Source: http://www.google.com/patents/US5997654?ie=ISO-8859-1
Timestamp: 2014-10-31 06:30:57
Document Index: 256404553

Matched Legal Cases: ['application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08']

Patent US5997654 - Potassium oleate, water soluble polyethylene glycol, neutralized phosphoric ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsBasic cleaning compositions using toxicologically-acceptable ingredients for cleaning fruits and vegetables are provided. Liquid formulations comprising detergent surfactant, such as oleate, alcohol ethoxylates, etc., and neutralized phosphoric acid are sprayed onto apples, lettuce and the like to remove...http://www.google.com/patents/US5997654?utm_source=gb-gplus-sharePatent US5997654 - Potassium oleate, water soluble polyethylene glycol, neutralized phosphoric acid, ph of 9.5 or greaterAdvanced Patent SearchPublication numberUS5997654 APublication typeGrantApplication numberUS 08/495,288Publication dateDec 7, 1999Filing dateJun 27, 1995Priority dateJun 27, 1995Fee statusPaidAlso published asCA2225685A1, CA2225685C, CA2415407A1, CA2415407C, CN1067870C, CN1193897A, CN1271549A, EP0835064A1, EP1146113A1, US6367488, US6831050, US20010009891, US20040043912, WO1997001289A1Publication number08495288, 495288, US 5997654 A, US 5997654A, US-A-5997654, US5997654 A, US5997654AInventorsBruce Prentiss Murch, Brian Joseph Roselle, Kyle David Jones, Keith Homer Baker, Thomas Edward Ward, Toan TrinhOriginal AssigneeThe Procter & Gamble CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (24), Non-Patent Citations (10), Referenced by (15), Classifications (26), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetPotassium oleate, water soluble polyethylene glycol, neutralized phosphoric acid, ph of 9.5 or greaterUS 5997654 AAbstract Basic cleaning compositions using toxicologically-acceptable ingredients for cleaning fruits and vegetables are provided. Liquid formulations comprising detergent surfactant, such as oleate, alcohol ethoxylates, etc., and neutralized phosphoric acid are sprayed onto apples, lettuce and the like to remove soil and unwanted deposits, especially wax. Articles for applying the compositions to produce by spraying are disclosed. Use of the compositions for disinfectancy/sanitization of produce and cleaning/disinfectancy/sanitization of non-food inantimate surfaces are disclosed.
What is claimed is: 1. A method for cleaning and/or sanitizing fruits and vegetables at a basic pH, using a solution comprising:(a) optionally, from about 0.1% to about 4%, by weight of nonionic surfactant; (b) from about 0.1% to about 5%, by weight of potassium oleate; (c) optionally, from about 0.2% to about 4% by weight of organic polycarboxylate detergency builder; (d) at least about 0.05%, by weight, of water-soluble polyethylene glycol having a molecular weight of about 200, or higher; (e) optionally, a toxicologically-acceptable basic buffer; (f) from about 0.05% to about 10% of neutralized phosphoric acid; and (g) the balance comprising an aqueous carrier selected from water and water-ethanol; wherein said composition has a pH of 9.5 or greater, wherein all of the ingredients of said solution are generally regarded as safe, wherein there is at least 0.5% detergent; and wherein said solution is contained in, and dispensed from, a spray container suitable for use by an individual. Description
TECHNICAL FIELD The present invention relates to methods for removing dirt and other unwanted residues from produce, e.g., fruits and vegetables, which is intended for ingestion by humans or lower animals and to detersive compositions, especially in liquid form, which are especially suitable for practicing said methods.
BACKGROUND OF THE INVENTION It is well-known and appreciated by consumers that fruits and vegetables 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. In addition, some consumers wish to remove the artificial "waxy" coatings which may be applied to some fruits to retard moisture loss for increased storage life and to enhance their appearance. 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 vegetables 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 fruits or vegetables 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 fruits and vegetables 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.
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 regarded 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.
SUMMARY OF THE INVENTION The present invention encompasses methods for cleaning produce, especially fruits and vegetables, (and compositions, as disclosed hereinafter, for practicing said methods) at a basic pH. The present invention comprises several aspects including:
(a) from about 0.01% to about 15% of C8 -C18 fatty acid;
(a) from about 0.01% to about 15% of C8 -C18 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;
wherein said aqueous cleaning solution has a pH of 9.5 or greater, and preferably employs carbonate salt, or salts, as buffer (e), preferably with hydroxide base, to provide a pH of from about 11 to about 12.5, more preferably from about 11.5 to about 12.5. The compostions 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.
DETAILED DESCRIPTION OF THE INVENTION 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 fruits or vegetables 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 C10-18 aliphatic alcohols or acids, C10-18 aliphatic alcohol adducts of glucose (alkyl polyglucosides). The specific nonionic surfactant selected ideally has a hydrophilic-lipophilic 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 to 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 (≧C12), or have unacceptable odor (≦C10). For example, stearic and/or tallow fatty acids soaps, even potassium soaps, do not have enough solubility at room temperature, where most produce 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.
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 Corporation) 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______________________________________            Viscosity  Viscosity            (cP* as made)                       (cP* as made)Composition      72� F. (22� C.)                       43� F. (6� C.)______________________________________Control (no PEG) 7          110Control + 0.674% Bz            23         1000Control + 0.118% Bz            7          159Control + 0.1% PEG 400            5           36Control + 0.5% PEG 400            2           17Control + 0.1% PEG 8000            5           23Control + 0.5% PEG 8000            8           4______________________________________ *Viscosity in centipoise as measured using Brookfield LVTD #2 spindle, 60 rpm 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.
Optional Surfactants--Optionally, base stable anionic surfactants can be employed, as allowed by the United States Code of Federal Regulations, Title 21, Section 173.315. Preferred are salts of dodecylbenzene sulfonate, typically at levels up to 0.2%. Also described in the CFR 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 provide ease of formulatability. 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 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 fruit or vegetable 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 2, preferably more than about 5, more preferably more than about 10 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.
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 do not require a preservative.
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 produce, to avoid an alcoholic odor, especially when spraying. Other compatible, water-soluble, low molecular weight solvents such as glycerol can also be used.
EXAMPLE 1 ______________________________________Product      Control  A        B      WaterIngredient   level %  level %  level %                                 level %______________________________________Water        90.93    90.90    88.20  100.00KOH          1.33     1.36     3.06   --Ethanol      2.00     2.00     2.00   --Glycerin     2.00     2.00     2.00   --Oleic acid   2.64     2.64     2.64   --Sodium Bicarbonate        0.55     0.55     0.55   --Phosphoric Acid        --       --       1.00   --Citric acid  0.52     0.52     0.52   --Essence      0.03     0.03     0.03   --Neat pH      11.5     12.0     12.2   �7.5______________________________________
Glass flasks are coated with AP-40 shellac and stress cured for 24 hours @ 140 F. The flasks at room temperature are then washed with �5 grams (5 squirts of a Calmar #TS-800 sprayer) of the respective products with a 10 sec. rub, followed immediately with a water rinse, and allowed to dry. The % Wax removal is determined gravimetrically.
% Wax Removal Control 14%, A 9%; B 38%; and Water 0%.
EXAMPLE 2 ______________________________________                                   WaterProduct Control  A        B      C      referenceIngredient   level %  level %  level %                            level %                                   level %______________________________________Water   90.93    88.08    88.05  88.05  100.00KOH     1.33      3.06*    3.06* 3.06   --Ethanol 2.00     2.00     2.00   2.00   --Glycerin   2.00     2.00     2.00   2.00   --Oleic acid   2.64     2.64     2.64   2.64   --Sodium  0.55     0.55     0.55   0.55   --BicarbonatePhosphoric   --       1.00     1.00   1.00   --AcidCitric acid   0.52     0.52     0.52   0.52   --Essence 0.03     0.03     0.03   0.03   --PEG 3350   --       0.12     0.15   0.15   0Neat pH 11.5     12.6     12.0   11.5   �7.5______________________________________ *Target KOH usage. Very small amount of additional KOH, replacing water, used to adjust to final pH.
Using varying wax, curing, rub time and flask temperature, the above compositions were used to clean in a manner similar to EXAMPLE 1, followed by a determination of the percentage of wax removed. The test conditions and results are as follows.
______________________________________            % Wax RemovalWax/Curing/Rub time/flask Temp.            Control A      B   C    Water______________________________________Shellac/60min. @75 C./10            51      97     73  82   9sec./room temp.Carnauba/60 min. @43 C./10            64      82     75  73   5sec./room temp.Shellac/60 min. @75 C./20            57      97     96  97   7sec./40� F.Shellac/30 min. @93 C./20            50      98     61  65   3sec./room temp.______________________________________
EXAMPLE 3 ______________________________________Product    A       B          C     DIngredient level % level %    level %                               level %______________________________________Water      89.79   90.63      88.068                               88.91KOH        2.12    1.28       2.842 2.00Ethanol    2.00    2.00       2.00  2.00Glycerin   2.00    2.00       2.00  2.00Oleic acid 2.643   2.643      2.643 2.643Sodium     0.547   0.547      0.547 0.547BicarbonatePhosphoric 0.00    0.00       1.00  1.00AcidCitric acid      0.52    0.52       0.52  0.52Essence    0.03    0.03       0.03  0.03PEG 3350   .350    .350       .350  .350Neat pH    11.5    10.5       11.5  10.5______________________________________
EXAMPLE 4 ______________________________________Product           A       BIngredients       Level % Level %______________________________________Oleic Acid        2.64    2.20Sodium Bicarbonate             0.55    0.55Phosphoric Acid   1.00    --Citric Acid       0.52    0.52EDTA, Sodium Salt 0.05    0.10GRAS Perfume      0.05    0.08PEG 3350          2.00    --KOH               *       **Ethanol           2.00    2.00Water             Balance Balance______________________________________ *Amount sufficient to attain a pH of about 11. **Amount sufficient to attain a pH of about 10.5.
Each of the Compositions of Examples 1 Control, 4A, and 4B is used to spray on a contaminated Formica� kitchen countertop, left on the surface for about 10 min., then rinsed off to provide a sanitizing benefit.
EXAMPLE 5 ______________________________________Ingredient        Wt %______________________________________Water             73.26PEG 3350          0.79KOH               5.70Ethanol           6.00Glycerin          3.00Oleic acid        7.90Sodium bicarbonate             1.60Phosphoric acid   1.00Citric acid       1.56Essence (Grapefruit oil)             0.09______________________________________
EXAMPLE 6 ______________________________________Ingredient           Wt %______________________________________Tri-Potassium Phosphate (TKP)                48.8Potassium Citrate    10.2PEG 3350              4.3Potassium Oleate     36.7______________________________________
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MeldrumCleaning crops by immersing in baths of electroconductive solutes, applying alternating currents at high frequency and ultrasonic vibrations to detach and neutralize phytopathogens and impuritiesUS6557568 *Jun 27, 1995May 6, 2003The Procter & Gamble CompanyCleaning/sanitizing methods, compositions, and/or articles for produceUS6613731Nov 4, 1998Sep 2, 2003The Procter & Gamble CompanyCleaning/sanitizing methods, compositions, and/or articles for non-food inanimate surfacesUS6808729Jun 26, 1998Oct 26, 2004The Procter & Gamble CompanyMicroorganism reduction methods and compositions for foodUS6821940Oct 5, 2001Nov 23, 2004The Procter & Gamble CompanyWipes for cleaning foods, toys and food/child contact surfacesUS6831050 *Sep 2, 2003Dec 14, 2004The Procter & Gamble CompanyCleaning/sanitizing methods, compositions, and/or articles for produceUS6964942 *Jun 11, 2003Nov 15, 2005The Procter & Gamble CompanyFor fruits, vegetables; liquid mixture of detergent surfactant, fatty acid, polycarboxylic acid and phosphoric acidUS7048956Mar 5, 2002May 23, 2006The Penn State Research FoundationContacting with electrolyzed basic water having a pH of at least about 9.0; rinsing with a pH-neutralizing solution having a pH sufficient to return the mushrooms to the mushroom physiological pH of about 6.5.US8632636 *Jul 17, 2007Jan 21, 2014Oral Health Technologies, LLCWet wiper articles and methods for cleaning removable dental appliancesUS8722123Feb 1, 2012May 13, 2014University Of Georgia Research Foundation, Inc.Antimicrobial composition and use as food treatmentUSRE39147 *Jul 5, 2001Jun 27, 2006The Penn State Research FoundationPreservative compositions and methods for mushroomsWO2001072149A1 *Mar 17, 2001Oct 4, 2001Henkel KgaaWashing of fruit and vegetables* Cited by examinerClassifications U.S. Classification134/6, 510/111, 134/25.3, 134/25.1International ClassificationC11D1/02, C11D1/66, B08B3/08, A61L2/18, A23N12/02, C11D3/06, C11D3/20, C11D1/04, C11D10/04, C11D1/83, C11D3/02, A23L1/00Cooperative ClassificationC11D10/04, A23L1/0011, C11D1/04, C11D3/2075, C11D3/042European ClassificationC11D3/04A, C11D3/20E, A23L1/00N, C11D10/04, C11D1/04Legal EventsDateCodeEventDescriptionJun 6, 2011FPAYFee paymentYear of fee payment: 12Aug 1, 2007ASAssignmentOwner name: HEALTHPRO BRANDS INC., OHIOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE PROCTOR & GAMBLE COMPANY;REEL/FRAME:019628/0127Effective date: 20070508May 14, 2007FPAYFee paymentYear of fee payment: 8Jun 26, 2003REMIMaintenance fee reminder mailedMay 29, 2003FPAYFee paymentYear of fee payment: 4Feb 20, 1996ASAssignmentOwner name: PROCTER & GAMBLE COMPANY, THE, OHIOFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MURCH, BRUCE PRENTISS;ROSELLE, BRIAN JOSEPH;JONES, KYLE DAVID;AND OTHERS;REEL/FRAME:007830/0376;SIGNING DATES FROM 19950627 TO 19950830RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google