CLEANING/SANITIZING METHODS, AND/OR ARTICLES FOR EDIBLE ANIMAL PROTEIN

Abstract: Basic cleaning compositions methods using toxicologically-acceptable ingredients for cleaning edible animal protein are provided. Liquid formulations comprising detergent surfactant, such as oleate, alcohol ethoxylates, etc., and alkaline buffer are sprayed onto meat, seafood, poultry and the like to remove soil and unwanted deposits. Articles for applying the compositions to edible animal protein by spraying are disclosed. Use of the compositions for disinfectancy/sanitization of edible animal protein and mitigation of malodor are disclosed.

Description: CLEANING/SANITIZING METHODS, AND/OR ARTICLES FOR EDIBLE ANIMAL PROTEIN TECHNICAL FIELD The present invention relates to methods for cleaning and/or sanitizing edible animal protein, e.g., meat, seafood and poultry, which is intended for ingestion by humans or lower animals and articles, which are especially suitable for practicing said methods. BACKGROUND OF THE INVENTION It is well-known and appreciated by consumers that edible animal protein sources such as meat, seafood and poultry should be thoroughly washed prior to ingestion in order to remove soils and other unwanted residues which may be undesirably clinging to the surfaces thereof. It has been estimated that 95% of consumers recognize the need for thorough washing but, ordinarily, only use tap water for this purpose. On the order of 5% of those consumers who do wash their food use a household cleaner, typically a liquid dishwashing product, to help ensure cleanliness. However, dishwashing products are not specifically intended for such use, inasmuch as they are usually designed to provide high, persistent suds which makes them inconvenient to remove from the meat, seafood or poultry which have been washed therewith. It will also be appreciated that the formulation of truly effective compositions, especially those which can be used safely by individual consumers, for washing edible animal protein such as meat, seafood, or poultry, presents a unique problem to the formulator, inasmuch as many art-disclosed cleaning ingredients would, presumably, not be desirable for use in direct contact with foods where they might not be fully removed. Moreover, it would be especially desirable to provide effective, toxicologically-acceptable cleaning compositions for edible animal protein, such as meat, seafood, or poultry, in the form of substantially low-sudsing liquid solutions which are clear or which have only minimal haziness. Liquid solutions are convenient for the user, since they can be applied directly to edible animal protein, followed by rinsing in tap water. The clarity ofthe liquids connotes cleanliness to the user and is thus highly desirable. Low sudsing is an important attribute so that removal of the solution by rinsing is achieved quickly and easily. It would also be of advantage if such compositions could be provided in the form of concentrates, which could be diluted by the consumer before use and/or applied to the edible animal protein as a direct spray-on. Unfortunately, many toxicologically-acceptable cleaning ingredients do not meet the aforesaid requirements for clear, low-sudsing, dilutable liquid products. Many detersive surfactants form cloudy or even opaque suspensions, even in soft water. Of course, many surfactants are specifically designed to be high sudsing. Still others form relatively intractable phases in their concentrated form. It has been disclosed that soap and/or certain nonionic surfactants, properly formulated, e.g., with water-soluble oleate or laurate salts and other ingredients can provide liquid compositions having the desired properties described above. It has also been disclosed that preferred compositions can be formulated in the basic pH range. It has now been discovered that methods using the preferred compositions as described herein are effective at reducing microbial contamination typically found on edible animal protein, e.g. meat, seafood, and/or poultry. Furthermore, it has been discovered that the methods described herein are effective at mitigating malodors that typically appear on such protein.. BACKGROUND ART The use and selection of cleaning ingredients for the purpose of washing fruits and vegetables is described by the United States Code of Federal Regulations, Title 21, Section 173.315: "Ingredients for use in washing or lye peeling of fruits and vegetables". These regulations restrict the ingredients that may be used for direct contact with food to those described as "generally recognized as safe" (GRAS), and a few other selected ingredients. These sections also provide certain limitations on the amount of material that can be used in a given context. Among these ingredients, the experienced formulator will find only a few ingredients which can provide effective cleaning of hydrophobic residues, such as oils, or man-made chemical residues such as pesticides. It is recognized these types of residues are removed most readily by surface active ingredients in water, or by organic solvents largely in the absence of water. Other types of soils, especially particulate insoluble soils that do not readily disperse in water, are effectively removed by surface active materials in water, especially when aided by complex anionic salts, such as citrates (polycarboxylates), or polyphosphate salts. Within this limited group of ingredients the range of effective cleaning compositions well suited to the task of cleaning edible animal protein, especially as practiced by individual consumers, have not been previously described. It is desirable to formulate liquid compositions which are amenable to either direct application to edible animal protein, preferably by spray application, or could be provided in suitable concentrated form to allow convenient dilution in a bowl or sink of water for washing of said protein by immersion. Further, it is desirable if the compositions are low sudsing, and easily rinsed, without leaving residue. Preferred compositions should be mild to the hands, especially for direct application. SUMMARY OF THE INVENTION The present invention encompasses methods for cleaning edible animal protein, especially meat, seafood and poultry, (and compositions, as disclosed hereinafter, for practicing said methods) at a basic pH. The present invention comprises several aspects including: I. A method for cleaning edible animal protein comprising contacting the surfaces of said protein by direct application of an aqueous cleaning solution typically comprising: (a) from about 0.01 % to about 15% of Cg-C i g fatty acid; (b) optionally, from about 0.1% to about 4% by weight of nonionic surfactant, especially ethoxylated and/or propoxylated adducts of aliphatic Cj2-18 alcohols, but preferably less than about one eighth of the amount of said fatty acid; (c) optionally, from about 0.1% to about 4% by weight of organic polycarboxylic acid, preferably citric acid; (d) optionally, up to about 0.2% by weight of base-stable anionic surfactant such as the alkali or alkaline earth salts of dodecylbenzene sulfonate; (e) optionally, toxicologically-acceptable basic buffer such as potassium and/or sodium basic materials, e.g., the hydroxides and/or salts of carbonate and/or bicarbonate; (f) optionally, toxicologically-acceptable preservative; (g) optionally, but preferably, from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.3% to about 2% of phosphoric acid; (h) optionally, at least about 0.05%, preferably from about 0.1% to about 10%, most preferably from about 0.25% to about 3.0%, by weight, of water-soluble polyethylene glycol having a molecular weight of about 200, or higher; and (i) the balance comprising an aqueous carrier selected from water and, optionally, low molecular weight, toxicologically-acceptable organic solvent such as ethanol, glycerol, etc.; all of the acidic materials above being, of course, neutralized under the alkaline conditions of the product, preferably neutralized with sodium and/or potassium, preferably potassium, compatible basic material, wherein said aqueous solution has a pH in the range of 9.5 or greater, preferably more than about 10.5, more preferably from about 11 to about 13.5, and even more preferably from about 11.5 to about 12.5, and said composition preferably being essentially free of any material that is not toxicologically acceptable. The inventions disclosed herein preferably encompass compositions for use in a method for cleaning edible animal protein at a basic pH above about 9.5, comprising: (a) from about 0.01% to about 15% of Cg-Cjg fatty acid which is neutralized, preferably a member selected from the group consisting of sodium or potassium oleate (preferred), or from about 0.5% to 10% by weight of sodium or potassium laurate; (b) optionally, from about 0.1% to about 4% by weight of nonionic surfactant, especially ethoxylated propoxylated adducts of aliphatic Cj2- 18 alcohols, but preferably less than about one eighth of the amount of said fatty acid; (c) optionally, but preferably, from about 0.2% to about 4% by weight of potassium and/or sodium polycarboxylate, having detergent building capability and preferably being derived from natural sources, such as potassium and/or sodium citrate, as a dispersant for particulate soils; (d) optionally, up to about 0.2% by weight of base-stable anionic surfactant such as the alkali or alkaline earth salts of dodecylbenzene sulfonate; (e) optionally, toxicologically-acceptable basic buffer such as potassium and/or sodium basic materials, e.g., the hydroxides and/or salts of carbonate and/or bicarbonate; (f) optionally, toxicologically-acceptable preservative; (g) optionally, but preferably, from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.3% to about 2% of phosphoric acid; and (h) optionally, at least about 0.05%, preferably from about 0.1% to about 10%, most preferably from about 0.25% to about 3.0%, by weight, of water-soluble polyethylene glycol having a molecular weight of about 200, or higher; (i) the balance preferably comprising aqueous carrier selected from water and, optionally, low molecular weight, toxicologically-acceptable organic solvent such as ethanol, glycerol, etc., preferably selected from water and water-ethanol; wherein said aqueous cleaning solution has a pH of 9.5 or greater, preferably greater than 10.5, and preferably employs carbonate salt, or salts, as buffer (e), preferably with hydroxide base, to provide a pH of from about 11 to about 13.5, preferably from about 11 to about 12.5, more preferably from about 11.5 to about 12.5. The compositions can also be formulated as concentrates, in which at least part of (i) is removed and the levels- of the remaining ingredients are adjusted to complete the formula. In all of the above lists of components, if an ingredient can be classified in more than one place, it will be classified in the first place it can appear. A more specific method for cleaning edible animal protein at a basic pH, preferably more than about 9.5, comprises contacting the surfaces of said protein with an aqueous cleaning solution comprising potassium oleate, preferably at a level of more than about 0.5%. Potassium oleate is mild, rinses well, has minimal odor, is effective in removing unwanted materials, does not oversuds, and is very safe, even when the composition is misused and said protein such as meat, seafood, or poultry, etc., is not completely rinsed. Therefore, it is a uniquely preferred surfactant for use in cleaning food materials like edible animal protein. The potassium cation is more useful than the sodium cation, especially in the absence of polyethylene glycol, since the potassium oleate is quite soluble whereas the sodium oleate tends to form a less soluble soap, especially at low temperatures. A concentrated, alkaline method for cleaning edible animal protein comprises contacting the surfaces of said protein with a cleaning solution containing from about 0.01% to about 15%, preferably from about 0.75% to about 8%, more preferably from about 1% to about 5%, detergent surfactant, preferably one that is GRAS, and more preferably said oleate surfactant, said cleaning solution having a pH of from about 9.5 to about 13.5, preferably from about 11 to about 12.5, especially when the detergent surfactant is a soap such as the said oleate, more preferably from about 11.5 to about 12.3. Another preferred variation in the above methods for cleaning edible animal protein involves placing said cleaning solutions in a spray container to provide a spray of said solution to distribute the said solution, or solutions, over the surfaces of the said protein while utilizing only a minimum amount of the cleaning solution and minimizing the exposure of the remaining solution to the atmosphere, where the solution is more likely to be contaminated and/or exposed to oxygen, both of which tend to cause undesirable changes in the solutions from aesthetic and/or performance considerations. In such spray processes, there is only need for a relatively small amount of material in the package, and for individual consumer use, this is desirable, since some consumers will not be able to manipulate large weights. For individual consumer usage, typically, the container will contain no more than about two gallons (about eight liters), preferably no more than about one gallon (about four liters), especially when the container is a spray container, even one that has a tube that permits the spray device to be manipulated while the bulk container remains in place. More preferably such spray containers contain about one liter, or less, of cleaning solution. The invention encompasses basic cleaning compositions in both concentrated and dilute forms, especially adapted for practicing said methods. (In the following disclosure, the lower amounts of the specified ingredients denote the dilute forms of the compositions herein and the higher amounts denote the concentrated forms which are typically diluted by a factor of from about 2 to about 3.) The compositions can be concentrated even more to non-aqueous liquids or solids according to the teaching in U.S. Pat. 5,280,042, Lopes, said patent being incoφorated by reference. Such compositions include the following. A composition for cleaning edible animal protein at a basic pH, comprising: (a) from about 0.01% to about 15%, preferably from about 1% to about 5%, by weight of a member selected from the group consisting of sodium or potassium oleate (preferred), sodium or potassium laurate, or mixtures thereof; (b) optionally, from about 0.1% to about 4%, preferably about 0.3% to about 1.0%, by weight of nonionic surfactant as described above; (c) from about 0.2% to about 4% by weight of polycarboxylic acid salt, especially potassium hydrogen citrate; (d) from about 0.3% to about 5% of ortho-phosphoric acid; and (e) the balance comprising aqueous carrier selected from water and water- ethanol; wherein said composition has a pH of 9.5 or greater. Preferably, the basic compositions herein contain from about 0.5% to about 1.5% by weight of potassium, and/or sodium, carbonate and/or bicarbonate buffer and have a pH of from about 11 to about 13.5, preferably from about 11.5 to about 12.5. Preferred compositions for use herein in a concentrated alkaline method contain from about 0.01% to about 15%, preferably from about 0.5% to about 8%, more preferably from about 1% to about 5%, detergent surfactant, preferably one that is GRAS; from about 0.3% to about 5% of ortho-phosphoric acid and have a pH of from about 9.5 to about 13.5, preferably from about 11.5 to about 12.3. The present invention also encompasses detersive compositions with an improved tactile impression which are especially adapted for cleaning edible animal protein, comprising: (a) at least about 0.1%, preferably from about 0.5% to about 8%, most preferably from about 1% to about 5%, by weight, of a C12-C18 fatty acid or salt thereof; (b) at lεast about 0.05%, preferably from about 0.1% to about 10%, most preferably from about 0.25% to about 3.0%, by weight, of water-soluble polyethylene glycol having a molecular weight of about 200, or higher; (c) from about 0.1% to about 5% of neutralized ortho-phosphoric acid; and (d) water or water-ethanol fluid carrier, said composition having a basic pH. The balance of the composition can comprise various optional adjunct materials, pH-adjusting agents, perfumes or essences, preservatives and the like. In a preferred mode, component (b) has a molecular weight in the range from about 300 to about 9500. Typical compositions herein are wherein component (a) is potassium oleate, and wherein the weight ratio of (a):(b) is in the range from about 1:2 to about 30: 1, preferably from about 1 :1 to about 15:1. The compositions having improved tactile impression are typically formulated in the basic pH range, preferably from about pH 9.5 to about pH 12.5. Preferred compositions have a viscosity at room temperature of less than about 100 centipoise, preferably less than about 50 centipoise for sprayable compositions. Preferred compositions for use herein contain only materials that are GRAS, including, of course, direct food additives affirmed as GRAS, to protect against possible misuse by the consumer. Traditionally, most suggestions for cleaning of edible animal protein have contemplated a commercial scale where there is typically more control over the conditions, especially the amount and thoroughness of rinsing. The present invention, especially the methods involving use of hand held trigger activated spray means are primarily/solely suitable for use by individual consumers so that it is essential that extra safety be built into the product. Failure to rinse thoroughly after cleaning is less of a concern if all of the ingredients are GRAS. This is especially important when concentrated basic compositions are used. The larger amounts of materials in concentrated basic compositions create a heretofore unknown level of risk for the individual consumers, many of whom are not likely to read, or follow, instructions which would permit safe use of non-GRAS materials. The ingredients in the above compositions are preferably selected and used in proportions which provide substantially clear compositions. "Substantially clear" includes only minimal haziness, and preferably the compositions are completely clear. The ingredients are also selected to have minimal odor, both initially and after storage. The lack of strong odor is especially important in compositions for use on food. The compositions preferably have a viscosity that is more than about 1 centipoise, preferably more than about 3 centipoise when at rest, but thin under shear to permit easy dispensing, especially from spray containers. Below pFLabout 9.7, the-compositions can exhibit some objectionable fatty acid odor. Even at the optimal pH's above 11, some odor can persist. In order to mask this odor, the compositions can contain a GRAS perfume, or essence, ingredient. Especially preferred for this use are oils derived from citrus fruit, e.g., oranges, lemons, limes, grapefruits, tangerines, tangelos, etc. which contain relatively large amounts of teφenes. All documents cited herein are incoφorated herein by reference. DETAILED DESCRIPTION OF THE INVENTION The present invention encompasses methods for cleaning edible animal protein, especially meat, seafood and poultry, (and compositions, as disclosed hereinafter, for practicing said methods) at a basic pH. By "edible animal protein" is meant to include foodstuffs which are comprised essentially of the protein found in such foods sources including, but not limited to, beef, pork, chicken, turkey, fish, shellfish and game meats such as venison, rabbit and the like. Said edible animal protein includes the processed forms of said protein sources, including, but not limited to, such forms as ground beef, ground turkey, bologna, hot dogs, sausages, fish cakes, and the like. The methods described herein employ the following toxicologically- acceptable ingredients are used in the preparation of the preferred compositions herein. By "toxicologically-acceptable" is meant that any residues from the ingredients of the compositions which may remain on the edible animal protein cleansed therewith are safe for ingestion by humans and/or lower animals. Nonionic Surfactant - The nonionic surfactant is preferably selected from materials known in the art, such as alkylene oxide (ethylene oxide and/or propylene oxide) adducts of Cιo-18 aliphatic alcohols or acids, CJO-18 aliphatic alcohol adducts of glucose (alkyl polyglucosides). The specific nonionic surfactant selected ideally has a hydrophilic-iipophilic balance (HLB) greater than about 10, and a cloud point above about 35°C in the composition. The United States Code of Federal Regulations (CFR) specifically describes an ethylene oxide/propylene oxide adduct of C12-18 aliphatic alcohol of molecular weight of about 800. Such a material is available as PLURAFAC RA-20 (BASF). Fatty Acid and/or Salts Thereof - The acidic compositions herein are preferably formulated using an unsaturated fatty acid; oleic acid is preferred and convenient for this use. However, the particular oleic acid that is selected should preferably be low in polyunsaturates, e.g., contain less than about 10%, preferably less than about 7%, more preferably less than about 5%, polyunsaturated acid minor components, and will typically have an Iodine Value (IV) of from about 70 to about 100, preferably from about 83 lo about 95, more preferably from about 85 to about 90. Polyunsaturated fatty acids are not preferred herein, due to odor problems. However, this is primarily from aesthetic considerations since such acids are effective in cleaning. The amount of polyunsaturated fatty acids should be less than about 8%, preferably 0%. The amount of polyunsaturated fatty acids with more than about two double bonds should be less than about 1%, preferably 0%. Saturated fatty acids are unacceptable as they have limited solubility for longer chainlength materials (>Ci2) . or have unacceptable odor (≤CJO). For example, stearic and/or tallow fatty acids soaps, even potassium soaps, do not have enough solubility at room temperature, where most food cleaning is done by individual consumers, to formulate even compositions containing the minimum of about 0.1% soap required for acceptable cleaning. Other specific solubilizing surfactants in higher proportions would be required to solubilize these saturated fatty acids. Pamolyn 100 FGK oleic acid is a good example of a suitable commercial fatty acid. Phosphoric Acid Phosphoric acid is an extremely desirable component for improving the cleaning. Polyethylene Glycol - The water-soluble polyethylene glycol polymer (PEG) employed herein is the known article of commerce and is available under a variety of trade names, of which CARBOWAX (Union Carbide Coφoration) is exemplary. PEG's in the average molecular weight range of from about 200 to about 20,000 can be used herein, and PEG as CARBOWAX in the average molecular weight range of at least about 200, typically 300 to about 9500, is convenient and preferred. As disclosed above, the compositions herein will comprise at least about 0.05%, by weight, of the PEG and will typically comprise from about 0.1% to about 10%, by weight, of PEG. The amounts used can vary with the molecular weight of the PEG, the amount of oleate or other fatty acid used in the composition, the desired viscosity of the composition, and like factors within the discretion of the formulator. The following Table 1 illustrates the variation in viscosity which can be effected using various levels of PEG and varying PEG molecular weights in a liquid composition (Control) comprising 3% potassium oleate. Table 1 also illustrates the effect of sodium benzoate (Bz) on viscosity. Table 1 Viscositv CcP* as made iscositv (cP* as made Composition 72°F (22°C 43°F (6°C) Control (no PEG) 7 IIO Control + 0.674% Bz 23 1000 Control + 0.118% Bz 7 159 Control + 0.1% PEG 400 5 36 Control + 0.5% PEG 400 2 17 Control + 0.1% PEG 8000 5 23 Control + 0.5% PEG 8000 8 4 •Viscosity in centipoise as measured using Brookfield LVTD #2 spindle, 60 φm at the designated temperature. In a typical mode, the preferred compositions herein that have an improved tactile impression will comprise oleate:PEG weight ratios in the range from about 1:2 to about 30:1, preferably from about 1:1 to about 15:1. Tactile Impression - The compositions herein which contain the polyethylene glycol are characterized not only by their excellent cleaning performance and sudsing rinsability properties, but also by their improved viscosity properties and improved "feel". While, as disclosed above, the improved viscosities of the compositions herein are readily demonstrated quantitatively using standard measurement techniques, the improved feel of the compositions which come into contact with the users' hands is a qualitative tactile impression. However, this improved, "non-slippery", "non-soapy" improvement in skin feel can be demonstrated by rubbing Test (PEG-containing) and Control (no PEG) compositions on the hands or inner forearms of volunteer graders. Even in such rudimentary tests, the graders can readily distinguish the improved tactile impression of the compositions made in accordance with this invention. Optional Surfactants - Optionally, base stable anionic surfactants can be employed, particularly those allowed by the United States Code of Federal Regulations, Title 21, Section 173.315, for fruits and vegetables. Preferred are salts of dodecylbenzene sulfonate, typically at levels up to 0.2%. Also described in the CFR for fruits and vegetables, and useful in the present context, are phosphate esters of ethylene and/or ethylene/propylene oxide adducts of aliphatic alcohols, dioctyl sulfosuccinate, and 2-ethylhexyl sulfate. Sequestrant/builder - The organic polycarboxylic acid, or salt thereof, e.g., citric acid, or sodium and/or potassium citrate, and/or ethylenediaminetetraacetic acid, or sodium and/or potassium ethylenediaminetetraacetate, are standard items of commerce and are GRAS. Other organic poly carboxylic acids, especially those that are GRAS, such as tartaric, malic, etc. acids, can also be used. When formulating the basic formulations herein, it is preferred to use the potassium salt, as compared with the sodium salt, to prσvide ease of fσrmulatability. Complex phosphates can also be used, but are generally avoided due to regulatory considerations. Buffer - Toxicologically-acceptable basic buffers can be used in the compositions herein to maintain product pH in the base range. For ease of formulatability, it is preferred that such buffers be carbonate based, it is highly preferred that such basic buffers be in their potassium salt form. Potassium citrate is a preferred dispersant for particulate soils. Potassium carbonate is a convenient and preferred basic pH buffer. Sodium bicarbonate is a highly desirable material to add to the compositions of this invention as a part of the buffering system since it is readily available as baking soda in food grade and is therefore relatively inexpensive, while providing a highly desirable purity to the composition. Compositions formulated with a mixture of potassium and sodium cations in molar ratios of from about 1:1 to about 10:1, preferably from about 2:1 to about 8:1, more preferably from about 4:1 to about 5: 1 potassium to sodium, e.g., as provided by mixtures of potassium hydroxide (hydrate) and sodium bicarbonate, have desirable rheological properties. The compositions are sufficiently viscous, so as to cling to the edible animal protein until spread, but are readily dispensed, e.g, by means of a spray device, either aerosol or finger-activated pump. The levels and identities of the ingredients are adjusted to provide products having the desired viscosities as set forth herein, e.g., more than about 1, preferably more than about 2, more preferably more than about 3 centipoise when at rest, and less than about 150, preferably less than about 100, more preferably less than about 50 centipoise under shear of > ~1000 sec" 1 The ability of the preferred compositions containing mixtures of both sodium and potassium cations to shear thin is important to promote easy dispensing, especially when the compositions are sprayed, while maintaining the ability to be thick, cling, and delay run off after being applied to the edible animal protein. The pH is preferably not greater than about 13.5, and especially does not contain large amounts of buffer at higher pHs for consumer safety, especially when the compositions are sprayed. Preservative - Formulating the present compositions at high pH reduces the tendency for biological growth of contaminants, such as bacteria, fungi, or molds. At neutral pH, an increased reliance on preservatives is required to insure the lack of biological growth through contamination in making or in use. Standard food-grade preservatives such as ethylenediaminetetraacetic acid and/or the salts thereof, at a level of from about 0.01% to about 0.2% of ethylenediaminetetraacetic acid, or its sodium and/or potassium salts, can be used although, in general, the basic pH compositions herein dc not require a preservative. Antioxidants The use of commercial oleic acid, or oleate salts, can be complicated by development of off-odors and/or yellowing of the compositions in which they appear. These undesirable properties are believed to be caused by complex side reactions initiated by the reaction of oxygen with primarily the polyunsaturated components ofthe fatty acid stock. These results can be avoided, or minimized, by avoiding contact with air, or by controlling the quality ofthe fatty acid stock so that the amount and type of polyunsaturates are minimized as described above, and/or by the addition of antioxidants. It has been found, that the addition of tocopherols (e.g., Vitamin E, or tocopherol acetates) in alkaline formulations is advantageous, as they do not degrade, nor do they impart a strong color. They inhibit the development of off-odors for extended periods of time so that the need for masking scents is minimized, or eliminated, particularly for oleic acid stocks of high quality, as described above. The use of butylated phenols, such as BHT and BHA is also useful, but the quantity should be limited to avoid imparting colors to the compositions. Other food grade antioxidants such as Vitamin C and sulfites, are desirable to prevent deterioration of the compositions by the action of oxygen, but care must be taken since vitamin C can suffer color degradation and sulfites can cause odor problems. Sulfites also have been the target of potential health concerns. Fluid Carrier - The major proportion, e.g., more than about two thirds, (typically, 80%-98%, by weight) of the compositions herein comprises water as the solubilizing carrier for the ingredients. As noted in the Examples hereinafter, water- ethanol can also be employed and is especially preferred when formulating the basic pH compositions herein. The ethanol level preferably should not exceed 2% in the solution used to clean the edible animal protein, to avoid an alcoholic odor, especially when spraying. Other compatible, water-soluble, low molecular weight solvents such as glycerol can also be used. The compositions herein are preferably used by placing them in a package comprising either an aerosol container or a non-aerosol spray device "spray means." Said spray means is any of the manually activated, preferably "trigger-type," means for producing a spray of liquid droplets as is known in the art. Typical spray means are disclosed in U.S. Pat. Nos.: 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161,288, McKinney, issued July 17, 1979; 4558,821, Tada et al., issued Dec. 17, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989, all of said patents being incoφorated herein by reference. The spray bottle, or container can be any of the ones commonly used for containing hard surface cleaner detergent compositions. Examples of bottles are those in U.S. Design Pat. Nos.: 244,991, Weekman et al., issued July 12, 1977; and 275,078, Wassergord et al., issued Aug. 14, 1984, said patents being incoφorated herein by reference. The spray means herein can also include those that incoφorate a compatible propellant gas into the liquid and those that will foam even detergent compositions having a viscosity of less than about 15 cps. The device can also be one that can be adjusted to either give a liquid spray or a foam. The spray means herein are typically those that act upon a discrete amount of the composition itself, typically by means of a piston that displaces the composition and expels the composition through a nozzle to create a spray of thin liquid. Preferred articles include the compositions herein that are suitable for use in the processes described herein, in a package that can provide a spray. Such articles are not widely marketed. This is suφrising in view of the clear advantages for such products for use by individual consumers. The typical use involves treating individual items of edible animal protein, which would make preparation of a "bath" wasteful. In a preferred process for using the products described herein, and especially those formulated to be used at full strength, the product is sprayed onto the food product to be cleaned, rubbed, rinsed and/or wiped off with a suitable clean material like cloth, sponge, a paper towel, etc. Suφrisingly, the compositions and processes described herein can provide effective disinfectancy/sanitization. In order to provide good kill of microorganisms, especially bacteria, one should use high concentrations and/or longer exposure times. Typically, the products should be used full strength and allowed to remain on the edible animal protein fr at least about one minute, preferably at least about five minutes, and, for some microorganisms, even ten minutes may be required. Longer exposure times (i.e., the time that the bacteria better antimicrobial benefits. The importance of time depends both on the pH ofthe product and on the formula concentration. At high pH (> 11.5) and high concentrations, antibacterial efficacy is achieved quickly. At lower pH values (pH < 11) and lower formula concentrations, a longer period of exposure time is required to achieve the same efficacy. Higher pHs are also better, in general. This factor is important for the product's performance on the Gram negative bacteria, e.g., Escherichia coli and Pseudomonas species. Higher product pH's produce quicker and more complete kill. The opposite is true for the Gram positive bacteria, e.g., Staphylococcus aureus. Performance is equal to, or slightly better, as the pH is lowered from 11.5 to 9.5. However, this is only true wherrthe formula contains oleic acid. As stated above, higher formula concentrations (when done independently of pH) enhance the antimicrobial efficacy of the product. The presence of oleic acid is likely a key factor for the performance on Gram positive organisms like S. aureus, while the pH is probably a bigger factor for the Gram negative bacteria, e.g., E. coli and Pseudomonas species. Packaging the products herein in a container with instructions for usage in terms of timing and avoidance of dilution in order to provide disinfectancy/sanitization, will help the individual consumer by providing information for proper usage in order to remove/kill microorganisms. It is a special advantage of the product that it can be used for this purpose at a time in the food production process where recontamination is minimized. The subject of this invention has also been shown to mitigate unpleasant "meaty/off 1 odors that appear on meat. Such odors in many cases could cause the food item to appear unusable resulting in disposal, when in fact it could be acceptable for use when adequately cooked. The use of the invention would therefore not only help reduce microbial contamination, but also eliminate off odors normally associated with meat, and help to prevent unnecessary disposal of an other wise usable meat product. As meat products tend to be expensive items, utilizing meat that otherwise would be disposed of represents monetary as well as resource savings. All parts, percentages, and ratios herein are "by weight" unless otherwise stated. All number values are approximate unless otherwise stated. The following Examples illustrate the compositions and processes of this invention, but are not intended to be limiting thereof. The exemplified basic liquid compositions can be prepared at pH 9.5-13.5 by dissolving the ingredients in water or water-ethanol using conventional mixing apparatus. In a convenient mode, water is placed in a mixing vessel. Potassium hydroxide, the ortho-phosphoric acid, any citric acid, any bicarbonate, glycerine (processing aid), and any ethanol are added in the named sequence, with stirring. The oleic acid is added with high shear and stirring is continued. The PEG (which can conveniently be predispersed in water) is then added. The optional perfume ingredients can be added any time after the oleic acid has been dissolved in the mixture. Example 1. 5 Sirloin strips (~2"x4") that had a some characteristic "off" or meaty odor were sprayed (~5 grams total product) respectively with wash solutions A,B,C,D and additionally a Tap water control, and allowed to sit for up to 30 minutes. The meat was evaluated for texture, color and odor over this time. Although no significant texture or color changes were noted for the products, test versions B,C, and D all took away much of the unpleasant meaty odor while A and the Tap water had retained much ofthe undesirable odor (as judged by 3 of 3 odor panelists). The test was repeated, this time with a tap water rinse to remove the applied product before odor evaluations. B, C, and D again had the best final odor, with A and the Tap water being the poorest. Chicken legs with & without skin were sprayed (~5 grams total product) with the wash solutions. Again no texture or color changes were noted. In this test, product D had the preferred odor. Salmon cuts were also evaluated. The results were the same as that on chicken. The odor evaluations show that embodiments of the present invention improve odor on meat relative to other methods of meat washing, with the higher bicarbonate version helping more on chicken and seafood. A B C D ComDonent wt% Component wt% ComDonent wt% Component wt% Water Balance Water Balance Water Balance Water Balance TKP 1 5 Oleic acid 2.643 Oleic acid 2.643 Oleic acid 0.441 Glycerol 2.0 Glycerol 2.0 Glycerol 2.0 Ethanol 2.0 Ethanol 2.0 Ethanol 2.0 Potassium 1.35 Potassium 2.8 Potassium 1.812 hydroxide hydroxide hydroxide Sodium .547 Sodium .547 Sodium 2.0 bicarbonate bicarbonate bicarbonate Citric acid .52 Citric acid .52 Citric acid 0.52 Grapefruit .03 PEG 3350 .35 Grapefruit 0.03 oil oil Grapefniit .03 oil Phosphoric 1.0 acid pH 12.5 pH 11.5 ρH 11.9 pH 10.7 1 TKP = Tri-Potassium Phosphate Example 2. 2 lb. of beef chuck boneless pot roast was cut into 5 pieces and each placed in a glass bowl. Each piece was treated by spraying the surface (~ 5 grams) with one of the respective treatments E, F, G, H or a Tap water control. The samples were allowed to sit for 30 minutes and then rinsed under tap water for 30 seconds. In this case a panel of 5 odor graders rated the respective samples from 1 to 5, with 5 being the most pleasant and 1 being the least. The results are as follows: Product Averace Grade E 4.6 H 3.8 G 3 F 2.6 Tap Water 1 £ F G H Component wt% Component wt% Component wt% ComDonent wt% Water Balanc Water Balance Water Balanc Water Balanc e e e Oleic acid 2.643 Oleic acid _ Oleic acid 2.643 Oleic acid 2.643 Glycerol 2.0 Glycerol 2.0 Glycerol 2.0 Glycerol 0.0 Ethanol 2.0 Ethanol 2.0 Ethanol 2.0 Ethanol 0.0 Potassium 1.35 Potassium 0.83 Potassium 0.99 Potassium 4.75 hydroxide hydroxide hydroxide hydroxide Sodium .547 Sodium 0.547 Sodium Sodium 0.547 bicarbonate bicarbonate bicarbonate bicarbonate Citric acid .52 Citric acid 0.52 Citric acid 0.52 Citric acid 0.52 Grapefruit .03 Grapefruit 0.03 Grapefruit 0.03 PEG 3350 0.35 oil oil oil Grapefruit 0.03 oil Phosphoric 2.0 acid pH 11.5 pH 11.6 pH ll.6 pH 12 Test results indicate again that the present invention improves meat odor. Removing the detergent surfactant (oleate in case F) and the carbonate source (in case G) reduces the effectiveness of odor mitigation. Example 3. Formulas are evaluated for ability to kill various standard microorganisms. Minor adjustments ofthe pH of the formulas were done immediately prior to antimicrobial testing to give the above neat pH values. The formulas kill standard microorganisms effectively. The amount of time required for control of microorganisms is more than would ordinarily be provided by a normal cleaning operation. Therefore, it is important to package the product in a container with instructions for allowing sufficient time for effective kill to take place. Examples of effectiveness of formulas evaluated via total plate count. Preparation of test cultures The test organisms used were: Escherichia coli ATCC # 25922; Staphylococcus aureus ATCC # 25923; and Pseudomonas aeruginosa ATCC # 27853. The cultures were prepared from Difco brand freeze dried culture disks. A fresh disk of each organism was placed in an 8 ml. tube of sterile trypticase soy broth and incubated overnight in 37°C. The number of CFUs (Colony Forming Units) in the original cell cultures was determined by serial dilution. Both the prepared trypticase soy broth and the culture disks were obtained from VWR Scientific. Antimicrobial testing A 100 g antimicrobial sample was used for each test. A 1 ml. aliquot of each culture was then pipetted into separate 100 g antimicrobial samples. The bottles were shaken vigorously to distribute the organisms. After 5, 10, and 20 minutes, 1 ml. aliquots of the inoculated antimicrobial samples were pipetted into 10 mis. of sterilized neutralizing broth. These bottles were also shaken vigorously to distribute any remaining organisms. Finally, 1 ml. aliquots from the neutralizing broth were plated on trypticase soy agar and incubated for ca., 66 hours, at 37°C. The prepared trypticase soy agar plates and trypticase soy broth were both obtained from VWR Scientific. After the indicated incubation period, the number of CFLPs was visually counted. The results were recorded as numbers of colonies CFU's per plate present after incubation. The term "TNC" refers to Too Numerous to Count. The term "<TNC" refers to visibly fewer colonies than TNC but still to "numerous to count." E.Coli I J K L Time Plate count Plate count Plate count Plate count 5 min. 0 17 TNC TNC 10 min. 0 0 350 500 20 min. 0 0 0 0 S. aureus I J K L Time Plate count Plate count Plate count Plate count 5 min. 200 75 100 150 10 min. 100 50 80 75 20 min. 75 20 40 20 P. aeruginosa I J K L Time Plate count Plate count Plate count Plate count 5 min. 0 0 0 0 10 min. 0 0 0 0 20 min. 0 0 0 0 Example Compositions Ingredients I J K L Water Balance Balance Balance Balance KOH 1.328 2.15 1.63 1.8 ethanol 1.5 1.5 1.5 1.5 glycerine 2 - 2.0 - oleic acid 2.643 2.643 .44 2.643 sodium .547 2.0 2.0 2.0 bicarbonate methanol .5 .5 .50 .5 citric acid .52 .52 .52 .52 PEG 3350 - .5 • .5

Claims: What is claimed is: 1. A method for cleaning and reducing the level of microorganisms on edible animal protein, comprising the step of contacting said protein with an aqueous cleaning solution comprising at least about 0.01% detergent surfactant and having a basic pH of greater than about 9.5 for a time in excess of about one minute and sufficient to effect a significant reduction in microorganisms as compared to the same process where the solution is immediately rinsed off. 2. The method of Claim 1 wherein said aqueous cleaning solution comprises: (a) from about 0.01% to about 15% of Cg-Cjg fatty acid, preferably from about 0.05% to about 10% of oleic acid; (b) optionally, from about 0.1% to about 4%, preferably from about 0.3% to about 1%, by weight of nonionic surfactant; (c) optionally, from about 0.1% to about 4%, preferably from about 0.2% to about 4%, by weight of organic polycarboxylic acid, preferably ethylenediaminetetraacetic acid; (d) optionally, up to about 0.2% by weight of base-stable anionic surfactant; (e) optionally, a toxicologically-acceptable basic buffer; (f) optionally, a toxicologically-acceptable preservative; (g) optionally, from about 0.05% to about 10%, from about 0.1% to about 5%, preferably from about 0.3% to about 2%, of phosphoric acid; and (h) the balance comprising an aqueous carrier selected from water and, optionally, low molecular weight, toxicologically-acceptable organic solvent; wherein said aqueous solution has a pH of more than about 10.5, preferably from about 11 to about 13.5, and, preferably, said aqueous cleaning solution has a viscosity less than about 100 centipoise, preferably less than about 50 centipoise, under shear of greater than about 1000 sec"l. 3. A method according to any of Claims 1-2 in which said aqueous cleaning solution has an improved tactile impression and comprises: (a) at least about 0.75%, by weight, of oleic acid or salt thereof; and (b) at least about 0.05%, by weight, of a water-soluble polyethylene glycol having a molecular weight of about 200, or higher, preferably from about 300 to about 9500, and wherein the weight ratio of (a):(b) is in the range from about 1:2 to about 30:1. 4. A method according to any of Claims 1-3 wherein component (a) is potassium oleate, and said organic polycarboxylate acid is citric acid, and preferably wherein said aqueous cleaning solution additionally comprises oil derived from grapefruit. 5. A method according to any of Claims 1-4 wherein the pH of said aqueous cleaning solution is in the range from about 11 to about 12.3, preferably said aqueous cleaning solution remains in contact with said edible animal protein, preferably for at least about five minutes, and wherein said microorganisms are bacteria. 6. The method according to any of Claims 1-5 in which said protein comprises meat, seafood, and poultry. 7. An article of commerce comprising a container containing an aqueous cleaning solution which comprises: (a) from about 0.01% to about 15%, preferably from about 0.05% to about 10%, of C8-C1 fatty acid, preferably oleic acid; (b) optionally, from about 0.1% to about 4%, preferably from about 0.3% to about 1%, by weight of nonionic surfactant; (c) optionally, from about 0.1% to about 4%, preferably from about 0.2% to about 4%, by weight of organic polycarboxylic acid; (d) optionally, up to about 0.2% by weight of a base-stable anionic surfactant; (e) optionally, a toxicologically-acceptable basic buffer; (f) optionally, a toxicologically-acceptable preservative; (g) optionally, from about 0.05% to about 10%, preferably from about 0.1% to about 5%, of phosphoric acid; and (h) the balance comprising an aqueous carrier selected from water and, optionally, low molecular weight, toxicologically-acceptable organic solvent; wherein said aqueous solution has a pH of more than about 10, preferably from about 11 to about 13.5, and where said container has instructions for treating surfaces selected from the group consisting of: edible animal protein surfaces; non-food, inanimate surfaces; and fabric surfaces, comprising the instruction to apply the solution to the said surfaces and to allow the solution to remain in contact for at least about one minute, preferably for at least about five minutes. 8. The article of Claim 9 wherein said container is a spray container, suitable for use by an individual to clean edible animal protein and, preferably, wherein all of the ingredients of said solution are GRAS, and, preferably, wherein there is at least 0.5% detergent.

Inventors: BAKER KEITH HOMER, BULLOCK STEVEN STEWART, JONES KYLE DAVID, ROSELLE BRIAN JOSEPH, WARD THOMAS EDWARD
Applicants: BAKER KEITH HOMER, BULLOCK STEVEN STEWART, JONES KYLE DAVID, PROCTER & GAMBLE, ROSELLE BRIAN JOSEPH, WARD THOMAS EDWARD
Application year: 1996
Main classification: A23P1
IPC codes: A23B4, A23B7, A23J3, A23L1, A23N12, C11D1, C11D3, C11D10, C11D11