambient conditions for 9 months. The initial test point of 10 minutes provided time for the tablets to dissolve in water so that PLA formation could begin.

[0308] Table 5

[0309] 10 6.06 22.43 0.5500 130 30 5.95 21.90 0.9160 222 60 5.64 25.13 1.1180 236 90 5.41 29.53 1.2080 217 120 5.23 21.62 0.8240 202 150 5.11 18.99 0.6740 188 180 5.01 19.26 0.6180 170 210 4.93 22.46 0.646 152 240 4.87 20.90 0.574 146

[0310] Table 6

[0311]

[0312]

[0313] Example 2

[0314] Antimicrobial efficacy of peroxylactic acid. The antimicrobial efficacy of peroxylactic acid generated from the solid peroxy α-hydroxycarboxylic acid composition in Table 4 was evaluated against Staphylococcus aureus and Escherichia coli according to the conditions shown in Table 7, based on the US EPA Food Contact Suspension Test Protocol (AOAC 960.09).

[0315] Table 7. Test Parameters

[0316]

[0317] The efficacy of peroxylactic acid at various concentrations derived from the lactide precursor as described in Example 1 is shown in Tables 8 and 9, demonstrating the minor efficacy (logarithmic reduction) achieved from peroxylactic acid compositions at different concentrations and plate dilutions.

[0318] Table 8. Results of minimal efficacy against Staphylococcus aureus

[0319]

[0320] Table 9. Results of micro-efficacy against Escherichia coli

[0321]

[0322] Example 3

[0323] Antimicrobial efficacy of peroxylactic acid. The antimicrobial efficacy of peroxylactic acid generated from the solid peroxy-α-hydroxycarboxylic acid composition shown in Table 4 against Salmonella was evaluated in chicken carcasses compared to peracetic acid (PAA). Test conditions are shown in Table 10. PLA has a molecular weight of 106, and PAA has a molecular weight of 76; therefore, a molar equivalent base of 500 ppm PLA equals 359 ppm PAA.

[0324] Table 10

[0325]

[0326] The comparative efficacy of peracetic acid compared to various concentrations of perlactic acid derived from lactide precursors as described in Example 1 is shown in Table 11. This demonstrates at least equivalent microefficacy (logarithmic reduction) achieved from perlactic acid compositions of different concentrations and plate dilutions, as well as improved microefficacy from 1000 ppm perlactic acid. Data show that 1000 ppm performs better than 2000 ppm in specific meat tissues. Differences in testing can exist between different meat tissues, which is not uncommon.

[0327] Table 11

[0328]

[0329]

[0330] Example 4

[0331] Additional antimicrobial effects of peroxylactic acidThe efficacy of the added antimicrobial agent against Salmonella, Escherichia coli, Campylobacter, and Listeria was evaluated according to the US EPA Food Contact Suspension Test Protocol (AOAC 960.09) under the conditions shown in Table 12.

[0332] Table 12. Test Parameters

[0333]

[0334] The results are as follows Figure 3 As shown, this demonstrates the efficacy of PLA against a variety of microorganisms at low concentrations (down to 25 ppm). Furthermore, 100 ppm PLA provides a more than 7-fold log reduction against Listeria, while peracetic acid is known to require at least approximately 180 ppm to achieve a more than 7-fold log reduction against Listeria.

[0335] Example 5

[0336] The tablet stability of the PLA tablets was further evaluated. The tablets analyzed in Example 1 were small (2.4 g), and their small size made dimensional stability testing unreliable. However, visual appearance was evaluated over time to assess any detectable changes in tablet formation over storage time. Evaluations were performed for one year and two years, respectively. No detectable visual changes were observed in the tablets. In addition to visually inspecting the tablets to confirm stability, the dimensional stability of larger tablets or solids can also be measured.

[0337] The stability of tablets can also be quantified by the chemical properties of the reagents, as they are capable of spontaneous reactions. Therefore, the stability of tablets (or solids) can also be assessed by the ability or performance of the tablets to generate PLA after storage, as another quantifiable mechanism for confirming stability. This is illustrated in Example 1; Table 6 is a direct comparison of the PLA formation profiles of tablets after 9 months of storage, compared to Table 5. The presence of minor changes confirms tablet stability. In some embodiments, preferably at least about 50% or preferably at least about 80% of PLA (or peroxy-α-hydroxycarboxylic acid) formation is maintained.

[0338] It should be understood that although the invention has been described in conjunction with specific embodiments, the foregoing description is intended to illustrate rather than limit the scope of the invention, which is defined by 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.

[0339] As appropriate, features disclosed in the foregoing description or the appended claims or drawings (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 method for forming a peroxy α-hydroxycarboxylic acid from a peroxy α-hydroxycarboxylic acid forming composition, the method comprising: The contact step is any one of the following: (a) Contacting a solid peroxy-α-hydroxycarboxylic acid composition with a liquid, wherein the solid composition comprises a cyclic carboxylate diester of an α-hydroxycarboxylic acid, a basicity source, and a substance that generates hydrogen peroxide upon contact with the liquid, and forming a liquid containing the peroxy-α-hydroxycarboxylic acid and having a pH less than 8 within 5 minutes after the solid composition is contacted with the liquid; or (b) A cyclic carboxylic acid diester containing α-hydroxycarboxylic acid dissolved together is brought into contact with a liquid peroxy α-hydroxycarboxylic acid in a solvent to form a composition, which is then contacted with an alkalinity source and hydrogen peroxide, and a liquid containing the peroxy α-hydroxycarboxylic acid and having a pH less than 8 is formed within 5 minutes after the solution is contacted with the alkalinity source and hydrogen peroxide. as well as At least 1 ppm of the peroxy α-hydroxycarboxylic acid is formed within 1 minute of the start of the contact step.

2. The method according to claim 1, wherein the cyclic carboxylic acid diester has the following structure: R is an H or alkyl group.

3. The method according to claim 2, wherein the α-hydroxycarboxylic acid is lactic acid or glycolic acid, and wherein the cyclic carboxylic acid diester of the α-hydroxycarboxylic acid is the corresponding lactide or glycolide.

4. The method according to claim 1, wherein the alkalinity source comprises alkali metal carbonate, alkali metal percarbonate or alkali metal borate.

5. The method according to claim 1, wherein the substance generating hydrogen peroxide comprises at least one of alkali metal percarbonate, alkali metal perborate, urea peroxide, or peroxide salt.

6. The method according to claim 5, wherein the substance generating hydrogen peroxide is sodium percarbonate, sodium perborate, calcium peroxide, magnesium peroxide, PVP peroxide, or urea peroxide.

7. The method according to claim 1, wherein the alkalinity source and the substance that generates hydrogen peroxide are single reagents in the solid composition.

8. The method according to claim 7, wherein the single reagent is sodium percarbonate.

9. The method of claim 1, wherein the reagent is contacted to form a liquid solution containing 0.1 ppm to 100,000 ppm of the peroxy α-hydroxycarboxylic acid, and / or wherein the peroxy α-hydroxycarboxylic acid has a vapor pressure of less than 1 kPa at 20°C.

10. The method of claim 9, wherein the reagent is contacted to form a liquid solution containing 10 ppm to 50,000 ppm of the peroxy-α-hydroxycarboxylic acid.

11. The method of claim 1, wherein the liquid comprising the peroxy α-hydroxycarboxylic acid contains at least 10 ppm of peroxy α-hydroxycarboxylic acid within 1 minute of contact between the solid composition and the liquid.

12. The method of claim 1, wherein the liquid comprising the peroxy α-hydroxycarboxylic acid contains at least 100 ppm of peroxy α-hydroxycarboxylic acid within 5 minutes of contact between the solid composition and the liquid.

13. The method of claim 1, wherein the reagent is in contact with ambient conditions, or at a temperature in the range of 4°C to 60°C, and at a pH range of 6 to 12.

14. The method of claim 1, wherein the formed liquid comprising the peroxy α-hydroxycarboxylic acid has a pH of less than 7 within 5 minutes after the contact step.

15. The method of claim 1, wherein the contacting step generates the peroxy α-hydroxycarboxylic acid in situ for use in applications of the formed peroxy α-hydroxycarboxylic acid.

16. The method of claim 1, wherein the peroxy α-hydroxycarboxylic acid forming composition further comprises a stabilizer, a disintegrant, a dispersant, and / or a pH buffer.

17. The method of claim 1, wherein neither the peroxy α-hydroxycarboxylic acid forming composition nor the contact step contains an enzyme and / or a catalyst.

18. The method of claim 1, wherein the peroxy α-hydroxycarboxylic acid forming composition, the contact step, and the formed peroxy α-hydroxycarboxylic acid do not contain a stabilizer.

19. The method of claim 1, wherein the method comprises sequentially contacting the liquid with a plurality of solid compositions.

20. The method of claim 1, wherein the additional C1-C22 peroxycarboxylic acid is formed in the liquid containing the peroxy α-hydroxycarboxylic acid, or wherein a pre-formed C1-C22 peroxycarboxylic acid composition is added to the liquid containing the peroxy α-hydroxycarboxylic acid.

21. The method of claim 20, wherein the ester precursor and / or carboxylic acid precursor of the additional C1-C22 peroxycarboxylic acid is contained in the solid composition and / or added to the liquid containing the peroxy-α-hydroxycarboxylic acid to react and generate the additional C1-C22 peroxycarboxylic acid.

22. The method according to claim 1, wherein the cyclic carboxylic acid diester has the following structure: , where R is CH3.

23. A peroxy α-hydroxycarboxylic acid forming composition, said peroxy α-hydroxycarboxylic acid forming composition comprising: a) Cyclic carboxylic acid diesters of α-hydroxycarboxylic acids, b) Alkalinity sources and substances that generate hydrogen peroxide upon contact with liquids; and c) Optional additional functional ingredients; Wherein, when the cyclic carboxylate diester of the α-hydroxycarboxylic acid is dissolved in a solvent, the composition is a liquid, and wherein the composition reacts to form the peroxy-α-hydroxycarboxylic acid, the peroxy-α-hydroxycarboxylic acid having a pH less than 8 within 5 minutes after the cyclic carboxylate diester of the α-hydroxycarboxylic acid comes into contact with the alkalinity source and the substance that generates hydrogen peroxide; or The composition is a solid, and the solid composition reacts when dissolved in a liquid to form the peroxy-α-hydroxycarboxylic acid, which has a pH of less than 8 within 5 minutes after the cyclic carboxylic acid diester of the α-hydroxycarboxylic acid comes into contact with the alkalinity source and the substance that generates hydrogen peroxide.

24. The composition according to claim 23, wherein the cyclic carboxylic acid diester has the following structure R is an H or alkyl group.

25. The composition of claim 24, wherein the α-hydroxycarboxylic acid is lactic acid or glycolic acid, and wherein the cyclic carboxylic acid diester of the α-hydroxycarboxylic acid is the corresponding lactide or glycolide.

26. The composition according to claim 23, wherein the alkalinity source comprises an alkali metal carbonate or percarbonate, an alkali metal borate, or urea peroxide.

27. The composition of claim 23, wherein the substance generating hydrogen peroxide comprises at least one of alkali metal percarbonate, alkali metal perborate, or peroxide.

28. The composition of claim 27, wherein the substance generating hydrogen peroxide is sodium percarbonate, sodium perborate, calcium peroxide, magnesium peroxide, PVP peroxide, or urea peroxide.

29. The composition of claim 23, wherein the alkalinity source and the substance that generates hydrogen peroxide are single agents in the solid composition.

30. The composition according to claim 29, wherein the single reagent is sodium percarbonate.

31. The composition according to claim 23 further comprises a stabilizer, a disintegrant, a dispersant, and / or a pH buffer.

32. The composition according to claim 31, further comprising citric acid.

33. The composition of claim 23, wherein the composition is a solid, and wherein the solid is in the form of powder, tablet, pellet, or other solid form, and optionally wherein the powder or other solid is contained in a pouch or sachet or PVA dosage package.

34. The composition of claim 33, wherein the solid is dimensionally stable at room temperature for at least one year.

35. The composition according to claim 23, wherein the cyclic carboxylic acid diester has the following structure: , where R is CH3.

36. A peroxy α-hydroxycarboxylic acid composition, said peroxy α-hydroxycarboxylic acid composition being formed by combining a solid composition according to any one of claims 33 to 34 with water or a non-aqueous liquid.

37. The composition of claim 36, wherein the composition is a liquid solution comprising 0.1 ppm to 100,000 ppm of the peroxy-α-hydroxycarboxylic acid, and / or wherein the peroxy-hydroxycarboxylic acid is in a concentration of 20 ppm. o It has a vapor pressure of less than 1 kPa at C.

38. A method of treating a target, the method comprising contacting the target with an effective amount of a peroxy-α-hydroxycarboxylic acid forming composition according to any one of claims 23 to 35 or a peroxy-α-hydroxycarboxylic acid composition according to any one of claims 36 to 37 to form a treated target composition, wherein the treated target composition comprises 0.1 ppm to 10,000 ppm of the peroxy-α-hydroxycarboxylic acid, and the contact lasting for a sufficient time to bleach, remove dirt, sterilize the target or the treated target composition, and / or stabilize or reduce the microbial community therein and / or thereon.

39. The method of claim 38, wherein the target is a surface requiring a high level of sterilization and the method comprises providing an effective amount of the peroxyhydroxycarboxylic acid to the surface to be treated, wherein the treated surface source comprises 1 ppm to 1,000 ppm of the peroxyhydroxycarboxylic acid.

40. The method of claim 38, wherein the contact step lasts from 1 second to 10 minutes.

41. The method of claim 38, wherein the contacting step is performed at a temperature in the range of 0°C to 70°C.

42. The method of claim 38, wherein the target is at least a portion of a food article or plant article and / or a medium, container, device, system, or facility for growing, maintaining, processing, packaging, storing, transporting, preparing, cooking, or serving the food article or plant article.

43. The method of claim 42, wherein the treatment does not cause any sensory effects in or on the food or plant article.

44. The method of claim 38, wherein the target is at least a part of a medium, container, equipment, system, or facility for producing, holding, processing, packaging, storing, or transporting pulp, and is used in the paper, textile, food, or pharmaceutical industries.

45. The method of claim 38, wherein the surface is a medical device that needs to be reused or reprocessed.

46. ​​The method of claim 38, wherein the target is a water source and / or a biofilm.

47. The method of claim 38, wherein the target is at least a portion of a medium, surface, container, device, or system in a healthcare facility.

48. The method of claim 38, wherein the surface is a laundry product.

49. The method of claim 48, wherein the laundry product is soiled and is in contact with the peroxyhydroxycarboxylic acid forming composition or the peroxyα-hydroxycarboxylic acid composition outside of a regular laundry application, a pre-wash step, a pre-bleach step, and / or a washing machine.

50. The method of claim 48, further comprising cleaning or washing the laundry product with a conventional aqueous detergent, and / or further comprising a bleaching step, one or more rinsing steps, an acidification step, and / or a softening step.

51. The method of claim 38, wherein the peroxy α-hydroxycarboxylic acid is used at a concentration of 1 ppm to 10,000 ppm.

52. The method of claim 38, wherein the peroxy α-hydroxycarboxylic acid forming composition or the peroxy α-hydroxycarboxylic acid composition is applied to the target by means of spraying, atomizing or foaming, or by immersing all or part of the target in a composition containing the peroxy α-hydroxycarboxylic acid.

53. The method of claim 38, wherein the contact step lasts for at least 5 seconds.

54. The method of claim 38, wherein the microbial community in and / or on the target or the treated target composition is reduced by at least 50%.

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