MXPA01005019A - Beverage manufacture and cold aseptic bottling using peroxyacid antimicrobial composition - Google Patents

Abstract

A peroxyacid antimicrobial concentrate and use composition is provided comprising a C1 to C4 peroxycarboxylic acid or a C1 to C4 peroxycarboxylic acid combined with a C6 to C18 peroxyacid in beverage processing. The combination of these materials produces a synergistic effect, providing a much more potent biocide than can be obtained by using these components separately. Other components can be added to the composition such as hydrotrope coupling agents, stabilizers, etc. An effective antimicrobial use solution is formed at low concentrations when the concentrate composition is diluted with water to a pH in the range of about 2 to 8. Sanitizing of substantially fixed,"in-place"processing lines in dairies, breweries, and other food and beverage processing operations is one utility of the composition. Another utility is in processes including aseptic cold filling of beverage containers such as cans, glass bottles or two liter PET bottles.

Description

MANUFACTURE OF BE BI DAS AND ASETOPTIC BOTTLED EM IN FRIÓ USE A COM POSITION ANTI M IC ROBI AN A DE PEROXIACI DO Field of the invention The invention relates generally to processes using antimicrobial or biocide compositions. More particularly, the invention relates to peroxy acid antimicrobial concentrates and use solutions, which sanitize various surfaces, such as facilities, containers or equipment found in the processing of food or beverages in food service industries to or near tem temperatures environment.

BACKGROUND OF THE INVENTION Numerous classes of chemical compounds exhibit varying degrees of antimicrobial or biocidal activity. Antimicrobial compositions are particularly necessary in the food and beverage industries to clean and sanitize processing facilities, such as pipes, tanks, mixers, etc. and homogenization or pasteurization devices that are continuously operating. The sanitization compositions have been formulated in the past to combat microbial growth in such facilities. For example, Grosse-Bwing, US Patent no. 4, 051, 058 and 4, 051, 059 shows peracetic acid materials. These peroxy-containing compositions are known to be used in the production of microbicidal agents. One such composition described in Grosse-Bowing et al, contains peracetic acid, acetic acid or mixtures of peracetic and acetic acid, hydrogen peroxide, anionic surface active compounds, such as sulfonates and sulfates, and water. Wang, US patent no. 4,404, 040, shows a short chain fatty acid sanitization composition comprising a short chain fatty acid, aliphatic, a hydrophobic solubilizer capable of solubilizing the fatty acid both in the concentrate and the solution of use and a hydrotrope compatible with acid, so that the use solution has a pH in the range of 2.0 to 5.0. Peracetic acid has been shown to be a good biocide, but only at fairly high concentrations (generally more than 1 00 parts per million (ppm)). Similarly, peroxy acids have also been shown to be biocides, but only at high high concentrations (more than 200 ppm), such as in the composition described in European patent application no. 233, 731. Antimicrobial compositions that have low use concentrations (less than 1000 ppm), which kill microbes effectively, are particularly desirable. The low concentrations minimize the cost of use, surface corrosion, odor, remnants of biocide in food and potential toxic effects to the user. Therefore, there continues to be a need to provide such antimicrobial compositions for use in food processing, food service and health care facilities. In contrast to the prior art, the compositions of the present invention have the unique advantage of having antimicrobial activity or biocide at low level use concentrations.

BRIEF DESCRIPTION OF THE INVENTION The invention is a peroxyacid antimicrobial concentrate and end-use composition comprising an effective microbicidal amount of a peroxycarboxylic acid of C! -C or an effective microbicidal amount of a C-peroxycarboxylic acid? -C combined with an effective microbicidal amount of a C6-C18 peroxyacid acid. The concentrated composition can be diluted with a higher proportion of water to form a solution of sanitizing, antimicrobial use, having a pH in the range of about 2 to 8, with a concentration of peroxycarboxylic acid of C? -C4 of at least about 1. 0 ppm, preferably about 10 to 75 ppm, and a C 6 -C 8 peroxy acid concentration of at least about 1 ppm, preferably about 1 to 25 ppm. Other components can be added, such as a hydrotrope coupling agent for solubilizing the peroxy acid in the concentrated form and when the concentrated composition is diluted with water. In contrast to the prior art, we have discovered that at a low pH (eg, preferably less than 5), the C6-C1-8 peroxyacids, such as peroxy acids, are very potent biocides at low levels. When used in combination with a C1-C4 peroxycarboxylic acid, such as peroxyacetic acid, a synergistic effect is obtained, providing a much more potent biocide that can be obtained by using these components separately. This means that substantially lower biocide concentrations can be used to obtain equal biocide effects, leading to lower product costs and less potential for corrosion. As the term is used herein, a C 6 -C 18 peroxyacid (or peracid) is meant to mean the oxidation product of a C 6 -C 8 acid, such as a fatty acid, or a mixture of acids, to form a peroxyacid having from about 6 to 1 8 carbon atoms per molecule. The C 1 -C 4 peroxycarboxylic acid is intended to mean the oxidation product of a C 1 -C carboxylic acid, or a mixture thereof. This includes both simple and substituted C ácidos-C carboxylic acids. A method for sanitizing installations or equipment comprises the steps of contacting the facilities or equipment with the use solution made from the concentrate composition of the invention at a temperature in the range of about 0 ° C to 80 ° C, preferably 20 ° C to 40 ° C, and often at ambient temperature conditions. The composition is then circulated or left in contact with the container, facilities or equipment for a sufficient time to sanitize (generally at least 30 seconds) and the composition is subsequently drained or removed from the container, facilities or equipment. We have found that the methods of the invention are capable of killing a variety of microorganisms including bacteria, yeasts and molds. In particular, the methods are surprisingly effective for aseptic cold filling of beverage containers. The com positions are effective against any fungal genus, Chaetomium or Arthirnium, which are a problem in bottling operations.

One aspect of the invention is the novel antimicrobial concentrate composition, which is capable of being diluted with a higher proportion of water to form a solution for sanitizing use. A further aspect of the invention is an aqueous antimicrobial sanitizing solution, which is particularly suitable for "on-site" cleaning applications. A further aspect of the invention is a method for employing the solution of use of the invention in the cleaning or sanitization of various facilities or process equipment as well as other surfaces.

Brief discussion of the drawings The Figure is a diagram of a beverage plant, including a cold aseptic filling plant, in which carbonated or non-carbonated drinks can be prepared and bottled.

DETAILED DESCRIPTION OF THE INVENTION The invention resides in a peroxy acid antimicrobial concentrate and use composition comprising an effective microbicidal amount of a peroxycarboxylic acid of an effective microbicidal amount of a Ci-C4 peroxycarboxylic acid combined with a Effective microbicidal amount of a C6-C1-8 peroxyacid We have found that combining these acids produces a synergistic effect, producing a much more potent biocide that can be obtained by using these components separately. The concentrated composition can be diluted with a higher proportion of water to form an antimicrobial sanitizing solution, having a pH in the range from about 2 to 8. The sanitizing solution can be used effectively to clean or sanitize facilities and equipment used in food processing, food service and health care industries.

Peroxyacids Concentrates containing peroxy can be obtained, which are stable in storage, which are useful for the production and complementation of microbicides based on aliphatic monopercarboxylic acids. These peroxy-containing concentrates are characterized by a content of 0.5% to 20% by weight of a peracid having 2 to 3 carbon atoms and / or the corresponding aliphatic non-carboxylic acid, as well as 25% to 40% by weight of H2O2, and the rest of water. More particularly, the invention relates to a storage-stable peroxy containing concentrate comprising from 0.5% to 20% by weight of an acid selected from the group consisting of peracetic acid, acetic acid, perpropionic acid, acid propionic, mixtures of peracetic acid and acetic acid, and mixtures of perpropionic acid and propionic acid, from 25% to 40% by weight of H2O, from 0 to 5% by weight of an anionic active surface compound, selected from the group consists of its lfonatos and sulfates, and the rest to 1 00% in weight, ag ua. Preferably, the storage-stable peroxy-containing concentrates contain from 5% to 10% by weight of the component (1) and a molar excess of H2O2, with reference to the acid component (1), calculated as the monocarboxylic acid, in a molar ratio of at least 2: 1, preferably 3: 1 to 50: 1. When the active surface anionic compound of the sulfonate and sulfate type is present, it is preferably in an amount from 0.5% to 5% by weight. Production is effected in a simple manner by mixing a H 2 O 2 solution, preferably at a concentration of about 33% by weight with peracid, such as peracetic acid and, optionally, acetic acid. The mixtures can also be produced in an advantageous manner by adding the corresponding amount of the acid, such as acetic acid, to the concentrated H2O2 solution. Because the products are not primarily used at once, but are first stored, a corresponding peracetic acid content is formed when acetic acid is used. The formation of peracetic acid can be accelerated catalytically, if desired, by adding a small amount of a mineral acid (0. 1% up to 1% by weight). However, in general, such addition is not necessary for the reasons mentioned above. Such concentrates, which are produced, for example, from 30% H2O2, 5% acetic acid and 65% water, do not have annoying odors and are easy to handle, that is, they can be easily diluted. the concentration of 0. 1% up to 1%, as they are used in food technology and in the medical field, without requiring special precautions. In view of the many possible uses of the above-described peroxy-containing concentrates as functional agents, for example, for the oxidation of organic material in general, or for the treatment of hair, straw and textiles, as well as the preparation of microbicides and virucides , sometimes it is advantageous to add a wetting agent in order to further improve the desired properties. It was found that stable concentrates of the type described above can be obtained if anionic surfactant-type active compounds of the surtate and sulfate type, such as alkynylbenzene and its lyophones having 6 to 18 carbon atoms in the alkyl, alkyl sulphates and / or alkane Sulfonates (each having 8 to 22 carbon atoms in the alkyl or alkane groups) are added in amounts of 0.05% up to 5% by weight. The alkylbenzene sulphonates, which may be used, are preferably those which contain an alkyl radical of 6 to 18 carbon atoms, preferably 9 to 15 carbon atoms. In place of the alkylbenzene sulphonates, alkyl sulfates or alkane sulphonates may be used with an alkyl or alkane radical of chain length 12 to 18 atoms. If desired, mixtures of the above-mentioned anionic surface active compounds can naturally also be used. It was found that, with the aforementioned additives, the concentrates remain stable over long periods and that this way the peracetic acid content in the concentrate also remains constant. However, if soaps or conventional anionic active surface compounds are used as the active surface additive, sufficient stability is not achieved. The new stable peroxy-containing concentrates are useful in the production of functional agents, which can be used for all purposes, where an oxidizing effect will be achieved and the disadvantages of the known pure peracids have been difficult or impossible to apply. The concentrates also have the advantage that they can be used to produce functional agents for static disinfection to prevent the growth of germs in machines after cleaning, particularly in the food industry. Due to their H2O2 content, they have a long-term effect on most microorganisms. The pH value of the solution produced is still slightly acidic, and the residues of acetic acid after disinfection are extremely small, so that the agents are also suitable for disinfections where flushing is no longer necessary. The peroxyacid sanitizing materials of the invention can be used in the manufacture of beverage materials including fruit juice, dairy products, malt beverages, bottled water products, teas and non-alcoholic beverages. The materials can be used to sanitize bottles, pumps, lines, tanks and mixing equipment used for the manufacture of such beverages. In addition, the peroxyacid materials can be used in cold, aseptic filling operations, in which the interior of the beverage container is sanitized prior to filling. In such operations, a beverage container is contacted with the peroxyacid sanitizer material, typically using a spray device to intimately contact the interior of the container with the peroxyacid, for a period sufficient to reduce the population of microorganisms within the container. container. The container is then emptied of the quantity of sanitizer used. After emptying, the container can be rinsed commonly with potable water or sterilized water and again emptied. After rinsing, the container is then filled with the liquid beverage. The container is then sealed, capped or closed and then packaged for shipment for final sale. The sealed container can be autoclaved or retorted to kill additional microorganisms. In the manufacture of beverages, we have found that a fungal microorganism of the genus Chaetomium or Arthrinium can be a significant problem in bottling processes, particularly in bottling, aseptic, cold processes. The peroxyacid sanitizing materials of the invention can be used for the purpose of controlling or reducing substantially (by more than one network of 5 log1 0), the number of Chaetomium or Arthrinium microorganisms in beverage bottling lines using bottling techniques. , aseptic, cold. In such techniques metal, aluminum or steel cans can be filled, plastic bottles or containers can be filled, or plastic bottles (PET, PBT or PEN) can be filled, using cold aseptic filling techniques. In such processes, the peroxyacid materials of the invention can be used to sanitize the interior of the beverage containers prior to filling with the carbonated beverage. Normal carbonated beverages in this application include cola beverages, fruit drinks, ginger ale drinks, root beer beverages, ice tea beverages, which may be non-carbonated, and other common beverages considered non-alcoholic beverages. The peroxyacid materials of the invention can be used to sanitize both tanks, lines, pumps and other equipment used for the manufacture and storage of the non-alcoholic beverage material and can also be used in bottles or containers for beverages. Peroxyacid sanitizing materials are useful for killing both bacterial and fungal microorganisms that may be present on the surfaces of production equipment and beverage containers. The present invention is based on the surprising discovery that when a peroxy acid of C5-C1-8 is combined with a C1-C peroxycarboxylic acid, a synergistic effect occurs and a greatly enhanced antimicrobial activity is exhibited, when it is com with the peroxy acid of C5-C? 8 or C1-C peroxycarboxylic acid alone. The present mixture of a C 5 -C 8 peroxyacid and a C 2 -peroxycarboxylic acid -C4 can effectively kill microorganisms (for example, a reduction of 5 log10 in 30 seconds) from a concentration level below 1 00 ppm and as low as 20 ppm of the peroxyacid mixture. A variety of peroxyacids of C5-C1 8 or C6-C can be used? 8 in the composition of the invention, such as peroxy acids, monoperoxy or diperoxydicarboxylic acids and peroxyaromatic acids. The C6-C1 peroxy acids used in the present invention can be represented structurally as follows: F CO3H, wherein P is a hydrocarbon portion having from about 5 to 17 carbon atoms (a C8 peroxyacid is generally represented structurally as C7-CO3H). R may have substituents in the cayenne, for example, -OH, CO2H, or heteroatoms (for example, -O- as in carboxylic alkaline ether acids), provided that the antimicrobial properties of the overall composition are not affected. meaningful way It should be recognized that the "RX" substituents or heteroatoms may change the overall acidity (ie, pKa) of the carboxylic acids described herein Such a modification is within the contemplation of the present invention, so long as the advantageous antimicrobial performance is maintained. Additionally, R ^ can be linear, branched, cyclic or aromatic The preferred hydrocarbon portions (i.e. preferred Rs) include linear aliphatic hydrocarbon portions, saturated having from 7 to 1 1 carbon atoms (or 8 to 1 2 carbon atoms per molecule). Examples of suitable C 6 -C 8 carboxylic acids, which can be reacted with hydrogen peroxide to form peroxyacids, include such saturated acids as hexanoic (C6), enanthanic (heptanoic) (C7), caprylic (octanoic) (C8) ), pelargonic (nonanoic) (C9), capric (decanoic) (C1 0), undecyclic (undecanoic) (Cn), lauric (dodecanoic) (C1 2), tridéclico (tridecanoic) (C1 3), myristic (tetradecanoic) (C1), palmic (hexadecanoic) (C16) and stearic (octodecanoic) (C1 8). These acids can be derived from both natural and synthetic sources. Natural sources include animal or vegetable fats or oils, which should be completely hydrogenated. Synthetic acids can be produced by the oxidation of petroleum wax. Particularly preferred peroxy fatty acids for use in the composition of the invention are linear, aliphatic, monoperoxy fatty acids, such as peroxioctanoic acid, peroxydocanoic acid or mixtures thereof. Other suitable C 6 -C 8 peroxyacids are derivatives of the oxidation of dicarboxylic acids and aromatic acids. Suitable dicarboxylic acids include adipic acid (C6), glutaric acid (C5) and sebacic acid (C or o) - An example of a suitable aromatic acid is benzoic acid. These acids can be reacted with hydrogen peroxide to form the peroxy acid form suitable for use in the composition of the invention. Preferred peroxyacids in this group include monoperoxy- or diperoxyadipic acid, monoperoxy- or diperoxysebacic acid and peroxybenzoic acid. The above peroxyacids provide antibacterial activity against a wide variety of microorganisms, such as, gram positive (e.g., Staphylococcus aureus) and gram negative (e.g., Escherichia coli) microorganisms. yeasts, molds (for example, Chaetonium, Arthrinium and similar genera), bacterial spores, etc. When the C6-C1 8 peroxyacids above are combined with a peroxycarboxylic acid of C? -C, our activity is greatly intensified compared to the C-C peroxycarboxylic acid alone or the C6-C1 8 peroxyacid alone. The peroxycarboxylic acid component of C? -C can be derived from a C? -C carboxylic or dicarboxylic acid by reacting the acid with hydrogen peroxide. Examples of suitable C-, -C carboxylic acids include acetic acid, propionic acid, glycolic acid and succinic acid. Preferred Ct-C peroxycarboxylic acids for use in the composition of the invention include peroxyacetic acid, peroxypropionic acid, peroxy glycolic acid, peroxysuccinic acid or mixtures thereof. The antimicrobial concentrate of the present invention may comprise about 0.01 to 10% by weight, preferably about 0.05 to 5% by weight, and most preferably about 0. 1 to 2% by weight of a C6-C1-8 peroxy acid and about 0.1 to 25% by weight, preferably approximately 0.5 to 20% by weight and most preferably approximately 1 to 15% by weight of a C 1 -C 4 peroxycarboxylic acid. The concentrate composition preferably has about 1 to 15% by weight of a C1-C peroxycarboxylic acid. The concentrate composition preferably has a weight ratio of peroxycarboxylic acid of C! -C4 to C6-C1 8 from about 1 5: 1 to 3: 1. The concentrate contains sufficient acid, so that the end-use solution has a pH of about 2 to 8, preferably about 3 to 7. Some acidity may come from an inert acidulant, which may optionally be added (e.g. , phosphoric acid). The peroxyacid components used in the composition of the invention can be produced in a simple manner by mixing a solution of hydrogen peroxide (H2O2) with the desired amount of acid. With higher molecular weight acids, a hydrotrope coupler may be required to help solubilize the acid. The H2O2 solution can also be added to previously made peroxyacids, such as, peracetic acid or various peroxyacids to produce the peroxyacid composition of the invention. The concentrate may contain about 1 to 50% by weight, preferably about 5 to 25% by weight of hydrogen peroxide. The concentrate composition may additionally comprise a free C6-C1-8 carboxylic acid, a free Ct-C carboxylic acid, or mixtures thereof. The free acids will correspond, preferably, to the starting materials used in the preparation of the peroxyacid components. The carboxylic acid of C6-C1-8 is preferably linear and saturated, has 8 to 12 carbon atoms per molecule, and may also comprise a mixture of acids. C6-C18 carboxylic acid free and carboxylic acid of C? -C free can be present as a result of an equilibrium reaction with hydrogen peroxide to form the peroxyacids.

Additional components Various additional materials may be added to the composition of the invention to help solubilize the fatty acids, restrict or enhance foaming, to control hard water, to stabilize the composition, or to further enhance the antimicrobial activity of the composition . The composition of the invention may contain a hydrotrope coupling agent, surfactant or solubilizer, which allows mixing short chain peroxyacids in aqueous liquids. Functionally speaking, suitable couplers that can be used are non-toxic and retain the fatty acid and peroxyacid in aqueous solution through the range of temperature and concentration at which a concentrate or any solution of use is exposed. Any suitable coupler can be used as long as it does not react with the other components of the composition or adversely affect the antimicrobial properties of the composition. Representative classes of hydrotropic coupling agents or solubilizers that may be employed include anionic surfactants, such as alkyl sulphates and alkane sulfonates, linear alkyl benzene or naphthalene sulfonates, secondary alkane sulphonates, alkyl ether sulfates or sulfonates, alkyl phosphates or phosphonates, esters of dialkyl sulfosuccinic acid, sugar esters (eg, sorbitan esters) and C8-C1 alkyl glucosides. Preferred coupling agents for use in the present invention include noctanesulfonate, available as Ecolab 8AS, and aromatic sulfonates commonly available, such as, the alkyl benzene sulfonates (eg, xylene sulfonates) or naphthalene sulfonates. Some of the above hyrotropic coupling agents independently exhibit the antimicrobial activity at low pH. This adds to the effectiveness of the present invention, but is not the primary criterion used to select an appropriate coupling agent. Because the presence of peroxyacid in the protonated neutral state is what provides the biocidal activity, the coupling agent should be selected not for its independent antimicrobial activity, but for its ability to provide effective interaction between the substantially insoluble peroxyacids described in the present and the microorganisms, which control the present com positions. The hydrotrope coupling agent may comprise about 0.1 to 30% by weight, preferably about 1 to 20% by weight, and most preferably about 2 to 15% by weight of the concentrate composition. Compounds such as mono, di and trialkyl phosphate esters can be added to the composition to suppress the foam. Such phosphate esters would generally be produced from aliphatic linear alcohols, there being from 8 to 12 carbon atoms in the aliphatic portions of the alkyl phosphate esters. The alkyl phosphate esters possess some antimicrobial activity in their own right under the conditions of the present invention. This antimicrobial activity also tends to be added to the overall antimicrobial activity of the present compositions, even though the phosphate esters can be added for other reasons. In addition, the addition of non-ionic surfactants would tend to reduce foam formation in the present. Such materials tend to intensify the performance of the other components of the composition, in particular in cold or soft water. A nonionic surfactant particularly useful for use as a defoamer is non-ilphenol, having an average of 1 2 moles of ethylene oxide condensed therein, being encapsulated with an idrophobic portion comprising an average of 30 moles of propylene oxide. .

Chelating agents can be added to the composition of the invention to enhance biological activity, performance of cleaning and stability of peroxyacids. For example, 1-h-idroxyethylidene-1,1-diphosphonic acid commercially available from Monsanto Company, under the designation "DEQU EST", has been found effective. Chelating agents may be added to the present composition to control or sequester hardness ions, such as calcium and magnesium. In this way, both sanitization capacity and detergency can be intensified. Other materials that are sufficiently stable at the low pH contemplated by the present composition can be added to the composition to impart desirable qualities depending on the intended end use. For example, phosphoric acid (H3PO) can be added to the composition of the invention. Additional compounds can be added to the concentrate (and thus finally to the use solution) to change its color or odor, to adjust its viscosity, to intensify its thermal stability (ie, freeze-thaw) or to provide other qualities that tend to make it more marketable. The composition of the invention can be made by combining, by simple mixing, an effective amount of a C 5 -C 18 or C 6 -C 8 peroxy acid, such as a peroxyacid with some source of a C 2 -peroxycarboxylic acid. -C4, such as a peroxyacetic acid. This composition would be formulated with preformed peroxyacid and preformed peroxyacetic acid. A preferred composition of the invention can be made by mixing a C-α-C4 carboxylic acid, a C6-C18 carboxylic acid, a coupler and a stabilizer, by reacting this mixture with hydrogen peroxide. A mixture of stable equil ibrio containing a peroxycarboxylic acid of C is produced! -C4 and a C6-C1-8 peroxy acid, a C1-C peroxycarboxylic acid, a C2Ct peroxyacid, water and various couplers and stabilizers. By using the above approach, the composition of the invention can be formulated by simply mixing readily available raw material, for example, acetic acid, hydrogen peroxide and fatty acid. By allowing the solution time for equilibrium to be obtained, the product containing both of the active biocides is obtained. By varying the carboxylic acid ratio of Ci-C to C6-C8 carboxylic acid, it is easy to vary the proportion of the C-C4 peroxycarboxylic acid to C6-C18 peroxyacid.

Concentrate and use compositions The present invention contemplates a concentrate composition, which is diluted to a use solution before its use as a sanitizer. Mainly for economic reasons, the concentrate would be commercialized normally and the end user would dilute the concentrate with water to a solution of use. A preferred antimicrobial concentrate composition comprises about 0.01 to 10% by weight, preferably about 0.05 to 5% by weight of a C6-C1 8 peroxy fatty acid, about 0.1 to 25% by weight, preferably about 0.5 to 20% by weight. % by weight, of a C-peroxycarboxylic acid! -C, about 0. 1 to 30% by weight of an idrótropo coupling agent and about 1 to 50% by weight of peroxide and hydrogen. Other acidulants may be optionally employed in the composition, such as phosphoric acid. The level of active components in the concentrate composition is dependent on the dilution factor sought and the desired acidity in the use solution. The peroxy acid component of C 6 -C 8 is generally obtained by reacting a C 6 -C 8 carboxylic acid with hydrogen peroxide in the presence of a C 1 -C 4 carboxylic acid. The resulting concentrate is diluted with water to provide the use solution. In general, a dilution of 0.02957 I to 1 5. 14 I (ie, dilution of 1 to 500 by volume) or to 30.28 I (ie, dilution of 1 to 1, 000 by volume) of water, can be obtained with 2 % to 20% of the total peroxyacids in the concentrate. The highest use dilution can be used if high-use temperature (greater than 20 ° C) or prolonged exposure time (greater than 30 seconds) are also used. In its intended final use, the concentrate is diluted with a greater proportion of water and is used for sanitation purposes. The normal concentrate composition described above is diluted with tap water or available service water to a formulation of approximately 0.02957 I of concentrate to 30.28 I of water. An antimicrobial, aqueous sanitizing use solution comprises at least about 1 part per million (ppm), preferably about 1 to 10 ppm of a C6-C1 peroxy acid, and at least about 10 ppm, preferably about 20 to 50 ppm of a C-peroxycarboxylic acid! -C. The weight ratio of peroxy acid of C6-C1-8 to Ci-C4 peroxycarboxylic acid ranges from about 0.01 to 0.5 parts, preferably about 0.02 to 0.2 parts of C6-C6 peroxy acid per part of C1-C4 peroxycarboxylic acid. . Preferably, the total peroxy acid concentration in the use solution is less than about 75 ppm and most preferably between about 5 to 50 ppm. Higher levels of peroxyacids can be used in the use solution to obtain disinfecting or sterilizing results. The aqueous use solution may further comprise at least about 1 ppm, preferably about 2 to 20 ppm of a hydrotrope coupling agent, at least about 1 ppm, preferably about 2 to 200 ppm hydrogen peroxide, and at least about 1 ppm, preferably about 2 to 200 ppm of a free C6-C18 carboxylic acid, a free CrC4 carboxylic acid, or mixtures thereof. The aqueous use solution has a pH in the range of about 2 to 8, preferably about 3 to 7.

Methods of use As noted above, the present composition is useful in cleaning or sanitizing facilities or processing equipment of containers in the food service, food processing or health care industries. Examples of processing facilities in which the composition of the invention can be employed include dairy line, a continuous brewing system, food processing lines, such as pumpable food systems and beverage lines., etc. The food service articles can also be disinfected with the composition of the invention. The composition is also useful for sanitizing or disinfecting solid surfaces, such as floors, countertops, furniture, tools and medical equipment, etc. , found in the health care industry. Such surfaces frequently become contaminated with spillages of body fluids, such as blood, other dangerous body fluids or mixtures thereof. Containers include glass bottles, PVC or polyolefin film sacks, cans, polyester, PEN or PET bottles of various volumes (1 00 ml to 2 liters, etc.), 3,785 I milk containers, cardboard containers for milk or juice, etc. In general, the actual cleaning of the system in its place or another surface (ie, removal of unwanted waste therein), is achieved with a different material, such as a formulated detergent, which is introduced with hot water. After this cleaning step, the present sanitization composition would be applied or introduced into the system at a concentration of use solution in unheated water, at room temperature. It is found that the present sanitizing composition remains in solution in cold water (eg, 4 ° C) and hot water (eg, 60 ° C). Although it is usually not necessary to heat the aqueous use solution of the present composition, heating may be desirable under some circumstances to further enhance its antimicrobial activity. These materials are useful at any conceivable temperature.

A method to sanitize its stationary process facilities in place, comprises the following steps. The use composition of the invention is introduced into the process facilities at a temperature in the range of about 4 ° C to 60 ° C. After the introduction of the use solution, the solution is held in a container or circulated through the system for a sufficient time to sanitize the process facilities (ie, to kill undesirable microorganisms). After the surfaces have been sanitized by means of the present composition, the use solution is drained. Upon completion of the sanitization step, the system may optionally be rinsed with other materials, such as potable water. The composition is circulated, preferably, through the process facilities for 10 minutes or less. The composition can also be used by immersing the food processing equipment in the use solution, soaking the equipment for a sufficient time to sanitize the equipment, and wiping or draining the excess solution from the equipment. The composition can be used additionally to atomize or wipe the processing surfaces of the ingredients with the use solution, keeping the surfaces moist for a sufficient time to sanitize the surfaces, and remove the excess solution when wiping, draining vertically, subjecting to vacuum, etc.

The composition of the invention can also be used in a method for sanitizing hard surfaces, such as institutional type equipment, utensils, dishes, equipment or tools for health care and other hard surfaces. The composition can also be used to sanitize articles of clothing or cloth, which have become contaminated. The use composition contacts any of the contaminated surfaces or articles prior to use temperatures in the range of about 4 ° C to 60 ° C, for an effective period to sanitize, disinfect or sterilize the surface or article. For example, the concentrate composition can be injected into the washing or rinsing water of a washing machine and can come into contact with contaminated fabric for a sufficient time to sanitize the fabric. The excess solution can then be removed by rinsing or centrifuging the fabric. As the term "sanitize" is used in the method of the present invention, it means a reduction in population numbers of undesirable microorganisms of about 5 powers of 10 or more (ie, at least 5 orders of magnitude) after an exposure time of 30 seconds. It will be emphasized that the present use solution provides cleaning as well as sanitizing performance although its primary utility is sanitizing. The composition can also be used to achieve disinfection or sterilization (ie, elimination of all microorganisms) by employing higher levels of peroxyacids in the use solution. The following examples are intended to illustrate the previous invention and should not be construed as narrowing its scope. One skilled in the art will readily recognize that these examples suggest many other ways in which the present invention could be practiced.

DETAILED DESCRIPTION OF THE DRAWINGS The Figure shows a schematic for bottle spraying / bottling operation using active peroxyacid sanitizing materials, including aseptic cold operation. In the figure, a plant 100 is shown that can contact beverage bottles with a peroxyacid sanitizer for a sanitizing regime. In the figure, the bottles 110 are passed through a sterilizing tunnel 102. The sanitized bottles 110a then pass through a rinsing tunnel 103 and emerge as sanitized, rinsed bottles 110b. In the process, bulk peroxyacid sanitizer is provided in a drum or vessel 104, and is added to a holding tank 101 at an effective concentration, comprising from about 0.1 to about 5% by weight, preferably 3% by weight to about 4% by weight. Commonly, the materials are maintained at a temperature of about 22 ° C in tank 101. To obtain the effective concentration of peroxyacid 105, replacement water is combined with the concentrate from drum 104 in tank 101. The peroxyacid sanitizing material at an appropriate concentration, it is passed through a heater 108 to reach a temperature of about 45-50 ° C. The heated peroxyacid material is sprayed into the sterilization tunnel 102 towards and over all the surfaces of the bottle 110. Intimate contact between the peroxyacid material and the bottle 110 is essential to reduce the microbial populations to a sanitizing level. After contact with the peroxyacid material and after emptying any excess material from the bottles, the sterilized bottles 110 are then passed to a fresh water rinse tunnel 103 Fresh water 108 is provided from fresh replacement water to a spray rinse tunnel 103 Excess spray is drained from rinse tunnel 103 to drain 106 Inside tunnel 103, sanitized bottles 110a are thoroughly rinsed with fresh water The complete removal of peroxyacid material from bottles 110a is important to maintain the high quality of the beverage product The sanitized, wiped bottles 110b are then removed from the rinse tunnel The tank in turn 101, the sterilization tunnel 102 and the rinse tunnel 103 are all expended respectively to a wet scrubber or vent 111a, 111b or 111c to remove vapors or fumes from system components Sanitize material before it has been atomized and drained from the bottles 110a is accumulated in the bottom of the atomization tunnel 102 and then it is recycled through the recycling line and heater 107 in the tank in turn 101. The day tank is used to mix and storing the peroxyacid material, which may be from 1 to 5% by weight, preferably from 2 to 4% by weight of peroxyacetic acid. All active treatment equipment should be ventilated to a wet scrubber to prevent the peroxide from emanations from Peracetic acid or acetic acid enters the atmosphere of the treatment equipment Draining the containers of their peroxyacid contents is important to reduce the loss of product minimized by remnants The water used to replace the active sanitizing material should be increased to maximize life Useful of the peroxyacid material. Deionized water maintains the highest effective concentration and reduces stains and film formation. The contact between the bottles and the peroxyacid material is usually at a temperature of more than about 40 ° C. In order to obtain sanitization of beverage containers at approximately 700 ppm per acid up to approximately 2500 ppm per acid, contact at 40-60 ° C is required for at least 7 seconds of contact time. Preferably, the sanitization equipment, tank in turn, sanitizing tunnel and rinsing tunnel, are made of polyolefin structural plastics, inert stainless steel or other production materials not sensitive to corrosion. In the cold aseptic filling of polyethylene terephthalate beverage containers (PET bottle) of 0.473 I, a process using a peroxy acid sanitizer or mixed peroxy acid sanitizer material has been adopted. The peroxyacid material is diluted to a concentration of about 0.1 to about 3% by weight and maintained at an effective elevated temperature of about 40 ° C to about 60 ° C, preferably about 50 ° C. The atomization or flooding of the bottle with the material ensures contact between the bottle and the sanitizing material for at least 7 seconds. After the flood is completed, the bottle is drained of all contents for a minimum of 2 seconds, followed by a 5 second rinse with sterile water using approximately 200 ml of water at 38 ° C. The bottle is then drained of the sterilized water rinse for at least 2 seconds and immediately filled with the liquid drink. After the rinse is complete, the bottles hold less than 3 milliliters of rinse water after draining.

Example 1 Experiments were conducted to determine the antimicrobial efficacy of pure peroxyacids. Table I below demonstrates the antimicrobial efficacy of pure peroxyacids at very low levels, when exposed to S. aureus and E. coli. The peroxyacids listed in Table I were tested by diluting them in 0.05M citrate buffer made in distilled water, and exposed to the bacteria for 30 seconds at 20 ° C. As indicated in Table I, the diperoxy acids were somewhat less active than the peroxygen acids. Peroxidanoic acid was very effective at very low levels against S. aureus, but higher levels were required to be effective against E. coli. Higher levels were also required at pH 5.

TABLE I Comparison of biocidal activity of peroxyacids Reduction of pJH Minimum concentration required peroxyacid (ppm) (a) for 5-log S. aureus E. coli Peroxyhexanoic (C6) 3.5 15 15 5.0 20 15 Diperoxiadípico (C6) 3.5 > 50 40 5.0 > 60 35 Peroxyoctanoic (C8) 3.5 5 5 5.0 10 15 Peroxidecanoic (C10) 3.5 3 10 5.0 1 30 Diperoxisebacic (C10) 3.5 15 15 5.0 10 50 (a) - Peroxyacids were tested in increments of 5 ppm, or 1, 3 and 5 ppm where appropriate.

In Table II below, the antimicrobial synergism between peroxy acids C2 and C3 is shown when combined with C8 and C10 peroxy acids. As shown in Table II, there was or was little antimicrobial activity when the peroxyacids of C2 and C3 and the peroxy acids of C8 and C10 were tested alone. However, when a C2 or C3 peroxyacid was combined with a C8 or C10 peroxigraphic acid, the bacterial death of E. coli multiplied exponentially.

These tests were conducted at pH 4.5 or 5, the pH at which it is more difficult to kill E. coli (see Table II).

TABLE II Synergistic interaction of peroxyacids [peroxyacetic] [peroxypropionic] [peroxioctanoic] [peroxydocanoic] Reduction (ppm) (ppm) (ppm) (ppm) log 25 0 0a 0 5 0.1a 25 5 3.8a 25 0 0.3b 0 6 0.1 b 25 6 3.9 30 0 0.7a 0 6 0a 30 6 2.6aa E. coli, pH 5, distilled water b E. coli, pH 4.5, 500 ppm hard water Example 2 A commercially available blend of short chain fatty acids from Emery Corporation under the designation "EMERY 658" was used to produce a sanitizing concentrate composition of the present invention. The acid "EMERY 658" is a mixture of caprylic acid (C8) and capric acid (C10). Peroxyacids were prepared by the method of Parker, et al., J. Amer. Chem. Soc, 77, 4037 (1955), which is incorporated herein by reference. The peroxyacid component (also containing 34% acetic acid and 10% hydrogen peroxide) was combined with a pre-made solution of 10.42% peracetic acid, a separate amount of acetic acid, water and a hydrotrope coupler. n-octanesulfonate (ÑAS 8D). The final composition of this Example was as listed in Table III.

Example 3 A second composition of the present invention was prepared as described in Example 2, except that caprylic acid (C8) and capric acid (C10) replaced some of the peroxyacid of Example 2. The concentration of peracetic acid was 5% , although the concentration of peroxyacids was reduced to 1.5% (see Table III).

Example 4 The composition of Example 4 was prepared according to the procedure of Example 2, except that no peracetic acid or hydrogen peroxide was added to the composition. The acetic acid component was increased to 39% by weight and the composition contained 5% peroxyacid (see Table III). In addition, a chelating agent (Dequest 2010) was added to the composition.

Example 5 The composition of Example 5 was prepared as in Example 4, except that caprylic acid and caprylic acid were added to the composition, in addition to the percaprilic and percapric acid of Example 4. The composition contained 3.5% fatty acid and .5% peroxyacid (see Table III).

Example 6 Example 6 was prepared only with peracetic acid, acetic acid, hydrogen peroxide and water. No peroxyacids or fatty acids were added to the composition of Example 6. The concentration of total peroxyacid was about 5% and the concentration of acetic acid was about 39% (see Table 11).

Example 7 Example 7 was prepared as in Example 5, except that no peroxyacids were used, only a mixture of fatty acids and acetic acid was used, together with water, ÑAS BD and Dequest 201 0. The composition contained 5% of fatty acid (see Table III).

TABLE III% by weight of ingredients Ingredient Ei.2 Ej.3 Ej.4 E¡.5 E¡.6 Ei.7 Peracetic acid (10.42% 50 50 - - 50 solution, 34% acetic acid, 10% H2O2) Acetic acid 22 22 39 39 22 39 Percaprylic acid (C8) 3.75 1.125 3.75 1.125 Percapric acid (Cío) 1.25 0.375 1.25 0.375 Caprylic acid (C8) 2.625 - 2.625 - 3.75 Capric acid (C10) 0.875 - 0.875 - 1.25 ÑAS 8D 10 10 10 10 - 10 Water 13 13 45 45 28 45 Dequest 2010 .. .. 1 1 .. 1 Antimicrobial Efficacy of Examples 2-7 The compositions prepared according to Examples 2-7 were tested for their antimicrobial efficacy using the sanitizing test procedure of A. O. A.C standard. All tested samples of Examples 2-7 were made about 1 hour before the test. The bacteria used in the test procedure were S. aureus and E. coli. Distilled water was used to dilute the concentrate compositions of Examples 2-7 and the composition was used at room temperature. The following neutralizers were used in the test: 0.1% thiosulfate, peptone, 0.5% K2HPO4, 0.025% catalase for peracetic acid; chambers for fatty acid; 0. 1% thiosulfate, peptone, 0.025% catalase for peracetic acid / fatty acid (peroxyacid). The antimicrobial activity of Examples 2-7 is summarized in Table IV. Examples 3 and 3 were tested using four samples (a, b, c, d) and Examples 4-7 were tested using two samples (a, b). As can be seen in Table IV, Examples 2-5 exhibited excellent death (> 6 log) of both S. aureus as from E. coli at 50 ppm of peroxyacid. Examples 6 and 7 (without containing peroxyacids) exhibited little or no activity. More specifically, Example 2 was tested at 1, 000 and 500 ppm of total product (50 and 25 ppm both peroxyacetic acid and peroxy acid). At these low concentrations, the peroxyacid combination gave a 6-7 log reduction in the bacterial count. Example 3 was tested at 1, 000 and 500 ppm of total product, and also had a 6-7 log reduction in the bacterial count. At the product concentration of 500 ppm, the product corresponds to 25 ppm of peroxyacetic acid and 7.5 ppm of peroxyacids. Example 4, at 1,000 ppm of total product (50 ppm of peroxyacid), completely killed all bacteria (reduction greater than 7 log). Example 5 also resulted in a complete mill using 1, 000 ppm of total product (15 ppm of peroxyacid). Example 6 did not contain peroxyacid (only 50 ppm of peroxyacetic acid) and showed no activity against S. aureus and poor activity against E. coli. This is due to the fact that peroxyacetic acid is generally not effective at this level, and is generally used at concentrations greater than 1 00 ppm. Example 7, containing 5% fatty acid (30 ppm) and no peroxyacid at 1,000 ppm of total product, showed no activity towards any organism.

TABLE IV Concentration of acid concentration mixed test product Death log10 Ex. Sample (ppm) [POAA1 / POA2 / FA3] (ppm) pH S. aureus E. coli 2 to 1000 50/50/0 3.5 6.13 > 7.30 b 1000 50/50/0 3.5 6.52 7.30 c 500 25/25/0 3.68 6.63 7.00 d 500 25/25/0 3.68 6.78 7.30 3 to 1000 50/15/35 3.52 7.18 7.30 b 1000 50/15/35 3.52 6.63 6.90 c 500 25 / 7.5 / 17.5 3.68 6.70 6J6 d 500 25 / 7.5 / 17.5 3.68 7.18 7.00 4 to 1000 0/50/0 3.5 > 7.18 > 7.30 b 1000 0/50/0 3.5 > 7.18 > 7.30 to 1000 0/15/35 3.5 > 7.18 > 7.30 b 1000 0/15/35 3.5 > 7.18 > 7.30 6 to 1000 50/0/0 3.49 NMA4 3.48 b 1000 50/0/0 3.49 NMA 3.80 7 to 1000 0/0/30 3.46 NMA NMA b 1000 0/0/30 3.46 NMA NMA - POAA = peroxyacetic acid - POA = peroxyacid 3 - FA = fatty acid 4 - NMA = no measurable activity Examples 8-11 Examples 8-11 were prepared by substantially the same procedure as the previous Examples, except that hydrogen peroxide (H2O2) was mixed with acetic acid and Cß-io fatty acids (Emery 658) to make the peroxyacids of the composition. Table V summarizes the components and amounts of the various compositions of Examples 8-11 that were made.

TABLE V Peroxyacid test formulations Ingredient Ex.8 Ex.9 Ex. 10 Ex. 11 Acetic acid 44 39 34 49 H2O2 (35%) 40 40 40 40 Dequest-L 2010 1 1 1 1 ÑAS 8D 10 10 10 10 Emery 658 5 10 15 ..

Peroxyacid stability, biocidal activity of Examples 8-11 Each of Examples 8-11 was tested for peroxyacid stability and biocidal activity, using the sanitizing test of A. O. A.C. against S. aureus and E. coli at room temperature with the formulations diluted in distilled water. Tables VI-IX show the biocidal activity of each formulation. In general, all formulations reached maximum peroxyacid formation within approximately 12 days. All formulations obtained approximately 12.5% peroxyacid except Example 10 (15% fatty acid), which obtained approximately 11.5% peroxyacid. Table VI summarizes the biocidal activity of Example 8, in which the composition was measured by biocidal activity on the first day through day 33. At 250 ppm of total product, there was about 4-5 ppm of peroxyacid and about 20 ppm of peracetic acid, as determined by carbon 13 NMR spectroscopy. The results are summarized in Table VI.

TABLE VI Peroxyacid Stability Biocidal Activity of Example 8 Day Percentage of Concentration pH of Reduction log average peroxyacid test (a) test S. aureus E. coli 1 4.28 250 ppm 3.92 6.28 NMA () 6 11.00 250 ppm 3.91 > 7.38 > 7.18 8 11.08 250 ppm 3.86 > 7.11 > 7.12 12 12.43 250 ppm 3.83 > 7.18 6.96 12.74 250 ppm 3.88 6.83 33 10.18 250 ppm 3.83 5.18 6.34 (a) ppm of total product (b) without measurable activity The biocidal activity of Example 9 is summarized in Table VII below. The concentration of peracetic acid at 250 ppm of product was about 20-21 ppm and the concentration of peroxyacid was about 11 ppm. The concentration of peracetic acid at 50 ppm of product was about 4 ppm and the concentration of peroxyacid was about 2 ppm.

TABLE VII Peroxyacid Stability Biocidal Activity of Example 9 Day Percentage of Concentration pH of Reduction log average peroxyacid test (a) test S. aureus E. coli 1 4.88 250 ppm 3.95 > 7.60 NMA (b) 6 10.62 250 ppm 3.92 > 7.38 > 7.18 8 11.61 250 ppm 3.98 > 7.11 > 7.12 12 12.47 250 ppm 3.91 > 7.18 > 7.23 15 12.00 250 ppm 3.95 6.95 120 ppm 4.18 > 7.13 50 ppm 4.41 6.39 33 10.49 250 ppm 3.85 5.20 6.22 (a) ppm of total product (b) without measurable activity The biocidal activity of Example 1 0 is summarized in Table VI I below. At 250 ppm of product, the concentration of peracetic acid was about 1 9 ppm and the concentration of peroxyacid was about 14 ppm.

TABLE VI I I Stability of peroxyacid Biocidal activity of Example 1 0 Day Percentage of Concentration pH of Reduction log average peroxyacid test (a) test S. aureus E. coli 1 4.84 250 ppm 3.90 > 7.60 NMA (b), 4.04 6 9.81 250 ppm 3.96 > 7.38 > 71.8 8 10.99 250 ppm 3.96 > 7.11 > 7.12 12 11.47 250 ppm 3.94 > 7.18 > 7.23 11.48 250 ppm 3.96 6.83 - 33 10.49 250 ppm 3.95 5.25 6.53 (a) ppm of total product () without measurable activity The biocidal activity of Example 1 1 is summarized in Table IX below. At 250 ppm of product, there was approximately 27 ppm of peracetic acid. At 1 000 ppm of product, there was approximately 1 08 ppm of peracetic acid. Acetic acid was not used in the composition of Example 1 1.

TABLE IX Biocidal activity of Example 1 1 Day Percentage of Concentration pH of Reduction log average peroxyacid test (a) test S. aureus E. coli 1 0.95 250 ppm 3.90 NMA (b) N MA 7 1 2.03 1 000 ppm 3.50 4.60 > 7.12 1 1 12.44 1 000 ppm 3.49 6.38 6.64 14 1 2.53 1 000 ppm 3.50 4. 1 7 32 1 0.77 1 000 ppm 3.45 4.77 6.44 (a) ppm of total product (b) without measurable activity When comparing the fatty acid-containing formulations (Tables VI-VI I I), poor activity against E. coli was measured one day after being formulated. Because the total peroxy acid values were low, more fatty acid was present and the gram negative bacteria tended to be less sensitive than the gram positive bacteria to the C8-C1 fatty acids 0. However, as more peroxyacid was developed On the days indicated, an increased biocidal activity was observed against E. coli. Table IX indicates that to obtain acceptable activity (greater than or equal to a 5 log reduction) using only peracetic acid, peracetic acid should be tested on 1 00 ppm active. Second, this oxidizing compound is more effective against E. coli than S. aureus.

In general, all formulations containing fatty acid remain stable after about 1 month. This was confirmed by repeated tests over time at 250 ppm of total product for each formulation, in which more than 5 log reductions against S. aureus and E. coli were measured.

Examples 12-17 The biocidal activity of a two component system containing both peracetic acid and fatty acid was investigated using the sanitizer test of A. O. A.C. Table X shows the product formulations examined. Test samples include controls that show ÑAS 8D biocidal activity, as well as death by fatty acid against S ^ aureus. All samples were tested in distilled water.

TABLE X% by weight of inqredient and Ingredient Ei. 12 E¡. 13 Ei. 14 Ei. 15 Ei. 16 E¡. 17 Base 1 (a) 80 80 80 80 - - Base 2 (b) - - - - 80 80 ÑAS 8D 10 - 10 10 10 10 Octanoic acid - - 10 - - 10 Emery 65820 - - - 10 10 - H2O 10 20 - -. -_ __ (a) H2O2, 35%; acetic acid, 35%; Dequest 2010, 1%; H3PO4 (85%), 29%.

() Acetic acid, 35%; Dequest 2010, 1%; H3PO4 (85%), 29%; H2O, 35%.

Table XI shows the activity measurement of each of Examples 12-17 at various test concentrations. When the formulation of peracetic acid of Examples 12 and 13 (which do not have a fatty acid) is tested, the biocidal activity occurred only at 100 ppm or more. The biocidal activity (greater than a 4 log reduction) was measured at a minimum concentration of 10 ppm of peroxyacid with fatty acid in the system (Example 14). At 10 ppm of peroxyacid, the composition containing Emery 658 (Example 15) had better activity than the system containing only C8 (octanoic) fatty acid (Example 14). In the fatty acid controls (Example 16 and 17), the Emery 658 had more biocidal activity than the C8 fatty acid. At total product test concentrations equivalent to 10 or 25 ppm of peroxyacid, the fatty acid in the system of Example 16 had no significant biocidal activity. Example 17 had no significant biocidal activity at any test concentration.

TABLE XI Peroxyacid biocidal activity against S. aureus Example% Concentration (ppm test pH Peroxyacid peroxyacid reduction) Log (a) 12 7.02 50 2.79 NMA (b) 100 2.54 5.45 150 2.41 > 7.70 13 6.25 50 2.76 NMA 100 2.52 4.51 150 2.40 5.84 14 9.32 10 3.52 4.22 25 3.16 > 7.70 50 2.90 > 7.70 9.73 10 3.50 6.82 25 3.19 7.55 50 2.88 > 7.70 16 .. < c) 3.53 0.70 3.18 1.04 2.88 4.07 17 _- (d) 3.51 0.93 - 0.66 (d-2) _- 0.97 (a) Test average in duplicate (b) Without measurable activity (c) Same total product concentration as Example 1 5 @ 1 0 ppm peroxyacid (approximately 1 00 ppm of product) (c- 1) ) Same total product concentration as Example 1 5 @ 25 ppm of peroxyacid (approximately 250 ppm of product) (c-2) Same total product concentration as Example 1 5 @ 50 ppm of peroxyacid (approximately 500 ppm of product) . (d) Same concentration of total product as Example 14 @ 10 ppm of peroxyacid (approximately 1000 ppm of product). (d- 1) Same concentration of total product as the Example 14 @ 25 ppm peroxyacid (approximately 250 ppm of product). (d-2) Same total product concentration as Example 14 @ 50 ppm of peroxyacid (approximately 500 ppm of product).

The biocidal activity of a peracetic acid / fatty acid system was measured by comparing fresh formulations with one month old formulations of Examples 14 and 1 5. These formulations are shown in Table XI I, which compares the values of titration of formulations of 1 month of age with the same ones just prepared. The Table XI I I shows the biocidal activity of one month old and fresh formulations of Examples 14 and 1 5.

TABLE XII Titration values of peroxyacid Ei. 14 E¡. 15 Ex. 14 Ei. fifteen Date of One month One month Fresh Fresh formulation% of H2O2 2.15 2.07 1.99 1.99 % of 5.37 5.35 4.85 4.86 peroxyacid% of total O2 2.14 2.10 1.96 1.96 TABLE XIII Peroxyacid biocidal activity against S. aureus Example% Concentration (ppm test pH Peroxyacid peroxyacid reduction) Log (a) 14 5.37 10 3.46 NMA () (one month) 25 3.07 > 7.48 14 4.85 10 3.34 5.07 (fresh) 25 2.97 7.30 5.35 10 3.52 5.29 (one month) 25 3.04 7.24 4.86 10 3.42 3.68 NMA (C) / (fresh) 25 2.99 7.48 (a) Test average in duplicate (b) No measurable activity (c) Test in duplicate in which only a sample exhibited biocidal activity As can be seen from Table XI I I, the biocidal activity in the peracetic acid / fatty acid system occurs at test concentrations as low as 10 or 25 ppm peroxy acid. The mixed results occurred at 10 ppm of peroxyacid between the one month and fresh formulations of Examples 14 and 15, however, increasing the concentration to 25 ppm resulted in a uniform death activity (reduction> 7 log) . An additional test was run to determine how rapidly the compounds exhibiting biocidal activity are formed on the addition of fatty acid to a peracetic acid system. Examples 1 2, 1 5 and 16 were tested. Examples 12 and 15 were formulated on the day before the test and there were samples of days. Another test sample of Example 1 5 was formulated just before the test. Example 1 6 containing Base 2 (without H2O2) was used to show the biocidal activity of the fatty acid at low test concentrations. Table XIV shows the biocidal activity of each Example in water distilled against S. aureus.

TABLE XIV Biocidal activity against S. aureus Example Age) m of test pH Reduction of the x-acid Log (a) 12 1 day 50 2.94 NMA () 100 2.71 6.60 15 1 day 10 3.68 7.02 25 3.35 > 7.20 15 Fresh 10 3.76 NMA 25 3.32 NMA 16 22 days .. < ) 3.74 NMA _- (d). - NMA (a) Test average in duplicate. (b) Without measurable activity (c) Equivalent total product concentration as Example 15 (one day of age) @ 10 ppm of peroxyacid. (d) Equivalent total product concentration as Example 15 (one day of age) @ 25 ppm of peroxy acid.

The data in Table XIV suggest that the formation of compounds containing biocidal activity, when fatty acid is added to a peracetic acid system is not immediate, but does occur within a day. The formation of compounds exhibiting biocidal activity occurred within a day after adding fatty acid to the peracetic acid system as in Example 15, with the biocidal activity occurring at such a low concentration with 1.0 ppm of peroxyacid. In this way, the biocidal activity is not due to the simple combination of fatty acid and peroxyacetic acid, but the fatty acid must be converted to the peroxyacid before a substantially intensified biocidal activity occurs.

EXAMPLES 1 8-22 A system of two components containing peracetic acid and peroxyacid was formed and tested to determine its sanitizing activity only on a peracetic acid system. Table XV shows the premixes 1 and 2 used to make the composition. Premixes were made with both H2O2 (35% solution), acetic acid, Dequest 201 0 and with / if n H3PO. Premix 1 was made about 5 months before premix 2. To each premix was added ΔAS 8D, a C8 fatty acid or Emery 658 as shown in Table XVI to complete the formulation of Examples 1 8-21. Example 22 was formulated as a control and had no fatty acid.

TABLE XV Premixes of peroxyacid% by weight of component Component Premix 1 Premix 2 H2O2 (35%) 75.0 35.0 Acetic acid (ice cream) 24.0 35.0 Dequest 2010 1.0 1.0 H3PO4 (85%) 29.0 TABLE XVI Peroxyacid / peracetic acid formulations% by weight of rediant ingient (control) Ei. 18 Ei. 19 Ei.20 Ei.21 Ei.22 Premix 1 80.0 - 80.0 - - Premix 2 - 80.0 - 80.0 - ÑAS 8D 10.0 10.0 10.0 10.0 - C8 fatty acid 10.0 10.0 - - - Emery 658 - - 10.0 10.0 - Acetic acid (ice cream) - - - - 24.0 H2O2 (35%) - - - - 75.0 Dequest 2010 - .. - - 1.0 Table XVII shows the measured sanitizing activity of each formulation of Examples 18-22 to 50, 100 or 150 ppm of peracetic acid against S. aureus.

TABLE XVII Sanitizing efficacy of peroxyacid / peracetic acid system vs. sanitizing efficiency of peracetic acid system Example Peroxyacid Fatty acid Concentration pH of Total reduction (a) (percentage) test test (percent) (ppm) Log (b) 18 7.69 10.0 150 3.53 > 7.06 100 3.64 > 7.06 50 3.83 > 7.06 19 11.21 10.0 150 2.71 > 7.06 100 2.80 > 7.06 50 3.08 > 7.06 9.08 10.0 150 3.64 > 7.06 100 3.65 > 7.06 50 3.85 > 7.06 21 10.92 10.0 150 2.68 > 7.06 100 2.77 > 7.06 50 3.10 > 7.06 22 10.40 - 150 3.56 7.06 (control) 100 3.68 3.89 50 3.93 NMA (C) (a) As peracetic acid (b) Test average in duplicate against S. aureus (c) Without measurable activity.

Extremely good death (log reduction> 7) with or without H3PO4 was obtained in the peroxyacid formulations of Examples 18-21. The two-component fatty acid system of C8 or Emery 658 in combination with peracetic acid (Examples 18-21) had a significantly better death than the peracetic acid system alone (Example 22) at a test concentration of 50 to 100 ppm . Activity was not measured at 50 ppm with the peracetic acid system alone of Example 22.

EXAMPLE 23-26 The effect of the length of the alkyl chain on the antimicrobial efficacy of peroxyacids was determined for percaprilic acid (C8), percapric acid (C10) and percapsilic acid / percapric acid mixture (3: 1), using the compositions of Examples 23-26 summarized in Table XVIII below. TABLE XVIII% by weight of ingredient Inquired Ei.23 Ei.24 Ei.25 Ei.26 Percaprylic acid (C8) 1 - - - Percapric acid (C10) - 1 - - Percent acid of C8 + C10 (3: 1) - - 1 - Acetic acid 10 10 10 10 Water 84 84 84 85 ÑAS 8D 5 5 5 5 The antimicrobial efficacy of Examples 23-26 is summarized in Table XIX below. Examples 23-25 were tested using three samples (a, b, c) of 5, 10 and 15 ppm of per fatty acid, respectively. Example 26, without containing perg oil, was diluted to an equivalent formulation of Examples 23-25 containing per-fatty acid. As can be seen from Table XIX, significant death occurred at 5 ppm for S. aureus, using Examples 23-25. Significant death occurred against E. coli at 10 ppm of per fatty acid in Examples 23-25. TABLE XIX Antimicrobial efficacy of Examples 23-261 Pregrase acid concentration Death log Example Sample (PP) S. aureus E. coli 23 to 5 > 7.0 3.6 b 1 0 - > 7.2 c 1 5 - > 7.2 24 to 5 > 7.0 3.0 b 1 0 - > 7.2 c 1 5 - > 7.2 to 5 > 7.0 < 3.0 b 1 0 - > 7.2, 5.5 c 1 5 -. > 7.2 26 a b Example 25 (without having per fatty acid) did not cause death of any microorganism. a - Equivalent total product concentration as Examples 23, 24, 25 to 5 ppm of per fatty acid. b - Equivalent total product concentration as Examples 23, 24, 25 to 15 ppm per fatty acid.

Example 27 The antimicrobial activity of percaprilic acid against E. coli was measured at a 30-second exposure at varying pHs. The formulation contained 94% water, 5% ÑAS 8D and 1% percaprilic acid. The formulation was diluted in a buffer of 0.05 M citrate and 0.05 M potassium phosphate. The logarithmic death of this formulation at increasing pH is summarized in Table XX. Samples containing 7 ppm and 25 ppm percaprilic acid were tested. As indicated in Table XX, significant death at 7 ppm occurred at a pH of 3.0. Significant mercury levels were maintained at 25 ppm through a pH of 7.0.

TABLE XX Antimicrobial efficacy of percaprilic acid against E. coli PH Death log Death log (per ppm concentration (per ppm concentration) per graff of 25 ppm) 3. 0 > 7.2 > 7.2 5.0 < 3.0 > 7.2 7.0 < 3.0 > 7.2 8.9 < 3.0 9.0 < 3.0 Examples 28-30 The compositions of Examples 28-30 were made to determine the limitations in the biocidal activity of the compositions containing at least 30% acetic acid. Greater acetic acid formulations were also tested for their biocidal activity. The composition of Example 30 was prepared without coupling (ÑAS 8D). The ingredients of the composition of Examples 28-30 are summarized below in Table XXI.

TABLE XXI% by weight of ingredient Inquired Example 28 Example 29 Example 30 Acetic acid 30.0 50.0 50.0 H2O2 (35%) 30.0 15.0 15.0 Dequest 2010 1.0 1.0 1.0 C8 fatty acid 4.0 6.0 5.0 ÑAS 8D (dry or 5.0 5.0 -spray) Distilled water 30.0 23.0 29.0 The antimicrobial efficacy of Examples 28-30 was determined using the sanitizing test procedure of A. O. A.C. standard. The compositions of Examples 28-30 were diluted with 500 ppm of hard water and used at 25 ° C. The bacteria used in the test procedure were S. aureus and E coli, and a TGE plating medium was used. The exposure time of the compositions to the bacteria was 30 seconds. The neutralizer used in the test procedure contained 0.1% thiosulfate, 1.0% peptone and 0.025% catalase. The antimicrobial activity of Examples 28-30 is summarized in Table XXII below.

TABLE XXII Biocidal activity of Examples 28-30 Log reduction Formulation Concentration pH S. aureus E. coli Example 28 0.02951: 30.281a 4.48 > 7.15 > 6.89 0.02951: 37.85 lb 4.83 > 7.15 > 6.89 0.02951: 45.42 I c 5.04 > 7.15 6.41 0.02951: 52.99 ld 5.52 > 7.15 5.76 0.02951: 60.56 le 5.94 > 7.15 2.95 Example 29 40 ppm of active 4.16 > 7.15 > 6.89 Example 30 40 ppm of active 4.04 > 7.15 > 6.89 to 54.2 ppm of peroxyacid b 43.3 ppm of peroxyacid c 36.1 ppm of peroxyacid d 31.0 ppm of peroxyacid e 27.2 ppm of peroxyacid As Table XXII indicates, very low concentrations of peroxyacetic acid and peroxyacetic acid combinations are very effective in killing bacteria. In addition, Example 30 showed that the composition of the invention is antimicrobially effective without a hydrotrope coupler.

Example A Objective: The objective of this analysis was to determine the antimicrobial efficacy of Example A, when prepared in synthetic hard water of 80 ppm and 500 ppm at a concentration of 2.2% against ascospores Chaetomium bostrychodes (isolated from mold of Coca-Cola Japan), using exposure times of 30 seconds, 1.0 minute, 2.0 minutes and 5.0 minutes.

Parameters of the method: Test system: Ascospores of Chaetomium bostrychodes (mold contaminant of Coca-Cola Japan) Test temperatures: 40 ° C and 50 ° C Exposure times: 30 seconds, 1.0, 2.0 and 5.0 minutes. Neutralizer: 1% sodium thiosulfate Platinum medium: Potato dextrose agar (PDA) Incubation: 5-7 days at 26 ° C Results: Control numbers (CFU / ml) Average survivors of Chaetomium bostrychodes (CFU / ml) at 40 ° C Average survivors of Chaetomium bostrychodes (CFU / ml) at 50 ° C Log reductions of Chaetomium bostrychodes at 40 ° C Log reductions of Chaetomium bostrychodes at 50 ° C Conclusions Example A to 2.2%, when diluted as much in 80 ppm as 500 ppm of synthetic hard water, reached a log reduction of > 6.08 (without survivors) after an exposure time of 2.0 minutes at 50 ° C, while reaching a reduction < 1 .00 log at 30 seconds and 1 .0 minute. At 40 ° C, Example A achieved a log reduction of 2.90 (80 ppm of synthetic hard water) and one of 2.72 (500 ppm of synthetic hard water), after an exposure time of 5.0 minutes, while a reduction < 1 .00 log to 30 seconds, 1 .0 m inuto and 2.0 minutes. To achieve a total mortality of the ascospores of Chaetomium bostrychodes, Example A should be used at a concentration of 2.2% at 50 ° C, using an exposure time of 2.0 minutes.

Example B Objective: The objective of this analysis was to determine the antimicrobial efficacy of Example B and Example C when prepared in 80 ppm and 500 ppm of synthetic hard water at concentrations of 0.85% of Example B and 0.05% of Example C, against ascospores of Chaetomium bostrychodes (isolated from Coca-Cola Japan mold), using exposure times of 30 seconds, 1 .0 m inuto, 2.0 m inutes and 5.0 minutes.

Method parameters: Test system: Ascospores of Chaetomium bostrychodes (mold contaminant of Coca-Cola Japan) Test temperatures: 40 ° C and 50 ° C Exposure time: 30 seconds, 1.0, 2.0 and 5.0 minutes. Neutralizer: 1% sodium thiosulfate Platinum medium: Potato dextrose agar (PDA) Incubation: 5-7 days at 26 ° C Results: Control numbers (CFU / ml) Test system A B C Average Chaetomium bostrychodes 5 x 104 4 x 104 7 x 104 5.3 x 104 Average survivors of Chaetomium bostrychodes (CFU / ml) at 40 ° C Average survivors of Chaetomium bostrychodes (CFU / ml) at 50 ° C Log reductions of Chaetomium bostrychodes at 40 ° C Log reductions of Chaetomium bostrychodes at 50 ° C Conclusions: Example B at 0.85% when diluted in both 80 ppm and 500 ppm synthetic hard water reached a reduction > 3J2 log after an exposure time of 5.0 minutes at 50 ° C, while reaching a reduction < 1.50 log to 30 seconds, 1.0 minute and 2.0 minutes. At 40 ° C, Example B achieved a reduction < 1.00 log at all exposure times. Example C achieved a reduction < 1.00 log when diluted in both 80 ppm and 500 ppm synthetic hard water at both 40 ° C and 50 ° C at all exposure times. Example C was prepared at 0.05%, which is the highest concentration possible to obtain solubility. The percentage of peracetic acid in Example C is 10.16, while Example C contains 11.4 percent. Although the concentrations of peracetic acid in both products are similar, Example C can be used at a much higher dilution due to the absence of octanoic acid in the formula. Example C performed similarly to Example A at 50 ° C after an exposure time of 5.0 minutes, while at 40 ° C, Example A demonstrated better efficiency by reaching approximately a reduction of 2.60 log after a while. of 5.0 minutes exposure.

Example C Objective: The objective of this analysis was to determine the antimicrobial efficacy of Example D and Example a when prepared in 500 ppm of synthetic hard water as CaCO3 at concentrations of 1.0% of Example A and 0. 1.75% of Example A against Chaetomium bostrychodes using exposure times of 30 seconds, 1.0 m inuto, 2.0 m inutes, 5.0 min utes and 1 0.0 minutes.

Parameters of the method: Test system: Ascospores of Chaetomium bostrychodes (mold contaminant of Coca-Cola Japan) Test temperatures: 25 ° C and 40 ° C Exposure times: 30 seconds, 1 .0, 2.0, 5.0 and 1 0.0 m inutes.

Neutralizer: 1% sodium thiosulfate / 1% peptone / 0.025% catalase Platinum medium: Potato dextrose agar (PDA) Incubation: 5-7 days (or until growth is visible at 26 ° C Results: Inoculation numbers (CFU / ml) Survivors of Chaetomium bostrychodes (CFU / ml) Log reduction of Chaetomium bostrychodes Conclusions: The results of this analysis showed that at 25 ° C, Example D and Example A were similar in efficacy against Chaetomium bostrychodes. Example A at the exposure time of 30 seconds, reached a log reduction of 2.38, while Example A D reached a log reduction of 2.26. Example A and Example D were relatively static at subsequent exposure times. The Example at 40 ° C achieved a log reduction of 2.23 at the exposure time of 30 seconds, while Example D had a log reduction of 2.32 at the exposure time of 30 seconds. Example A and Example D were both static at subsequent exposure times. Additional tests will be performed using 2.2% of Example A and 4.0% of Example D in 500 ppm of synthetic hard water such as CaCO3 and deionized water.

Example D Objective: The objective of this analysis was to determine the antimicrobial efficacy of the Alo ploy A when prepared in 80 ppm and 500 ppm of synthetic hard water at a concentration of 2.2% against ascospores of Arthrinium sacchari (isolated from Coca-Cola Japan mold. ), using exposure times of 30 seconds, 1.0 m inuto, 2.0 minutes and 5.0 minutes.

Parameters of the method: Test system: Ascospores of Arthrinium sacchari (mold contaminant of Coca-Cola Japan) Test temperatures: 40 ° C and 50 ° C Exposure times: 30 seconds, 1.0, 2.0 and 5.0 minutes. Neutralizer: 1% sodium thiosulfate Platinum medium: Potato dextrose agar (PDA) I incubation: 5-7 days at 26 ° C Resuted: Control numbers (CFU / ml) Average survivors of Arthrinium sacchari (CFU / ml) at 40 ° C Average survivors of Arthrinium sacchari (CFU / ml) at 50 ° C Log reductions of Arthrinium sacchari at 40 ° C Log reductions of Arthrinium sacchari at 50 ° C Conclusions: Axis A to 2.2% when diluted as much in 80 ppm as 500 ppm of synthetic hard water, reached a reduction > 6.95 log (without survivors) after an exposure time of 1.0 minute at 50 ° C, while reaching an average log reduction of 2.34 after 30 seconds. At 40 ° C, Example A achieved an average log reduction of 2.16, when diluted both in 80 ppm and 500 ppm of synthetic hard water at all exposure times. To achieve total death of ascorpores from Arthrinium sacchari, Example A should be used at a concentration of 2.2% at 50 ° C, using an exposure time of 1.0 minute. The discussion and previous Examples are illustrative of the invention. However, because many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides fully in the claims appended hereto.

Claims (13)

1. CLAIMS 1 . A method for sanitizing a plant beverage, the plant comprising an assembly of tanks, pipes or lines, bom bas and valves or other mixing equipment, said com method comprises contacting the plant with a ución sun sanitizer use peroxyacid for at least 30 seconds, to achieve at least a reduction in fungal microbial population 5 log 1 0, wherein the solution of peroxyacid sanitizer use com turns at least 1 0 parts per million (ppm) of a peroxycarboxylic acid of C? C4 and at least 1 ppm of a C6-C1 peroxyacid 8. 2. a method em botellado beverage, aseptic, cold, obtaining at least a reduction in microbial population fungal log1 0 5, resulting in a sanitized beverage container , comprising the method: contacting a beverage container with an antimicrobial use of peroxyacid for at least 30 seconds, to reduce the fungal microbial population; rinse the container and fill the container with a carbonated drink followed by a sealing step; wherein the solution of peroxyacid icrobiana antim use com turns at least 1 0 parts per million (ppm) of a peroxycarboxylic acid of C1 -C and at least 1 ppm of a C6-C1 peroxyacid 8. 3. The method of Claim 1 or 2, wherein the use solution is formed by diluting a concentrate composition having a weight ratio of about 20 to 1 part of (a) per part of (b), and which is capable of being diluted with a greater proportion of water for ¿*. forming an antimicrobial use solution having a pH in the range of 2 to 8. The method of claim 1 or 2, wherein the use solution is formed from diluting a concentrate composition, which comprises 0.01 to 25% by weight of said C-peroxycarboxylic acid? -C4. The method of claim 1 or 2, wherein said C 1 -C peroxycarboxylic acid comprises peroxyacetic acid, peroxy glycolic acid or mixtures thereof. 6. The method of claim 1 or 2, wherein said peroxyacid Zeal C-i ß comprises peroxyoctanoic acid, peroxidecanoico acid, monoperoxy- or Ipeak diperoxiad, monoperoxy- or di peroxisebácico acid, or mixtures thereof. 7. The method of claim 1 or 2, wherein the weight ratio of said peroxycarboxylic acid of C? -C4 to said C6-C18 peroxyacid is 15 1 5: 1 to 3: 1. 8. The method of claim 1 or 2, further com- prizing an effective amount of an hydrotrope coupling people capable of solubilizing said C6-C1-8 peroxy acid in the concentrate, when the concentrate is diluted with water. 9. The method of claim 1 or 2, wherein said use solution is formed from a concentrate stream comprising from 1 to 50% by weight of hydrogen peroxide. The method of claim 1 or 2, wherein the fungus is of the genus Chaetomium. 11. The method of claim 1 or 2, wherein the fungus is of the genus Arthrinium. 12. The method of claim 1 or 2, wherein the beverage is carbonated. The method of claim 1 or 2, wherein the beverage is a noncarbonated fruit beverage or tea.