Title of the Invention

FOOD AND BEVERAGE PRESERVATIVES CONTAINING D-LIMONENE Cross Reference to Related Applications

[0001] This application claims priority to and benefit of U.S. Provisional Application

No. 60/801,459, filed May 17, 2006, and is a continuation-in-part of U.S. Application No. 10/662,774, filed September 15, 2003, which claims priority to and benefit of U.S. Provisional Application No. 60/447,592, filed February 14, 2003. The contents of each of the above referenced applications are incorporated herein by reference.

Field of the Invention

[0002] The present invention relates to preservatives formulated to reduce growth of microbial contaminants such as bacteria and spores that cause spoilage of food, beverages and other goods. This application also relates to particularly advantageous synergistic combinations of antimicrobial ingredients that can be used in food and beverages without imparting off- flavors.

Background of the Invention

[0003] Bacteria and other microbial organisms cause food and beverage products as well as other products and goods to spoil thereby reducing the shelf life or useful life of such products or goods. Numerous efforts have been made to reduce the deleterious effects of microbial contaminants in food and beverage products and other materials. Previous food and beverage preservative compositions include those using chemical preservatives which can cause adverse side effects when consumed. Many existing preservatives must be regulated and have legally imposed upper limits on the amounts of preservatives allowable. In addition, many preservatives, such as sodium benzoate, proprionates, aromatic benzenes, organic acids, propylene glycol and glycerol, for example, when used at levels sufficient for

antimicrobial effects, impart an unpleasant taste on the beverage or food, masking or altering to some degree the taste expected by the consumer.

[0004] Other food preservatives such as salt and vinegar have been used for generations and while relatively safe to use, their preservative effect is limited in both duration of effect and the types of food and beverages for which they can be used. In addition, at higher levels, preservatives such as salt and vinegar can effect the taste of the product.

[0005] Accordingly, a great need exists for effective, relatively inexpensive, nontoxic, naturally derived preservative compositions that are capable of reducing microbial contamination and concomitant spoilage in a wide range of food, beverages and other consumer goods, but without altering the taste or function of the product.

Summary of the Invention

[0006] The present invention relates to preservative compositions formulated to reduce growth of contaminants such as bacteria, mold, yeast and spores that cause spoilage of food, beverages and other goods. The preservative compositions of the present invention include combinations of natural wax, such as beeswax, d-limonene and monohydric alcohol, such as ethanol. Applicants have unexpectedly found that this and similar combinations of ingredients provide compositions that are capable of preserving food and beverage products and other consumer products for long periods of time, significantly exceeding the time provided by preservative compositions containing just one of these ingredients. In addition, preservative compositions according to the certain embodiments of the present invention do not interfere with the taste of beverage and food products and do not interfere with the function of other consumer products.

[0007] Further, since compositions according to the present invention avoid the use of toxic chemicals or chemicals at toxic levels, there are fewer regulatory limitations for the use

of such compositions in food or beverages. Also, without the problem of toxicity, concentrations of preservatives according to the present invention can be increased or decreased to accommodate the amount of liquid in a particular product.

[0008] The present invention also provides methods of manufacturing such preservative compositions. In one embodiment, a method of this invention includes the steps of (1) heating water; (2) adding natural wax, such as beeswax, and mixing; (3) allowing the wax solution to cool; (4) removing solid wax; (5) mixing the water and wax extract mixture with potassium hydroxide; (6) providing d-limonene and an emulsifier, such as soy lecithin, in a separate container and mixing; (7) adding the d-limonene and emulsifier mixture to the water, wax extract and potassium hydroxide mixture; and (8) adding monohydric alcohol, such as ethanol, to the mixture formed by step 7.

[0009] Accordingly, one object of the present invention is to provide preservative compositions for beverage products comprising various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol.

[00010] Another object of the present invention is to provide preservative compositions for food products comprising various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol.

[00011] A further object of the present invention is to provide preservative compositions for a large variety of consumer products comprising various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol.

[00012] Another object of the invention is to provide beverage products comprising preservative compositions which comprise various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol.

[00013] An additional object of the invention is to provide food products comprising preservative compositions which comprise various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol.

[00014] Yet another object of the invention is to provide a large variety of consumer products comprising preservative compositions which comprise various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol. [00015] Another object of the invention is to provide methods of making preservative compositions for beverages, food and other consumer products, the preservative compositions comprising various combinations of natural wax, such as beeswax, d-limonene, and monohydric alcohol, such as ethanol.

[00016] And a further object of the invention is to provide methods of making beverage products, food products and other consumer products comprising preservative compositions which comprise various combinations of natural wax, such as beeswax, d- limonene, and monohydric alcohol, such as ethanol.

Detailed Description of the Invention

[00017] The present invention provides non-toxic, naturally derived preservative compositions formulated to reduce growth of microbial contaminants such as bacteria (both gram positive and gram negative), mold, yeast and spores that cause spoilage in various beverage products, food products and other consumer products.

[00018] The preservative compositions of the present invention may natural wax, such as beeswax, d-limonene, emulsifiers, such as soy lecithin and monohydric alcohol, such as ethanol. Applicants have unexpectedly found that this and similar combinations of ingredients provide compositions that are capable of preserving food and beverage products and other products for long periods of time, significantly exceeding the time provided by preservative compositions containing just one of these ingredients. Importantly, these

preservative compositions are effective without altering the taste of the beverage or food product and without altering the function of other consumer products. [00019] As used herein, unless otherwise stated, percentage amounts of an ingredient are by total weight of the preservative composition in which that ingredient is included. [00020] Preservative compositions of the present invention may include wax material.

The preferred wax material is beeswax. Natural wax, such beeswax may comprise from about 0.005 to about 10.0%, preferably from about 0.1 to about 5.0%, and more preferably from about 1.0 to about 2.0% and even more preferably about 1.4% of the preservative composition. Optionally, as a substitute for, or in addition to beeswax, the preservative compositions of the present invention may include other natural waxes, benzoic acid, salicylic acid and/or paraffin, alone or in various combinations, in amounts by weight totaling those given above for beeswax alone. Natural wax, such as beeswax, benzoic acid, salicylic acid and paraffin are commercially available from many sources. [00021] Preservative compositions of the present invention may also include d- limonene. D-limonene is the major component of the oil extracted from citrus rind. D- limonene has been used extensively as an ingredient in cleaning products. D-limonene may be obtained in various levels of purity ranging from ultra pure forms to regular forms. In certain embodiments of the present invention regular forms of d-limonene preferred over ultra pure forms. D-limonene in preservative compositions of the present invention may comprise from about 0.5% to about 20.0%, preferably from about 5.0 % to about 15.0%, and more preferably from about 9.0% to about 11.0%. D-limonene is commercially available from many sources.

[00022] Preservative compositions of the present invention also may include emulsifiers such as soy lecithin. Among the advantages of emulsifϊers such as soy lecithin are surface-active properties which provide, for example, the reduction in mixing time and

the maintenance of stability of dispersions. Emulsifϊers such as soy lecithin also provide a desirable homogenous appearance and prevent surface separation. When lecithins are used as emulsifϊers, in certain embodiments it is generally desirable to add them in the oil phase first. Heating the compositions promotes dispersion and may improve handling and mixing characteristics. In addition, phospholipids contained in lecithins have nutritional values of their own. Emulsifϊers used in the present invention may comprise from about 0.05 to about 15%, more preferably from about 0.5 to about 10%, and more preferably from about 1 to about 5%. Lecithins, particularly soy lecithins are preferred in certain embodiments of the present invention. Emulsifϊers such as soy lecithin are commercially available from many sources.

[00023] Preservative compositions of the present invention also may include monohydric alcohols such as methanol, ethanol and butanol, alone or in various combinations. Non aromatic monohydric alcohols are preferred since they minimize the potential off flavor effects caused by benzene ring based molecules. A preferred monohydric alcohol is ethanol. A preferred combination of monohydric alcohols includes ethanol and methanol. Monohydric alcohols according to the present invention may be either denatured or non-denatured. The monohydric alcohol may comprise from about 0.5% to about 15.0%, more preferably about 2.0 to about 12.0%, and even more preferably from about 4.0 to about 9.0% of the preservative composition. Monohydric alcohols are commercially available from many sources.

[00024] Compositions of the present invention also may include other excipients.

Other excipients may include potassium hydroxide, xanthan gum, and hydrochloric acid. Potassium hydroxide and hydrochloric acid may be used to control and adjust pH levels. Xanthan gum may be used to control and adjust viscosity and also provide product stability. When included in preservative compositions according to the present invention, potassium

hydroxide may comprise from about 0.01 to about 5.0%, more preferably from about 0.05% to about 2.0%, and even more preferably from about 0.1 to about 0.5% of the preservative composition. When included in preservative compositions according to the present invention, xanthan gum may comprise from about 0.01 to about 2.0%, preferably from about 0.01 to about 1.0%, and more preferably 0.1% of the preservative composition. The preservative compositions of the present invention may also include aqueous extracts from citrus leaves. The balance of the composition may comprise water. The water is preferably purified and preferably has a bacterial colony count of less than about 100 colonies per ml. The amount of water used may be varied based on the desired concentration of the preservative. The water may be made alkaline by the addition of potassium hydroxide and preferably has a pH above about 10.0. The preferred water hardness is less than 1 grain per gallon or less than 50 ppm. These particular combinations of food grade ingredients permit the compositions to be altered or changed depending on the food, beverage or other product to be preserved while adjusting the pH range to suit the food, beverage or other product. [00025] Preservative compositions according to the present invention may have a pH of from about 5 to 10, more preferably from about 6 to 9, and even more preferably from about 7 to 8.

[00026] An effective amount of the preservative compositions of the present invention is added to or combined with beverage products, food products and other consumer products. In this context an effective amount means an amount that is sufficient to prevent or reduce microbial contamination and spoilage of beverage, food and other consumer products. Accordingly, an effective amount can vary depending on the type of product being preserved and the length of time preservation is desired. Factors such as pH and/or the potential microbial load are factors to consider when determining what amounts of the preservative to use. In general, however, the preservative compositions of the present invention can

comprise up to 5% of the total weight of the beverage, food or other product. Preferably the preservative will comprise up to 3% of total weight and more preferably up to 1% of the total weight of the beverage, food or other product. The preservative compositions will usually comprise at least 0.1% of the weight of the beverage food or other product. [00027] Preservative compositions of the present invention may reduce or eliminate the growth of a wide range of spoilage-causing microorganisms including but not limited to bacteria (both gram positive and gram negative), mold, yeast and spores. For example, such preservative compositions have been very effective in preventing food and beverage spoilage caused by the following yeasts: Saccharomyces cerevisiae, Zygosaccharomyces rouxii, Zygosaccharomyces baillii, and Candida albicans. Likewise, such compositions have been effective against the molds Aspergillus niger and Penicillium notatum. In addition, these compositions have been very effective in controlling the growth of bacteria including Escherichia coli, Leuconostoc citreum, and Leuconostoc gelidium.

[00028] The preservative compositions of the present invention may be used to treat many types of beverage products normally susceptible to beverage spoiling microorganisms. For example, such beverages types include, but are not limited to, dilute juice beverages, dairy beverages, calcium fortified beverages, and beverages containing tea solids. Some specific non-limiting examples include orange juice, orange drinks, fruit drinks (e.g., apple, grape, pineapple, pear, peach, grapefruit, cranberry, nectarine, raspberry, blackberry, kiwi, mango, cherry and various combination fruit drinks), acidified soy beverages, acidified milk beverages, and flavored carbonated beverages, including "soft" carbonated beverages. [00029] The present invention also provides novel beverage products comprising preservative compositions described herein.

[00030] The preservative compositions of the present invention may be used in many types of food products for both human and animal consumption. These food products include

high moisture content, moderate moisture content and low moisture content foods. Some specific non-limiting examples include apple sauce, fruit butters and yogurt. These preservative compositions can also be used in a variety of animal foods and feeds. [00031] The present invention also provides novel human and animal food products comprising preservative compositions described herein.

[00032] In addition, such preservative compositions may be added to non food and beverage consumer products including, but not limited to cosmetic and personal care products, cleaning agent products, and other products. Cosmetic and personal care products may include: pigmentation and sun care products; diaper, baby wipe and hand wipe, baby powder and body powder and diaper rash products; nursing pads (for bras); makeup products; tampon, maxipad and pantiliner products; acne prevention and treatment products; facial cleansing, toning and exfoliating products and makeup removal products; facial moisturizing, anti-wrinkle, eye treatment, hand lotion and body lotion products; foot care products; anti- itch products; anti-bacterial, antiseptic, antibiotic and first aid products; bath and shower soap in bar, liquid and gel form and bath salt products; shampoo and hair detangling products; hair mousse, hair gel and hair spray products; anti-perspirant and deodorant products in powder, creme, roll-on, aerosol and stick form; aftershave and shaving lotion products; shaving products in creme, gel, powder and soap forms; depilatory, epilatory and hair bleaching products in creme, wax and powder forms; toothpaste products; mouthwash and mouth rinse products; wig and toupee powder products; shoulder pads; freckle coating products, eye drop products; and contact lens treatment products.

[00033] Cleaning agent products may include: laundry detergents, stain removers, and fabric softening products, dish washing products, air fresheners, deodorizing products, bathroom tissues, facial tissues, paper towels, napkin products, cotton swabs, handiwipes, scouring and sponge products, oven cleaning products, toilet cleaning products, tub and

shower cleaning products, carpet cleaning products, all purpose cleaning products, and jewelry and metal cleaning products.

[00034] In addition to the products listed above, preservatives according to the present invention may be added to or included in the following household products: dust filters, wall paint/wallpaper, toilet seat covers, mold remover, ceramic/bathroom tile laminates, water filters, mattress fillers, cleaning agents for solariums and sun beds, toilet brushes, pet litter, and cutting boards to make these products highly resistant to microbial contamination. [00035] The present invention also provides novel products useful in the animal care and veterinary fields. Preservative compositions according to the present invention may also be added to or included, for example, in the following animal/veterinary products to make these products highly resistant to microbial contamination: sand for bird cages, kitty litter, flea powder, and dry shampoos for animals.

[00036] Preservative compositions according to the present invention may also be added to or included in the following products: fungicide/pesticide for agriculture, marine antifoulant, coating for glass and cleaners for industrial food and beverage containers, concrete, ceramics, and tile, to name a few, to make these products highly resistant to microbial contamination.

[00037] Accordingly, the present invention also provides novel consumer products (in addition to the beverage and food products described above) comprising the preservative compositions described herein

Methods of Making

[00038] The present invention also provides methods of making the preservative compositions described herein. Such methods may include (1) heating water; (2) adding natural wax, such as beeswax, and mixing; (3) allowing the wax solution to cool; (4) removing solid wax; (5) mixing the water and wax extract mixture with potassium hydroxide;

(6) providing d-limonene and an emulsifϊer, such as soy lecithin, in a separate container and mixing; (7) adding the d-limonene and emulsifϊer mixture to the water, wax extract and potassium hydroxide mixture; and (8) adding monohydric alcohol, such as ethanol, to the mixture formed by step 7.

[00039] In one embodiment of the present invention, preservatives may be produced by (1) heating water up to a temperature of about 180F; (2) adding natural wax, such as beeswax, and mixing; (3) allowing the wax solution to cool to about room temperature; (4) removing solid wax formed by step 3; (5) mixing the water and wax extract mixture with potassium hydroxide; (6) providing d-limonene and an emulsifϊer, such as soy lecithin, in a separate container and mixing until the emulsifϊer is dissolved; (7) adding the d-limonene and emulsifϊer mixture to the water, wax extract and potassium hydroxide mixture and mixing at a high shear and high mixing speed; and (8) adding monohydric alcohol, such as ethanol, to the mixture formed by step 7.

[00040] Another embodiment of the present invention includes the steps of (1) heating water up to a temperature of about 180F; (2) adding natural wax, such as beeswax in an amount from about 0.1 to about 5.0%, and mixing until the wax is thoroughly dispersed in solution; (3) allowing the wax solution to cool to about room temperature; (4) removing solid wax formed by step 3; (5) adding additional water to the water and wax extract mixture formed in step 2; (6) mixing the product of step 5 with potassium hydroxide in an amount from about 0.01 to about 1.0%; (7) providing regular d-limonene in an amount from about 2.0 to about 20.0% and an emulsifϊer, such as soy lecithin in an amount from about 0.1 to about 10.0% in a separate container and mixing until the emulsifϊer is dissolved; (8) adding the d- limonene and emulsifϊer mixture to the water and wax extract mixture and mixing at a high shear and high mixing speed; and (9) adding monohydric alcohol, such as ethanol in an

amount from about 1.0 to about 15.0% to the mixture formed by step 8 and mixing at a high mixing speed.

[00041] While satisfactory preservatives may be formed by including a monohydric alcohol in earlier steps, applicants have unexpectedly found that a superior preservative composition may be formed by adding the monohydric alcohol, preferably ethanol, as the last step in the process. Without being bound by a particular theory, it is believed this may be due to partial incompatibility between emulsifiers such as soy lecithin and monohydric alcohols such as ethanol.

[00042] Applicants have also unexpectedly found that superior preservative compositions may be formed by adding an emulsifϊer and d-limonene mixture to the water, wax and potassium hydroxide mixture and then mixing the resulting combination of components at a high shear and high speed. For example, mixing speeds around, for example, 20,000 rpm provide excellent preservative compositions, although higher and lower rates also can be effective. In addition, applicants have found that mixing a monohydric alcohol such as ethanol into the composition at a similarly high mixing speed provides surprisingly useful preservative compositions. Again, somewhat higher or lower mixing rates also can be effective.

[00043] Applicants have also found that stainless steel containers are preferred for mixing since such containers avoid the possibility of contamination from other types of containers. In addition, mixing times of around 15 to 20 minutes prior to and after the addition of a monohydric alcohol, such as ethanol, provide satisfactory results, but greater or less time may be acceptable under certain circumstances. Generally, the mixing time should be sufficient to mix the components thoroughly.

[00044] In certain embodiments of the present invention, the resultant composition may be pumped through filters at a pressure sufficient to effectively collect the preservative

composition. The filtering pressure may be from about 5 to about 100 psi, preferably is from about 10 to about 40 psi, and more preferably is about 30 psi. The preservative composition may be cooled before use. Preferably the composition may be cooled to at least about 95°F. Cooling may be facilitated by the use of a heat exchanger.

[00045] Preservative compositions according to the present invention may also be formed into a crystalline powder form to facilitate packaging and use. This may be achieved, for example, by reducing the water content to about 10% of the composition, adding xanthan gum and gum arabic in roughly equal amounts, drying the composition, and then grinding to break up larger particles. Drying may be achieved by, for example, a vacuum drier, a fluidized bed drier, a low temperature roller drier, a vacuum extrusion drier or by other drying means.

[00046] Generally, preservative compositions according to the present invention may be added to the beverage product, food product or other consumer product, such that the preservative composition comprises from about 0.05 to about 5.0% by weight of the food, beverage or other product.

[00047] Any method insuring that the preservative compositions of the present invention are incorporated into the beverage, food or other consumer product is suitable. For example, such compositions may be sprayed, injected, dipped or poured directly onto products. Alternatively, preservative compositions may be frozen and products may be placed in contact with the frozen preservative compositions. Further, preservative compositions may be spray dried, freeze-dried and/or powdered and then applied to products. Preservative compositions may be added to a finished product or may be added at any step in the production processes of a beverage, food or other consumer product. [00048] Alternatively, the ingredients of the preservative of the invention as described above can be individually or collectively added to the final product or to what becomes the

final product, or in a process of making the final product, either separately or all together at once.

Examples Example 1

[00049] The composition as shown in Table 1 is prepared in a manner described above and is used to demonstrate preservative properties of an exemplary embodiment of the present invention:

[00050] The preservative composition of Table 1 is added to orange juice (100% real juice from concentrate, 11.8 brix (acid corrected) and 3.9 pH) at 0.5%, 1% and 2% and inoculated with Saccharomyces cerevisiae to the following levels; 30 yeast/ml, 300 y/ml, and 3,000 y/ml. The samples are stored at 30 ⁰ C and evaluated for yeast growth and yeast growth by-products. The preservative composition will effectively inhibit yeast growth for an extended duration. A control sample containing none of the preservative composition will spoil quickly.

Example 2

[00051] The preservative composition of Example 1 is added to fruit punch drink (15% real juice, 12.0 brix, 3.0 pH) at 0.25%, 0.5%, 1%, and 2% and inoculated with Saccharomyces cerevisiae to the following levels; 50 yeast/ml, 400 y/ml, and 4,000 y/ml. The samples are stored at 30 ⁰ C and evaluated for yeast growth and yeast growth by-products. The preservative composition will effectively inhibit yeast growth for an extended duration. A control sample containing none of the preservative composition will spoil quickly. Example 3

[00052] The preservative composition of Example 1 is added to grape drink (10% real juice, 12.5 brix, 2.6 pH) at 0.5%, 1%, and 2% and inoculated with Saccharomyces cerevisiae to the following levels; 50 yeast/ml and 150 y/ml. The samples are stored at 30 ⁰ C and evaluated for yeast growth and yeast growth by-products. The preservative composition will effectively inhibit yeast growth at all levels for an extended duration. A control sample containing none of the preservative composition will spoil quickly. Example 4

[00053] The preservative composition of Example 1 is added to strawberry kiwi flavored drink (0% real juice, 12.0 brix, 3.0 pH) at 0.5% and 1% and inoculated with Saccharomyces cerevisiae to the following levels; 50 yeast/ml and 500 y/ml. The samples are stored at 30 ⁰ C and evaluated for yeast growth and yeast growth by-products. The preservative composition will effectively inhibit yeast growth for an extended duration. A control sample containing none of the preservative composition will spoil quickly. Example 5

[00054] The preservative composition of Example 1 is added to a margherita mix (20% real juice, 60 brix, 1.9 pH) at 1 and 2% and inoculated with Saccharomyces cerevisiae to the following levels; 50 yeast/ml and 500 y/ml. The samples are stored at 25°C and evaluated for

yeast growth and yeast growth by-products. The preservative composition will effectively inhibit yeast growth for an extended duration. A control sample containing none of the preservative composition will spoil quickly. Example 6

[00055] The preservative composition of Example 1 is added to a fruit punch beverage syrup (0% real juice, 37 brix, 2.6 pH) at 1 and 2% and inoculated with Saccharomyces cerevisiae to the following level; 500 y/ml. The samples are stored at 30 ⁰ C and evaluated for yeast growth and yeast growth by-products. The preservative composition will effectively inhibit yeast growth for an extended duration. When the syrup is diluted 5 fold with water for retail preparation, no yeast growth will be seen for an extended duration. A control sample containing none of the preservative composition will spoil quickly.