BEVERAGE MANUFACTURE AND COLD ASEPTIC BOTTLING USING PEROXYACID ANTIMICROBIAL COMPOSITION

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: BEVERAGE MANUFACTURE AND COLD ASEPTIC BOTTLING USING PEROXYACID ANTIMICROBIAL COMPOSITION Field of the Invention The invention relates generally to processes using antimicrobial or biocidal compositions. More particularly, the invention relates to peroxyacid antimicrobial concentrates and use solutions which can sanitize various surfaces such as facilities, containers or equipment found in the food or beverage processing in food service industries at or near ambient temperatures. Background of the Invention Numerous classes of chemical compounds exhibit varying degrees of antimicrobial or biocidal activity. Antimicrobial compositions are particularly needed in the food and beverage industries to clean and sanitize processing facilities such as pipelines, tanks, mixers, etc. and continuously operating homogenation or pasteurization apparatus. Sanitizing compositions have been formulated in the past to combat microbial growth in such facilities. For example, Grosse-Bδwing, U.S. Patent No. 4,051,058 and 4,051,059 teaches peracetic acid materials. These peroxy- containing compositions are known for use in the production of microbicidal agents. One such composition is disclosed in Grosse-Bδwing 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, U.S. Patent No. 4,404,040, teaches a short chain fatty acid sanitizing composition comprising an aliphatic short chain fatty acid, a hydrotrope solubilizer capable of solubilizing the fatty acid in both the concentrate and use solution, and a hydrotrope compatible 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 greater than 100 part per million (ppm)). Similarly, peroxyfatty acids have also been shown to be biocidal, but only at high concentrations (greater than 200 ppm), such as in the composition disclosed in European Patent Application No. 233,731. Antimicrobial compositions having low use concentrations (less than 100 ppm) which effectively kill microbes are particularly desirable. Low concentrations minimize use cost, surface corrosion, odor, carryover of biocide into foods and potential toxic effects to the user. Therefore, a continuing need exists to provide such an antimicrobial composition for use in food processing, food service and health care facilities. In contrast to the prior art, the composition of the present invention has the unique advantage of having antimicrobial or biocidal activity at low level use concentrations. Summary of the Invention The invention is a peroxyacid antimicrobial concentrate and diluted end use composition comprising an effective microbicidal amount of a C,-C 4 peroxycarboxylic acid or an effective microbicidal amount of a C,-C 4 peroxycarboxylic acid combined with an effective microbicidal amount of a C 6 -C 18 peroxyacid. The concentrate composition can be diluted with a major proportion of water to form an antimicrobial, sanitizing use solution having a pH in the range of about 2 to 8, with a C r C 4 peroxycarboxylic acid concentration of at least about 10 ppm, preferably about 10 to 75 ppm, and a C 6 -C ]8 peroxyacid concentration of at least about 1 ppm, preferably about 1 to 25 ppm. Other components may be added such as a hydrotrope coupling agent for solubilizing the peroxyfatty acid in the concentrate form and when the concentrate composition is diluted with water. In contrast to the prior art, we have discovered that at a low pH, (e.g. preferably less than 5) C 6 -C 18 peroxyacids such as peroxyfatty acids are very potent biocides at low levels. When used in combination with a C,-C 4 peroxycarboxylic acid such as peroxyacetic acid, a synergistic effect is obtained, providing a much more potent biocide than can be obtained by using these components separately. This means that substantially lower concentrations of biocide can be used to obtain equal biocidal effects, leading to lower costs of the product and less potential for corrosion. As the term is used herein, a C 6 -C 18 peroxyacid (or peracid) is intended to mean the product of the oxidation of a C 6 -C 18 acid such as a fatty acid, or a mixture of acids, to form a peroxyacid having from about 6 to 18 carbon atoms per molecule. The C,-C 4 peroxycarboxylic acid is intended to mean the product of oxidation of a C,-C 4 carboxylic acid, or a mixture thereof. This includes both simple and substituted C,- C 4 carboxylic acids. A method of sanitizing facilities or equipment comprises the steps of contacting the facilities or equipment with the use solution made from the above 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 or room temperature conditions. The composition is then circulated or left in contact with the container, facilities or equipment for a time sufficient to sanitize (generally at least 30 seconds) and the composition is thereafter 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, yeast and mold. In particular the methods are surprisingly effective for aseptic cold filling of beverage containers. The compositions are effective against either fungal genus, Chaetomium or Arthrinium, that 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 major proportion of water to form a sanitizing use solution. A further aspect of the invention is an aqueous antimicrobial sanitizing use solution which is particularly suited for "in-place" cleaning applications. A further aspect of the invention is a method of employing the use solution of the invention in the cleaning or sanitizing of various process facilities or 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 either carbonated or non-carbonated beverages can be prepared and bottled. Detailed Description of the Invention The invention resides in a peroxyacid antimicrobial concentrate and use composition comprising an effective microbicidal amount of a C,-C 4 peroxycarboxylic acid or an effective microbicidal amount of a C,-C 4 peroxycarboxylic acid combined with an effective microbicidal amount of a C 6 -C 18 peroxyacid. We have found that combining these acids produces a synergistic effect, producing a much more potent biocide than can be obtained by using these components separately. The concentrate composition can be diluted with a major proportion of water to form an antimicrobial sanitizing use solution having a pH in the range of about 2 to 8. The sanitizing use solution can be used effectively to clean or sanitize facilities and equipment used in the food processing, food service and health care industries. Peroxyacids Peroxy-containing concentrates which are stable in storage can be obtained which are useful for the production and supplementation of microbicides based in aliphatic monopercarboxylic acids. These peroxy-containing concentrates are characterized by a content of 0.5% to 20% by weight of a per acid with 2 to 3 carbon atoms and/or the corresponding aliphatic noncarboxylic acid, as well as 25% to 40% by weight of H 2 O 2 , and the balance, water. More particularly, the invention relates to a peroxy-containing concentrate, stable in storage, comprising from 0.5% to 20% by weight of an acid selected from the group consisting of peracetic acid, acetic acid, perpropionic acid, propionic acid, mixtures of peracetic acid and acetic acid, and mixtures of perpropionic acid and propionic acid, from 25% to 40% by weight of H 2 O 2 , from 0 to 5% by weight of an anionic surface-active compound selected from the group consisting of sulfonates and sulfates, and the remainder to 100%) by weight, water. Preferably, the storage-stable peroxy-containing concentrates contain from 5% to 10%o by weight of component (1), and a molar excess of H 2 O 2 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 anionic surface- active compound of the sulfonate and the sulfate type is present, it is preferably in an amount of from 0.5% to 5% by weight. The production is effected in a simple manner by mixing an H 2 O 2 solution, preferably with a concentration of about 33% by the weight with per acid 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 H 2 O 2 solution. Since the products mainly are not used at once, but are first stored, a corresponding content of peracetic acid is formed when acetic acid is employed. The formation of peracetic acid can be catalytically accelerated, if desired, by adding a small amount of a mineral acid (0.1 % to 1% by weight). In general, however, such an addition is not necessary for the above-mentioned reasons. Such concentrates, which are produced, for example, from 30% of H 2 O 2 , 5% of acetic acid and 65% of water, have no annoying odor and are easy to handle, that is, they can be easily diluted to the concentration of 0.1% 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, it is sometimes of advantage to add a wetting agent in order to improve the desired properties further. It was found that stable concentrates of the above-described type can be obtained if anionic surface-active compounds of the sulfonate and sulfate type, such as alkylbenzene sulfonates having 6 to 18 carbon atoms in the alkyl, alkyl sulfates and/or alkane sulfonates (each having 8 to 22 carbon atoms in the alkyl or alkane groups) are added in amounts of 0.05% to 5% by weight. The alkylbenzene sulfonates which can be employed are preferably those which contain an alkyl radical of 6 to 18 carbon atoms, preferably 9 to 15 carbon atoms. Instead of the alkylbenzene sulfonates, alkyl sulfates or alkane sulfonates with an alkyl or alkane radical of the chain length 12 to 18 carbon atoms, can be employed. If desired, mixtures of the above-mentioned anionic surface-active compounds can naturally also be used. It was found that, with the above-mentioned additives, the concentrates remain stable over long periods of time and that the content of peracetic acid in the concentrate thus also remains constant. However, if soaps or the conventional nonionic surface-active compounds are employed as the surface-active additive, a 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 is to be achieved and the disadvantages of the known pure per acids render their application difficult or impossible. The concentrates have, furthermore, the advantage that they can be employed to produce function agents for static disinfections to prevent the growth of germs on machines after cleaning, particularly in the food industry. Due to their content of H 2 O 2 , they have a long-term effect on most microorganisms. The pH-value of the solution produced is still weakly acid, and the residues of acetic acid after the disinfection are extremely small, so that the agents are also suitable for disinfections where rinsing 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 soft drinks. The materials can be used to sanitize bottles, pumps, lines, tanks and mixing equipment used in the manufacture of such beverages. Further, the peroxyacid materials can be used in aseptic, cold 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 sanitizing peroxyacid material, typically using a spray device to intimately contact the inside of then container with the peroxyacid, for sufficient period of time to reduce microorganism populations within the container. The container is then emptied of the amount of sanitizer used. After emptying, the container can then be commonly rinsed 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 packed for shipment for ultimate sale. The sealed container can be autoclaved or retorted for added microorganism kill. In beverage manufacture, we have found that a fungal microorganisms of the genus Chaetomium or Arthrinium can be a significant problem in bottling processes, particularly in cold aseptic bottling processes. The peroxyacid sanitizer materials of the invention can be used for the purpose of controlling or substantially reducing (by more than a 5 log 10 reduction) the number of Chaetomium or Arthrinium microorganisms in beverage bottling lines using cold aseptic bottling techniques. In such techniques, metallic, aluminum or steel cans can be filled, glass bottles or containers can be filled or plastic (PET or PBT or PEN bottles) 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. Typical carbonated beverages in this application include cola beverage, fruit beverages, ginger ale beverages, root beer beverages, iced tea beverages which may be non-carbonated, and other common beverages considered soft drinks. The peroxyacid materials of the invention can be used to sanitize both the tanks, lines, pumps, and other equipment used for the manufacture and storage of the soft drink material and also used in the bottling or containers for the beverages. The peroxyacid sanitizing materials are useful for killing both bacterial and fungal microorganisms that can be present on the surfaces of the production equipment and beverage containers. The present invention is based upon the surprising discovery that when a C 5 - C ]8 peroxyacid is combined with a C,-C 4 peroxycarboxylic acid, a synergistic effect is produced and greatly enhanced antimicrobial activity is exhibited when compared to the C 5 -C 18 peroxyacid or the C C 4 peroxycarboxylic acid alone. The present blend of a C 5 -C 18 peroxyacid and a C,-C 4 peroxycarboxylic acid can effectively kill microorganisms (e.g., a 5 log 10 reduction in 30 seconds) from a concentration level below 100 ppm and as low as 20 ppm of the peroxyacid blend. A variety of a C 5 -C 18 or a C 6 -C 18 peroxyacids may be employed in the composition of the invention such as peroxyfatty acids, monoperoxy or diperoxydicarboxylic acids, and peroxyaromatic acids. The C 6 -C 18 peroxyacids employed in the present invention may be structurally represented as follows: R,- CO 3 H, wherein R, is a hydrocarbon moiety having from about 5 to 17 carbon atoms (a C 8 peroxyacid is generally represented structurally as C 7 -CO 3 H). R, may have substituents in the chain, e.g., -OH, CO 2 H, or heteroatoms (e.g., -0- as in alkylether carboxylic acids), as long as the antimicrobial properties of the overall composition are not significantly affected. It should be recognized that "R," substituents or heteroatoms may change the overall acidity (i.e., pKa) of the carboxylic acids herein described. Such modification is within the contemplation of the present invention provided the advantageous antimicrobial performance is maintained. Furthermore, R, may be linear, branched, cyclic or aromatic. Preferred hydrocarbon moieties (i.e. preferred R s) include linear, saturated, hydrocarbon aliphatic moieties having from 7 to 11 carbon atoms (or 8 to 12 carbon atoms per molecule). Specific examples of suitable C 6 -C 18 carboxylic acids which can be reacted with hydrogen peroxide to form peroxyacids include such saturated acids as hexanoic (C 6 ), enanthic (heptanoic) (C 7 ), caprylic (octanoic) (C 8 ), pelargonic (nonanoic) (C g ), capric (decanoic) (C 10 ), undecyclic (undecanoic) (C n ), lauric (dodecanoic) (C 12 ), trideclic (tridecanoic) (C 13 ), myristic (tetradecanoic) (C 14 ), palmitic (hexadecanoic) (C 16 ), and stearic (octodecanoic) (C ι8 ). These acids can be derived from both natural and synthetic sources. Natural sources include animal and vegetable fats or oils which should be fully hydrogenated. Synthetic acids can be produced by the oxidation of petroleum wax. Particularly preferred peroxyfatty acids for use in the composition of the invention are linear monoperoxy aliphatic fatty acids such as peroxyoctanoic acid, peroxydecanoic acid, or mixtures thereof. Other suitable C 6 -C 18 peroxyacids are derived from the oxidation of dicarboxylic acids and aromatic acids. Suitable dicarboxylic acids include adipic acid (C 6 ), glutaric acid (C 5 ) and sebacic acid (C I0 ). An example of a suitable aromatic acid is benzoic acid. These acids can be reacted with hydrogen peroxide to form the peroxyacid 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, yeast, molds (e.g. Chaetonium, Arthrinium and similar genera), bacterial spores, etc. When the above C 6 -C 18 peroxyacids are combined with a C,-C 4 peroxycarboxylic acid, greatly enhanced activity is shown compared to the C,-C 4 peroxycarboxylic acid alone or the C 6 -C 18 peroxyacid alone. The C,-C 4 peroxycarboxylic acid component can be derived from a C r C 4 carboxylic acid or dicarboxylic acid by reacting the acid with hydrogen peroxide. Examples of suitable C,-C 4 carboxylic acids include acetic acid, propionic acid, glycolic acid, and succinic acid. Preferable C,-C 4 peroxycarboxylic acids for use in the composition of the invention include peroxyacetic acid, peroxypropionic acid, peroxyglycolic acid, peroxysuccinic acid, or mixtures thereof. The antimicrobial concentrate of the present invention can comprise about 0.01 to 10 wt-%, preferably about 0.05 to 5 wt-%, and most preferably about 0.1 to 2 wt-% of a C 6 -C 18 peroxyacid, and about 0.1 to 25 wt-%, preferably about 0.5 to 20 wt-%, and most preferably about 1 to 15 wt-% of a C r C 4 peroxycarboxylic acid. The concentrate composition preferably has a weight ratio of C,-C 4 peroxycarboxylic acid to C 6 -C 18 peroxyacid of about 15:1 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 be optionally 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 hydrogen peroxide (H 2 O 2 ) solution with the desired amount of acid. With the higher molecular weight acids, a hydrotrope coupler may be required to help solubilize the acid. The H 2 O 2 solution also can be added to previously made peroxyacids such as peracetic acid or various peroxyacids to produce the peroxyacid composition of the invention. The concentrate can contain about 1 to 50 wt-%, preferably about 5 to 25 wt-% of hydrogen peroxide. The concentrate composition can further comprise a free C 6 -C, 8 carboxylic acid, a free C,-C 4 carboxylic acid, or mixtures thereof. The free acids will preferably correspond to the starting materials used in the preparation of the peroxyacid components. The free C 6 -C, 8 carboxylic acid is preferably linear and saturated, has 8 to 12 carbon atoms per molecule, and can also comprise a mixture of acids. The free C 6 -C 18 carboxylic acid and free C,-C 4 carboxylic acid can be present as a result of an equilibrium reaction with the hydrogen peroxide to form the peroxyacids. Optional Components Various optional materials may be added to the composition of the invention to help solubilize the fatty acids, restrict or enhance the formation of foam, to control hard water, to stabilize the composition, or to further enhance the antimicrobial activity of the composition. The composition of the invention can contain a surfactant hydrotrope coupling agent or solubilizer that permits blending short chain peroxy acids in aqueous liquids. Functionally speaking, the suitable couplers which can be employed are non-toxic and retain the fatty acid and the peroxy acid in aqueous solution throughout the temperature range and concentration to which a concentrate or any use solution is exposed. Any hydrotrope coupler may be used provided it does not react with the other components of the composition or negatively affect the antimicrobial properties of the composition. Representative classes of hydro tropic coupling agents or solubilizers which can be employed include anionic surfactants such as alkyl sulfates and alkane sulfonates, linear alkyl benzene or naphthalene sulfonates, secondary alkane sulfonates, alkyl ether sulfates or sulfonates, alkyl phosphates or phosphonates, dialkyl sulfosuccinic acid esters, sugar esters (e.g., sorbitan esters) and C 8 -C ]0 alkyl glucosides. Preferred coupling agents for use in the present invention include noctanesulfonate, available as NAS 8D from Ecolab, and the commonly available aromatic sulfonates such as the alkyl benzene sulfonates (e.g. xylene sulfonates) or naphthalene sulfonates. Some of the above hydrotropic coupling agents independently exhibit antimicrobial activity at low pH. This adds to the efficacy of the present invention, but is not the primary criterion used in selecting an appropriate coupling agent. Since it is the presence of peroxy acid in the protonated neutral state which provides 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 peroxy acids described herein and the microorganisms which the present compositions control. The hydrotrope coupling agent can comprise about 0.1 to 30 wt-%, preferably about 1 to 20 wt-%, and most preferably about 2 to 15 wt-% of the concentrate composition. Compounds such as mono, di and trialkyl phosphate esters may be added to the composition to suppress 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. Alkyl phosphate esters possess some antimicrobial activity in their own right under the conditions of the present invention. This antimicrobial activity also tends to add to the overall antimicrobial activity of the present compositions even though the phosphate esters may be added for other reasons. Furthermore, the addition of nonionic surfactants would tend to reduce foam formation herein. Such materials tend to enhance performance of the other components of the composition, particularly in cold or soft water. A particularly useful nonionic surfactant for use as a defoamer is nonylphenol having an average of 12 moles of ethylene oxide condensed thereon, it being encapped with a hydrophobic 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, cleaning performance and stability of the peroxyacids. For example, l-hydroxyethylidene-l,l-diphosphonic acid commercially available from the Monsanto Company under the designation "DEQUEST" has been found to be effective. Chelating agents can be added to the present composition to control or sequester hardness ions such as calcium and magnesium. In this manner both detergency and sanitization capability can be enhanced. Other materials which are sufficiently stable at the low pH contemplated by the present composition may be added to the composition to impart desirable qualities depending upon the intended ultimate use. For example, phosphoric acid (H 3 PO 4 ) can be added to the composition of the invention. Additional compounds can be added to the concentrate (and thus ultimately to the use solution) to change its color or odor, to adjust its viscosity, to enhance its thermal (i.e., freeze-thaw) stability or to provide other qualities which 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 18 peroxyacid such as a peroxyacid with some source of a C,-C 4 peroxycarboxylic acid such as 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,-C 4 carboxylic acid, a C 6 -C 18 carboxylic acid, a coupler and a stabilizer and reacting this mixture with hydrogen peroxide. A stable equilibrium mixture is produced containing a C,-C 4 peroxycarboxylic acid and a C 6 -C 18 peroxyacid by allowing the mixture to stand for from one to seven days at 15°C to 25°C. As with any aqueous reaction of hydrogen peroxide with a free carboxylic acid, this gives a true equilibrium mixture. In this case, the equilibrium mixture will contain hydrogen peroxide, a C,- C 4 carboxylic acid, a C 6 -C I8 carboxylic acid, a C,-C 4 peroxycarboxylic acid, a C 6 -C 18 peroxyacid, water, and various couplers and stabilizers. By using the above approach, the composition of the invention can be formulated by merely mixing readily available raw materials, e.g., acetic acid, hydrogen peroxide and fatty acid. By allowing solution time for equilibrium to be obtained, the product containing both of the active biocides is obtained. In varying the ratio of C r C 4 carboxylic acid to C 6 -C 18 carboxylic acid, it is easy to vary the ratio of C Γ C 4 peroxycarboxylic acid to C 6 -C, 8 peroxyacid. Concentrate and Use Compositions The present invention contemplates a concentrate composition which is diluted to a use solution prior to its utilization as a sanitizer. Primarily for reasons of economics, the concentrate would normally be marketed and the end user would dilute the concentrate with water to a use solution. A preferred antimicrobial concentrate composition comprises about 0.01 to 10 wt-%, preferably about 0.05 to 5 wt-%), of a C 6 -C 18 peroxyfatty acid, about 0.1 to 25 wt-%, preferably about 0.5 to 20 wt-%), of a C,-C 4 peroxycarboxylic acid, about 0.1 to 30 wt-% of a hydrotrope coupling agent, and about 1 to 50 wt-% of hydrogen peroxide. Other acidulants may optionally be employed in the composition such as phosphoric acid. The level of active components in the concentrate composition is dependent upon the intended dilution factor and desired acidity in the use solution. The C 6 -C 18 peroxyacid component is generally obtained by reacting a C 6 -C 18 carboxylic acid with hydrogen peroxide in the presence of a C r C 4 carboxylic acid. The resulting concentrate is diluted with water to provide the use solution. Generally, a dilution of 1 fluid oz. to 4 gallons (i.e. dilution of 1 to 500 by volume) or to 8 gallons (i.e. dilution of 1 to 1,000 by volume) of water can be obtained with 2% to 20% total peroxyacids in the concentrate. Higher use dilution can be employed if elevated use temperature (greater than 20°C.) or extended exposure time (greater than 30 seconds) are also employed. In its intended end use, the concentrate is diluted with a major proportion of water and used for purposes of sanitization. The typical concentrate composition described above is diluted with available tap or service water to a formulation of approximately 1 oz. concentrate to 8 gallons of water. An aqueous antimicrobial sanitizing use solution comprises at least about 1 part per million (ppm), preferably about 2 to 10 ppm of a C 6 -C 18 peroxyacid, and at least about 10 ppm, preferably about 20 to 50 ppm of a C,-C 4 peroxycarboxylic acid. The weight ratio of C 6 -C 18 peroxyacid to C,-C 4 peroxycarboxylic acid ranges from about 0.01 to 0.5 parts, preferably about 0.02 to 0.2 parts of C 6 -C 18 peroxyacid per part of C,-C 4 peroxycarboxylic acid. Preferably the total peroxyacid 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 employed in the use solution to obtain disinfecting or sterilizing results. The aqueous use solution can 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 of hydrogen peroxide, and at least about 1 ppm, preferably about 2 to 200 ppm of a free C 6 -C 18 carboxylic acid, a free C,-C 4 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 the cleaning or sanitizing of containers processing facilities or equipment in the food service, food processing or health care industries. Examples of process facilities in which the composition of the invention can be employed include a milk line dairy, a continuous brewing system, food processing lines such as pumpable food systems and beverage lines, etc. Food service wares can also be disinfected with the composition of the invention. The composition is also useful in sanitizing or disinfecting solid surfaces such as floors, counters, furniture, medical tools and equipment, etc., found in the health care industry. Such surfaces often become contaminated with liquid body spills such as blood, other hazardous body fluids or mixtures thereof. Containers include glass bottles , , PVC or polyolefm film sacks, cans, polyester, PEN or PET bottles of various volumes (100 ml to 2 liter, etc.), one gallon milk containers, paper board juice or milk containers, etc. Generally, the actual cleaning of the in-place system or other surface (i.e., removal of unwanted offal therein) is accomplished with a different material such as a formulated detergent which is introduced with heated water. After this cleaning step, the instant sanitizing composition would be applied or introduced into the system at a use solution concentration in unheated, ambient temperature water. The present sanitizing composition is found to remain in solution in cold (e.g., 40°F./4°C.) water and heated (e.g., 140°F./60° C.) water. Although it is not normally necessary to heat the aqueous use solution of the present composition, under some circumstances heating may be desirable to further enhance its antimicrobial activity. These materials are useful at any conceivable temperatures. A method of sanitizing substantially fixed in-place process facilities 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 introduction of the use solution, the solution is held in a container or circulated throughout the system for a time sufficient to sanitize the process facilities (i.e., 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 sanitizing step, the system optionally may be rinsed with other materials such as potable water. The composition is preferably circulated through the process facilities for 10 minutes or less. The composition may also be employed by dipping food processing equipment into the use solution, soaking the equipment for a time sufficient to sanitize the equipment,, and wiping or draining excess solution off the equipment, The composition may be further employed by spraying or wiping food processing surfaces with the use solution, keeping the surfaces wet for a time sufficient to sanitize the surfaces, and removing excess solution by wiping, draining vertically, vacuuming, etc. The composition of the invention may also be used in a method of sanitizing hard surfaces such as institutional type equipment, utensils, dishes, health care equipment or tools, and other hard surfaces. The composition may also be employed in sanitizing clothing items or fabric which have become contaminated. The use composition is contacted with any of the above contaminated surfaces or items at use temperatures in the range of about 4°C to 60°C, for a period of time effective to sanitize, disinfect, or sterilize the surface or item. For example, the concentrate composition can be injected into the wash or rinse water of a laundry machine and contacted with contaminated fabric for a time sufficient to sanitize the fabric. Excess solution can then be removed by rinsing or centrifuging the fabric. As the term "sanitizing" is used in the method of the instant invention, it means a reduction in the population numbers of undesirable microorganisms by about 5 powers of 10 or greater (i.e., at least 5 orders of magnitude) after a 30 second exposure time. It is to be emphasized that the instant use solution provides cleaning as well as sanitizing performance although its primary utility is sanitizing. The composition may also be used-to achieve disinfection or sterilization (i.e., elimination of all microorganisms) by employing higher levels of peroxyacids in the use solution. The following Examples are intended to illustrate the above invention and should not be construed as to narrow 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 a bottle spraying/bottling operation using a peroxyacid active sanitizer materials including a cold aseptic operation. In the figure, a plant 100 that can contact beverage bottles with a peroxyacid sanitizer for a sanitizing regiment is shown. In the figure, 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 container 104 and added to a holding tank 101 at an effective concentration comprising about 0.1 to about 5 wt%, preferably 3 wt% to about 4 wt%. Commonly, the materials maintained at a temperature of about 22°C in tank 101. To obtain the effective concentration of the peroxyacid make-up water 105 is combined with the concentrate from drum 104 into the tank 101. The peroxyacid sanitizer material in an appropriate concentration is passed through a heater 108 to reach a temperature of about 45-50°C. The heated peroxyacid material is sprayed within sterilizing tunnel 102 into and onto all surfaces of the bottle 110. An intimate contact between the peroxyacid material and the bottle 110 is essential for reducing microbial populations to a sanitizing level. After contact with the peroxyacid material and after dumping 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 a fresh water make-up into a spray rinsing tunnel 103. Excess spray drains from rinsing tunnel 103 to drain 106. Within the tunnel 103, sanitized bottles 110a are thoroughly rinsed with fresh water. The complete removal of the peroxyacid material from the bottles 110a is important for maintaining high quality of the beverage product. The rinsed sanitized bottles 110b are then removed from the rinsing tunnel. The day tank 101, the sterilizing tunnel 102 and the rinsing tunnel 103 are all respectively vended to wet scrubber or vent I l ia, 11 lb or 11 lc to remove vapor or fumes from the system components. The sanitizer material that has been sprayed and drained from the bottles 110a accumulate in the bottom of the spray tunnel 102 and is then recycled through recycle line and heater 107 into the day tank 101. The day tank is used for mixing and storing the peroxyacid material which can be a 0.1 to 5 wt%, preferably 2 to 4 wt%> peroxyacetic acid. All active treating equipment should be vented to a wet scrubber to prevent peroxide peracetic acid or acetic acid fumes from entering the atmosphere from the treatment equipment. Draining of the containers of their peroxyacid contents is important to reduce carry over minimized product loss. Water used to make up the active sanitizer material should be deionized to maximize the useful life of the peroxyacid material. Deionized water maintains the highest effective concentration and reduces spotting and filming. The contact between the bottles and the peroxyacid material is typically at a temperature of greater than about 40°C. In order to obtain sanitization of beverage containers at about 700 ppm per acid to about 2500 ppm per acid contact at 40°-60°C for at least 7 seconds contact time is required. Preferably, the sanitization equipment, day tank, sanitizing tunnel and rinsing tunnel are manufactured from polyolefm structural plastics, passivated stainless steel or other non-corrosion sensitive production materials. In the cold aseptic filling of 16 ounce polyethylene terephthalate (PET bottle) beverage containers, a process has been adopted using a peroxyacid sanitizer or mixed peroxyacid sanitizer material. The peroxyacid material is diluted to a concentration of about 0.1 to about 3 wt% and is maintained at an effective elevated temperature of about 40°C to about 60°C, preferably about 50°C. The spray or flood of the bottle with the material ensures contact between the bottle and the sanitizer material for at least 7 seconds. After flooding is complete, the bottle is drained of all contents for a minimum of 2 seconds followed by a 5 second water rinse with sterilized water using about 200 milliliters of water at 38°C (100°F). The bottle is then drained of the sterilized water rinse for at least 2 seconds and is immediately filled with liquid beverage. After the rinse is complete, the bottles maintain 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 0.05 M citrate buffer made in distilled water and were exposed to the bacteria for 30 seconds at 20°C. As Table I indicates, the diperoxyacids were somewhat less active than the peroxyfatty acids. Peroxydecanoic 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 Comp arison of biocidal Activity of Peroxyacids Peroxyacid pH Minimum concentration required for 5-log reduction (ppm) (a) S. aureus E . coli Peroxyhexanoic (C 6 ) 3.5 15 15 5.0 - 20 15 Diperoxyadipic (C 6 ) 3.5 >50 40 5.0 >60 35 Peroxyoctanoic (C 8 ) 3.5 5 5 5.0 10 15 Peroxy decanoic (C 10 ) 3.5 3 10 5.0 1 30 Diperoxysebacic (C 10 ) 3.5 15 15 5.0 10 50 (a) - Peroxyacids tested at 5 -ppm increments, or at 1, 3, and 5 ppm where appropriate. In Table II below, the antimicrobial synergism between the C 2 and C 3 peroxyacids when combined with C 8 and C 10 peroxyfatty acids is shown. As Table II shows, there was little or no antimicrobial activity when the C 2 and C 3 peroxyacids and the C 8 and C 10 peroxyfatty acids were tested alone. However, when a C 2 or C 3 peroxyacid was combined with a C 8 or C 10 peroxyfatty acid, the bacterial kill of E. coli multiplied exponentially. These tests were conducted at pH 4.5 or 5, the pH at which E. coli is more difficult to kill (see Table II).. TABLE II Synergistic Interaction of Peroxyacids C 2 C 3 C 8 JO [Peroxyacetic] [Peroxypropionic [Peroxyoctano [Peroxydecan (ppm) ] (ppm) ic] (ppm) . oic] (ppm) Log Reduction 25 0 0 a 0 5 0.1 a 25 5 3.8 a 25 0 0.3 b 0 6 0.1 b 25 6 3.9 30 0 0.7 a 0 6 0 a 30 6 2.6 a E. coli, pH 5, distilled water b E. coli, pH 4.5, 500 ppm hard water Example 2 A mixture of short chain fatty acids commercially available from Emery Corporation under the designation "EMERY 658" was employed in producing a sanitizing concentrate composition of the present invention. The "EMERY 658" acid is a mixture of caprylic acid (C 8 ) and capric acid (C, 0 ). The peroxyacids were prepared by the method of Parker, et al, J. Amer. Chem. Soc, 77, 4037 (1955) which is incorporated 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 an n- octanesulfonate hydrotzope coupler (NAS 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 (C 8 ) and capric acid (C 10 ) replaced some of the peroxy acid of Example 2. The concentration of peracetic acid was 5% while the concentration of peroxy acids 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 wt-% and the composition contained 5%> peroxy acid (see Table III). Also, a chelating agent (Dequest 2010) was added to the composition. Example 5 The composition of Example 5 was prepared the same as Example 4 except that caprylic acid and capric acid were added to the composition in addition to the percaprylic and percapric acid of Example 4. The composition contained 3.5% fatty acid and 1.5% peroxy acid (see Table III). Example 6 Example 6 was prepared with only peracetic acid, acetic acid, hydrogen peroxide, and water. No peroxy acids or fatty acids were added to the composition of Example 6. The concentration of total peroxyacid was about 5% and the acetic acid concentration was about 39% (see Table III). Example 7 Example 7 was prepared the same as Example 5 except that no peroxyacids were employed, only a mixture of fatty acids and acetic acid was used, along with water, NAS BD, and Dequest 2010. The composition contained 5%> fatty acid (see Table III). TABLE III Wt-% of Ingredients Ingredient Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Peracetic Acid 50 50 50 (10.42% solution, 34%) acetic acid, 10% H 2 O 2 ) Acetic Acid 22 22 39 39 22 39 Percaprylic Acid 3.75 1.125 3.75 1.125 (C 8 ) Percapric Acid 1.25 0.375 1.25 0.375 (C 10 ) Caprylic Acid — 2.625 — 2.625 3.75 (C 8 ) Capric Acid (C 10 ) — 0.875 — 0.875 1.25 NAS 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 testing procedure of the standard A.O.A.C. sanitizing test. All of the samples tested of Examples 2-7 were made about 1 hour prior to testing. 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 employed at room temperature. The following neutralizers were employed in the test: 0.1% thiosulfate, peptone, 0.5% K 2 HPO 4 , 0.025% catalase for peracetic acid; chambers for fatty acid; 0.1% thiosulfate, peptone, 0.025%) catalase for peracetic acid/fatty acid (peroxy acid). The antimicrobial activity of Examples 2-7 are summarized in Table IV. Examples 2 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 25 exhibited excellent kill (> log 6) of both S aureus and E. coli at 50 ppm of peroxyacid. Examples 6 and 7 (containing no peroxy acids) exhibited little or no activity. More specifically, Example 2 was tested at 1,000 and 500 ppm total product (50 and 25 ppm of 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 total product, and also had a 6-7 log reduction in the bacterial count. At the 500 ppm product concentration the product corresponds to 25 ppm of peroxyacetic acid and 7.5 ppm of peroxy acids. Example 4, at 1,000 ppm of total product (50 ppm of peroxy acid), completely killed all bacteria (greater than 7 log reduction). Example 5 also resulted in a complete kill using 1,000 ppm of total product (15 ppm peroxy acid). Example 6 contained no peroxy acid (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 100 ppm. Example 7, containing 5% fatty acid (30 ppm) and no peroxy acid at 1,000 ppm total product showed no activity toward either organism. TABLE IV Test Product Mixed Acid Concentration [POAA1/POA2/FA3] Logu) Kill Concentration Ex Sample (ppm) (ppm) pH S aureus E coli 2 a 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 a 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 6 76 d 500 25/7 5/17 5 3 68 7 18 7 00 4 a 1000 0/50/0 3 5 >7 18 >7 30 b 1000 0/50/0 3 5 >7 18 >7 30 5 a 1000 0/15/35 3 5 >7 18 >7 30 b 1000 0/15/35 3 5 >7 18 >7 30 6 a 1000 50/0/0 3 49 NMA4 3 48 b 1000 50/0/0 3 49 NMA 3 80 7 a 1000 0/0/30 3 46 NMA NMA b 1000 0/0/30 3 46 NMA NMA 1 - POAA = Peroxyacetic Acid 2 - POA = Peroxy Acid 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 (H 2 O 2 ) was mixed with acetic acid and C 8 - 10 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 which were made. TABLE V Peroxyacid Test Formulations Ingredient Ex. 8 Ex. 9 Ex. 10 Ex. 11 Acetic Acid 44 39 34 49 H 2 O 2 (35%) 40 40 40 40 Dequest-L 2010 1 1 1 1 NAS 8D 10 10 10 10 Emery 658 5 10 15 — Peroxyacid Stability, Biocidal Activity of Examples 8-11 Each of Examples 8-11 were tested for peroxyacid stability and biocidal activity using the A.O.A.C. sanitizing test 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. Generally all of the formulations reached maximum peroxyacid formation within about 12 days. All of the formulations obtained about 12.5% peroxyacid except Example 10 (15% fatty acid) which obtained about 11.5%> peroxyacid. Table VI summarizes the biocidal activity of Example 8 in which the composition was measured for biocidal activity on the first day up to day 33. At 250 ppm of total product, there were about 4-5 ppm of peroxy acid and about 20 ppm of peracetic acid as determined by carbon 13 NMR spectroscopy. The results are summarized in Table VI. TAB: LE VI Peroxyacid Stability, Biocidal Activity of Example 8 Peroxyacid Test (a) Test Ave. Log Reduction Day Percent Concentration Pϋ S. aureus E. coli 1 4.28 250 ppm 3.92 6.28 NMA (b) 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 15 12.74 250 ppm 3.88 6.83 — 33 10.18 250 ppm 3.83 5.18 6.34 (a) ppm total product (b) No measurable activity The biocidal activity of Example 9 is summarized in Table VII below. The peracetic acid concentration at 250 ppm of product was about 20-21 ppm and the concentration of peroxy acid was about 11 ppm. The concentration of peracetic acid at 50 ppm of product was about 4 ppm and the concentration of peroxy acid was about 2 ppm. TABLE VII Peroxyacid Stability Biocidal Activity of Example 9 Peroxyacid Test (a) Test Ave Log Reduction Day Percent Concentration pH 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 1 1 >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 total product (b) No measurable activity The biocidal activity of Example 10 is summarized in Table VIII below. At 250 ppm of product the peracetic acid concentration was about 19 ppm and the peroxy acid concentration was about 14 ppm. TABLE VIII Peroxyacid Stability Biocidal Activity of Example 10 Peroxyacic I Test (a) Test Ave. Log Reduction Day Percent Concentration pH 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 >7.18 8 10.99 250 ppm 3.96 >7.11 >7.12 12 11.47 250 ppm 3.94 >7.18 >7.23 15 11.48 250 ppm 3.96 6.83 ~ 33 10.49 250 ppm 3.95 5.25 6.53 (a) ppm total product <b) No measurable activity The biocidal activity of Example 11 is summarized in Table IX below. At 250 ppm of product there was about 27 ppm of peracetic acid. At 1000 ppm of product there was about 108 ppm of peracetic acid. No fatty acid was employed in the composition of Example 11. TABLE IX Biocidal Activity of Example 11 Peroxyacid Test (a) Test Ave. Log Reduction Day . Percent Concentration pH S. aureus E. coli 5 10.95 250 ppm 3.90 NMA (b) NMA 7 12.03 1000 ppm 3.50 4.60 >7.12 11 12.44 1000 ppm 3.49 6.38 6.64 14 12.53 1000 ppm 3.50 4.17 — 32 10.77 1000 ppm 3.45 4.77 6.44 (a) ppm total product ^ No measurable activity When comparing the formulations containing fatty acid (Tables VI- VIII), poor activity was measured against E. coli one day after being formulated. Since the total peroxyacid values were low, more fatty acid was present and gram negative bacteria tend to be less sensitive than gram positive bacteria to the C 8 -C I0 fatty acids. However, as more peroxyacid developed over the days indicated, increased biocidal activity against E. coli was observed. Table IX indicates that to obtain acceptable activity (greater than or equal to 5 log reduction) using only peracetic acid, the peracetic acid must be tested over 100 ppm active. Secondly, this oxidizing compound is more effective against E. coli than S. aureus. Generally all the formulations containing fatty acid remain stable after about 1 month. This was confirmed by repeated testing over time at 250 ppm total product for each formulation in which greater than 5 log reductions were measured against S. aureus and E. coli. Examples 12-17 The biocidal activity of a two-component system containing both peracetic acid and fatty acid was investigated using the A.O.A.C. sanitizing test. Table X shows the product formulations examined. The test samples include controls showing biocidal activity of NAS 8D as well as fatty acid kill against S. aureus. All the samples were tested in distilled water. TABLE X Wt-%) Ingredient Ingredient Ex.12 Ex.13 Ex.14 Ex.15 Ex.16 Ex.17 Base l (a) 80 80 80 80 ~ — Base 2 ^ — — — ~ 80 80 NAS 8D 10 — 10 10 10 10 Octanoic Acid — — 10 — — 10 Emery 658 — — — 10 10 — H 2 O 10 20 ~ ~ — — (a) H 2 O 2 , 35%; acetic acid, 35%; Dequest 2010, 1%; H 3 PO 4 (85%), 29%. (b) Acetic acid, 35%; Dequest 2010, 1%; H 3 PO 4 (85%), 29%; H 2 O, 35%. Table XI shows the activity measurement of each of Examples 12-17 at various test concentrations. When testing the peracetic acid formulation of Examples 12 and 13 (having no fatty acid), biocidal activity occurred only at 100 ppm or greater. Biocidal activity (greater than 4 log reduction) was measured at a minimal concentration of 10 ppm peroxyacid with fatty acid in the system (Example 14). At 10 ppm peroxyacid, the composition containing Emery 658 (Example 15) had better activity than the system containing only C 8 (octanoic) fatty acid (Example 14). In the fatty acid controls (Examples 16 and 17), the Emery 658 had more biocidal activity than the C 8 fatty acid. At total product test concentrations equivalent to 10 or 25 ppm peroxyacid, the fatty acid in the system of Example 16 did not have significant biocidal activity. Example 17 did not have significant biocidal activity at any test concentration. TABLE XI Peroxyacid Biocidal Activity Against S. aureus Peroxyacid Concentration Test Log .'(a) Example % (ppm Peroxyacid) pH . Reduction 12 7.02 50 2.79 NMA ( ) 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 15 9.73 10 3.50 6.82 25 3.19 7.55 50 2.88 >7.70 16 _. (c > 3.53 0.70 __(c-l) 3.18 1.04 __(c-2) 2.88 4.07 17 — <* 3.51 0.93 __( -l) ~ 0.66 (d-2) «._ 0.97 w Average of duplicate testing (b) No measurable activity (c) Same total product concentration as Example 15 @10 ppm peroxyacid (about 100 ppm product) (c " Same total product concentration as Example 15 @25 ppm peroxyacid (about 250 ppm product) <c 2) Same total product concentration as Example 15 @50 ppm peroxyacid (about 500 ppm product) "Same total product concentration as Example 14 @10 ppm peroxyacid (about 100 ppm product) Same total product concentration as Example 14 @25 ppm peroxyacid (about 250 ppm product). Id~2 Same total product concentration as Example 14 @50 ppm peroxyacid (about 500 ppm product). The biocidal activity of a peracetic acid/fatty acid system was measured comparing freshly made formulations to month-old formulations of Examples 14 and 15. These formulations are shown in Table XII which compares the titration values of month-old formulations to the same freshly prepared. Table XIII shows the biocidal activity of month-old and fresh formulations of Examples 14 and 15. TABLE XII Peroxyacid Titration Values Ex. 14 Ex. 15 Ex. 14 Ex. 15 Date formulated Month-Old Month-Old Fresh Fresh % H 2 O 2 2.15 2.07 1.99 1.99 % Peroxyacid 5.37 5.35 4.85 4.86 % Total O, 2.14 2.10 1.96 1.96 TABLE XIII Peroxyacid Biocidal Activity Against S. aureus Peroxyacid Test Concentration Test Log 1 (a) Example (%) (ppm Peroxyacid) pH Reduction 14 5.37 10 3.46 NMA (b) (Month-Old) 25 3.07 >7.48 14 4.85 10 3.34 5.07 (Fresh) 25 2.97 7.30 15 5.35 10 3.52 5.29 (Month-Old) 25 3.04 7.24 15 4.86 10 3.42 NMA (C) / 3.68 (Fresh) 25 2.99 7.48 (a) Average of duplicate testing. ( > No measurable activity <c) Duplicate testing in which only one sample exhibited biocidal activity As can be seen from Table XIII, biocidal activity in the peracetic acid/fatty acid system occurs at test concentrations as low as 10 or 25 ppm peroxyacid. Mixed results occurred at 10 ppm peroxyacid between the month-old and fresh formulations of Examples 14 and 15, however, increasing the concentration to 25 ppm resulted in a uniform kill activity (>7 log reduction). An additional test was run to determine how quickly compounds exhibiting biocidal activity are formed upon adding fatty acid to a peracetic acid system. Examples 12, 15 and 16 were tested. Examples 12 and 15 were formulated the day before testing and were day-old samples. Another test sample of Example 15 was formulated immediately prior to testing. Example 16 containing Base 2 (no H 2 O 2 ) was used to show biocidal activity from the fatty acid at low test concentrations. Table XIV shows the biocidal activity of each Example in distilled water against S. aureus. TABLE XIV Biocidal Activity Against S. aureus ppm Test Log (a) Example Age Peroxyacid P H Reduction 12 1 day 50 2.94 NMA (b) 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 -i c > 3.74 NMA -i d) — NMA (a) Average of duplicate testing. (b) No measurable activity. (c) Equivalent total product concentration as Example 15 (day old) @ 10 ppm peroxyacid. (d) Equivalent total product concentration as Example 15 (day old) @ 25 ppm peroxyacid. The data from Table XIV suggests that the formation of compounds containing biocidal activity when adding fatty acid 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 biocidal activity occurring at a concentration as low as 10 ppm peroxyacid. Thus, the biocidal activity is not due to the mere combination of fatty acid and peroxyacetic acid, but the fatty acid must be converted to the peroxy acid before substantially enhanced biocidal activity occurs. Examples 18-22 A two-component system containing peracetic acid and peroxy acid was formulated and tested to determine its sanitizing activity over just a peracetic acid system. Table XV shows premixes 1 and 2 used in making the composition. The premixes were both made with H 2 O 2 (35% solution), acetic acid, Dequest 2010, and with/without H 3 PO 4 . Premix 1 was made about 5 months before premix 2. To each premix was added NAS 8D, a C 8 fatty acid or Emery 658 as shown in Table XVI to complete the formulation of Examples 18-21. Example 22 was formulated as a control and had no fatty acid. TABLE XV Peroxyacid Premixes Wt-% Cor nponent Component Premix 1 Premix 2 H 2 O 2 (35%) 75.0 35.0 Acetic acid (glacial) 24.0 35.0 Dequest 2010 1.0 1.0 H 3 PO 4 (85%) 29.0 Table XVI Peroxy Acid/Peracetic Acid Formulations Wt-%) Ingredient (Control) Ingredient Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Premix 1 80.0 80.0 Premix 2 — 80.0 80.0 NAS 8D 10.0 10.0 10.0 10.0 C 8 Fatty Acid 10.0 10.0 Emery 658 ~ 10.0 10.0 Acetic Acid — 24.0 (Glacial) H 2 O 2 (35%) — 75.0 Dequest 2010 ~ 1.0 Table XVII shows the sanitizing activity measured from each formulation of Examples 18-22 at 50, 100, or 150 ppm peracetic acid against S. aureus. Table XVII Sanitizing Efficacy of Peroxy Acid/ Peracetic Acid System vs. Sanitizing Efficacy of Peracetic Acid System Total Fatty Test Peroxyacid 0 a) Acid Concentration Test Log (b| Example (Percent) (Percent) (ppm) pH Reduction 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 20 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) Average of duplicate testing against S. aureus. (c) No measurable activity. Extremely good kill (>7 log reduction) was obtained with or without H 3 PO 4 in the peroxy acid formulations of Examples 18-21. The two component system of C 8 fatty acid or Emery 658 in combination with peracetic acid (Examples 18-21) had significantly better kill than the peracetic acid system alone (Example 22) at a test concentration of 50 to 100 ppm. No activity was measured at 50 ppm with the single peracetic acid system of Example 22. Examples 23-26 The effect of alkyl chain length on antimicrobial efficacy of peroxy acids was determined for percaprylic (C 8 ) acid, percapric (C 10 ) acid and a percaprylic/percapric (3:1) perfatty acid mixture using the compositions of Examples 23-26 summarized in Table XVIII below. TABLE XVIII Wt-% of Ingredient Ingredient Ex. 23 Ex. 24 Ex. 25 Ex. 26 Percaprylic (C 8 ) Acid 1 — — — Percapric (C 10 ) Acid — 1 — — C g + C 10 (3:l) Perfatty Acid — — 1 — Acetic Acid 10 10 10 10 Water 84 84 84 85 NAS 8D 5 5 5 5 The antimicrobial efficacy of Examples 23-26 are summarized in Table XIX below. Examples 23-25 were tested using three samples (a, b, c) of 5, 10, and 15 ppm of perfatty acid respectively. Example 26, containing no perfatty acid, was diluted to an equivalent formulation of Examples 23-25 containing perfatty acid. As can be seen from Table XIX, significant kill occurred at 5 ppm for S. aureus using Examples 23-25. Significant kill occurred against E. coli at 10 ppm of perfatty acid in Examples 23-25. TABLE XIX Antimicrobial Efficacy of Examples 23-26' Perfatty Acid Concentration Log Kill Example Sample (ppm) S. aureus E. coli 23 a 5 >7.0 3.6 b 10 — >7.2 c 15 — >7.2 24 a 5 >7.0 3.0 b 10 — >7.2 c 15 — >7.2 25 a 5 >7.0 <3.0 b 10 — >7.2, 5.5 c 15 — >7.2 26 a a 0 — b b 0 a - Equivalent total product concentration as Examples 23, 24, 25 at 5 ppm perfatty acid b - Equivalent total product concentration as Examples 23, 24, 25 at 15 ppm perfatty acid Example 27 The antimicrobial activity of percaprylic acid against E. coli was measured at a 30 second exposure at varying pH's. The formulation contained 94%o water, 5% NAS 8D, and 1% percaprylic acid. The formulation was diluted in a buffer of 0.05 M citrate and 0.05 M potassium phosphate. The log kill of this formulation at increasing pH's is summarized in Table XX. Samples containing 7 ppm and 25 ppm of percaprylic acid were tested. As Table XX indicates, significant kill at 7 ppm occurred at a pH of 3.0. Significant kill levels were maintained at 25 ppm through a pH of 7.0. Example 26 (having no perfatty acid) did not produce any kill of either microorganism. TABLE XX Antimicrobial Efficacy < of Percaprylic Acid against E.. coli Log Kill (Perfatty Log Kill (Perfatty pH Concentration 7 ppm) Concentration 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 on biocidal activity of compositions containing at least 30% acetic acid. Higher acetic acid formulations were also tested for their biocidal activity. The composition of Example 30 was prepared with no coupler (NAS 8D). The compositional ingredients of Examples 28-30 are summarized below in Table XXI. TABLE XXI Wt-%-of Ingredient Ingredient Example 28 Example 29 Example 30 Acetic Acid 30.0 50.0 50.0 H 2 O 2 (35%) 30.0 15.0 15.0 Dequest 2010 1.0 1.0 1.0 C 8 Fatty Acid 4.0 6.0 5.0 NAS 8D (Spray 5.0 5.0 - Dried) Distilled Water 30.0 23.0 29.0 The antimicrobial efficacy of Examples 28-30 was determined using the procedure of the standard A.O.A.C. sanitizing test. The compositions of Examples 28-30 were diluted with 500 ppm hard water and employed at 25°C. The bacteria used in the test procedure were S. aureus and E. coli, and a TGE plating medium was employed. Exposure time of the compositions to the bacteria was 30 seconds. The neutralizer employed in the testing 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 1 oz:8 gal. a 4.48 >7.15 >6.89 1 oz:10 gal. 4.83 >7.15 >6.89 l oz:12 gal. c 5.04 >7.15 6.41 1 oz:14 gal. d 5.52 >7.15 5.76 1 oz:16 gal. e 5.94 >7.15 2.95 Example 29 40 ppm Active 4.16 >7.15 >6.89 Example 30 40 ppm Active 4.04 >7.15 >6.89 a 54.2 ppm peroxyacid b 43.3 ppm peroxyacid c 36.1 ppm peroxyacid d 31.0 ppm peroxyacid e 27.2 ppm peroxyacid As Table XXII indicates, very low concentrations of combinations of peroxyacetic acid and peroxyfatty acid are very effective in killing bacteria. Also, 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 80 ppm and 500 ppm synthetic hard water at a concentration of 2.2% against Chaetomium bostrychodes ascospores (Coca-Cola Japan mold isolate), utilizing exposure times of 30 seconds, 1.0 minute, 2.0 minutes and 5.0 minutes. Method Parameters: Test System: Chaetomium bostrychodes ascospores (mold contaminant from 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 Plating Medium: Potato Dextrose Agar (PDA) Incubation: 5-7 days at 26°C Results: Chaetomium bostrychodes Average Survivors (CFU/mL) at 40°C Chaetomium bostrychodes Average Survivors (CFU/mL) at 50°C Chaetomium bostrychodes Log Reductions at 40°C Chaetomium bostrychodes Log Reductions at 50°C Conclusions: Example A at 2.2% when diluted in both 80 ppm and 500 ppm synthetic hard water achieved a >6.08 log reduction (no survivors) after a 2.0 minute exposure time at 50°C, while achieving a <1.00 log reduction at 30 seconds and 1.0 minute. At 40°C, Example A achieved a 2.90 (80 ppm synthetic hard water) and a 2.72 (500 ppm synthetic hard water) log reduction after a 5.0 minute exposure time, while achieving a <1.00 log reduction at 30 seconds, 1.0 minute and 2.0 minutes. To achieve total kill of Chaetomium bostrychodes ascospores, Example A should be used at a concentration of 2.2% at 50°C, utilizing 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 synthetic hard water at concentrations of 0.85% Example B and 0.05% Example C against Chaetomium bostrychodes ascospores (Coca-Cola Japan mold isolate), utilizing exposure times of 30 seconds, 1.0 minute, 2.0 minutes and 5.0 minutes. Method Parameters: Test System: Chaetomium bostrychodes ascospores (mold contaminant from 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 Plating Medium: Potato Dextrose Agar (PDA) Incubation: 5-7 days at 26°C Results: Control Numbers (CFU/mL) Chaetomium bostrychodes Average Survivors (CFU/mL) at 50°C Chaetomium bostrychodes Log Reductions at 40°C Chaetomium bostrychodes Log Reductions at 50°C Conclusions: Example B at 0.85%> when diluted in both 80 ppm and 500 ppm synthetic hard water achieved a >3.72 log reduction after a 5.0 minute exposure time at 50°C, while achieving a <1.50 log reduction at 30 seconds, 1.0 minute and 2.0 minutes. At 40°C, Example B achieved a <1.00 log reduction at all exposure times. Example C achieved a <1.00 log reduction 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 percent 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 use dilution due to the absence of octanoic acid in the formula. Example C performed similarly to Example A at 50°C after a 5.0 minute exposure time, while at 40°C Example A demonstrated better efficacy by achieving approximately a 2.60 log reduction after a 5.0 minute exposure time. Example C Objective: The objective of this analysis was to determine the antimicrobial efficacy of Example D and Example A when prepared in synthetic hard water 500 ppm as CaCO 3 at concentrations of 1.0% Example A and 0.175% Example A against Chaetomium bostrychodes utilizing exposure times of 30 seconds, 1.0 minute, 2.0 minutes, 5.0 minutes and 10.0 minutes. Method Parameters: Test System: Chaetomium bostrychodes ascospores (mold contaminant from Coca-Cola Japan) Test Temperatures: 25°C and 40°C Exposure Times: 30 seconds, 1.0, 2.0, 5.0 and 10.0 minutes Neutralizer: 1%) Sodium thiosulfate/ 1% Peptone/0.025% Catalase Plating Medium: Potato Dextrose Agar (PDA) Incubation: 5-7 days (or until growth is visible at 26°C Results: Inoculum Numbers (CFU/mL) Chaetomium bostrychodes Survivors (CFU/mL) Conclusions: The results of this analysis demonstrated that at 25°C, Example D and Example A were similar in efficacy against Chaetomium bostrychodes. Example A at the 30 second exposure time achieved a log reduction of 2.38, while Example D achieved a log reduction of 2.26. Example A and Example D were relatively static at subsequent exposure times. Example A at 40°C achieved a log reduction of 2.23 at the 30 second exposure time, while Example D had a 2.32 log reduction at the 30 second exposure time. Example A and Example D both were static at subsequent exposure times. Further testing will be performed using 2.2% Example A and 4.0% Example D in 500 ppm synthetic hard water as CaCO 3 and deionized water. Example D Objective: The objective of this analysis was to determine the antimicrobial efficacy of Example A when prepared in 80 ppm and 500 ppm synthetic hard water at a concentration of 2.2% against Arthrinium sacchari ascospores (Coca-Cola Japan mold isolate), utilizing exposure times of 30 seconds, 1.0 minute, 2.0 minutes and 5.0 minutes. Method Parameters: Test System: Arthrinium sacchari ascospores (mold contaminant from Coca-Cola Japan) Test Temperatures: 40°C and 50°C Exposure Times: 30 seconds, 1.0, 2.0, and 5.0 Neutralizer: 1%) Sodium thiosulfate Plating Medium: Potato Dextrose Agar (PDA) Incubation: 5-7 days 26°C Results: Arthrinium sacchari Average Survivors (CFU/mL) at 40°C Arthrinium sacchari Average Survivors (CFU/mL) at 50°C Arthrinium sacchari Log Reductions at 50°C Conclusions: Example A at 2.2% when diluted in both 80 ppm and 500 ppm synthetic hard water achieved a >6.95 log reduction (no survivors) after a 1.0 minute exposure time at 50°C, while achieving 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 in both 80 ppm and 500 ppm synthetic hard water at all exposure times. To achieve total kill of Arthrinium sacchari ascospores, Example A should be used at a concentration of 2.2%o at 50°C, utilizing an exposure time of 1.0 minute. The foregoing discussion and Examples are illustrative of the invention. However, since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides wholly in the claims hereinafter appended.

Claims: WE CLAIM: 1. A method for sanitizing a beverage plant, the plant comprising an assembly of tanks, pipes or lines, pumps and valve or other mixing equipment, which method comprises contacting the plant with a peroxyacid sanitizer for an effective period of time to substantially reduce the populations of the microorganisms, sufficient to sanitize the plant. 2. A cold aseptic bottling method for beverages that obtains a significantly reduced population of microorganisms resulting in a sanitized beverage container, the method comprising contacting a beverage container with a peroxyacid antimicrobial composition for sufficient period of time to reduce the microorganism population, rinsing the container and filling the container with a carbonated beverage followed by a sealing step. 3. The method of claim 1 or 2 wherein the population is reduced by more than 5 log 10 , and the peroxyacid antimicrobial concentrate composition comprises: (a) an effective biocidal amount of a C,-C 4 peroxycarboxylic acid; and (b) an effective biocidal amount of an aliphatic C 6 -C 18 peroxyacid; wherein the concentrate composition has a proportional weight ration of about 20 to 1 parts of (a) per part of (b) and is capable of being diluted with a major proportion of water to form an antimicrobial use solution having a pH in the range of about 2 to 8. 4. The method of claim 1 or 2 which comprises about 0.01 to 25 wt-% of said C,-C 4 peroxycarboxylic acid. 5. The method of claim 1 or 2 wherein said C,-C 4 peroxycarboxylic acid comprises peroxyacetic acid, peroxyglycolic acid or mixtures thereof. 6. The method of claim 1 or 2 wherein said C 6 -C 18 peroxyacid comprises peroxyoctanoic acid, peroxydecanoic acid, monoperoxy- or diperoxyadipic acid, monoperoxy- or diperoxysebacic acid, or mixtures thereof. 7. The method of claim 1 or 2 wherein the weight ration of said C,-C 4 peroxycarboxylic acid to said C 6 -C 18 peroxyacid is about 15:1 to 3:1. 8. The method of claim 1 or 2 further comprising an effective amount of a hydrotype coupling agent capable of solubilizing said C 6 -C 18 peroxyacid in the concentrate when the concentrate is diluted with water. 9. The method of claim 1 or 2 wherein said composition comprises about 1 to 50 wt-%) of hydrogen peroxide. 10. The method of claim 1 or 2 wherein the peroxyacid antimicrobial composition comprises: (a) at least about 10 parts per million (ppm) of a C,-C 4 peroxycarboxylic acid; and (b) at least about 1 ppm of a C 6 -C 18 peroxyacid; wherein the aqueous composition has a pH in the range of about 2 to 8. 11. The method of claim 10 which comprises about 0.01 to 25 wt-% of said C,-C 4 peroxycarboxylic acid. 12. The method of claim 10 wherein said C,-C 4 peroxycarboxylic acid comprises peroxyacetic acid, peroxyglycolic acid or mixtures thereof. 13. The method of claim 10 wherein said C 6 -C 18 peroxyacid comprises peroxyoctanoic acid, peroxydecanoic acid, monoperoxy- or diperoxyadipic acid, monoperoxy- or diperoxysebacic acid, or mixtures thereof. 14. The method of claim 10 wherein the weight ratio of said C,C 4 peroxycarboxylic acid to said C 6 -C 18 peroxyacid is about 15:1 to 3:1. 15. The method of claim 10 further comprising an effective amount of a hydrotype coupling agent capable of solubilizing said C-C 18 peroxyacid in the concentrate when the concentrate is diluted with water. 16. The method of claim 10 wherein said composition comprises about 1 to 50 wt-%) of hydrogen peroxide. 17. The method of claim 1 or 2 wherein the microorganism is a fungus. 18. The method of claim 1 or 2 wherein the fungus is of the genus Chaetomium. 19. The method of claim 1 or 2 wherein the fungus is of the genus Arthrinium. 20. The method of claim 1 or 2 wherein the beverage is carbonated. 21. The method of claim 1 or 2 wherein the beverage is a non-carbonated fruit drink or a tea.

Inventors: BESSE MICHAEL E, CORDS BRUCE R, NOGAMI KENJI, RICHTER FRANCIS L, BESSE, MICHAEL, E., CORDS, BRUCE, R., NOGAMI, KENJI, RICHTER, FRANCIS, L.
Applicants: ECOLAB INC, ECOLAB INC.
Application year: 1999
Main classification: A61L2
IPC codes: A23F3, A23G9, A23L2, A61L2, B67C3, B67C7, C11D3, C11D11