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WO2005068598A1 - Procedes et compositions pour l'elimination d'amidon - Google Patents

Procedes et compositions pour l'elimination d'amidon Download PDF

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Publication number
WO2005068598A1
WO2005068598A1 PCT/US2004/034477 US2004034477W WO2005068598A1 WO 2005068598 A1 WO2005068598 A1 WO 2005068598A1 US 2004034477 W US2004034477 W US 2004034477W WO 2005068598 A1 WO2005068598 A1 WO 2005068598A1
Authority
WO
WIPO (PCT)
Prior art keywords
cleaning agent
acid
alkaline
article
applying
Prior art date
Application number
PCT/US2004/034477
Other languages
English (en)
Other versions
WO2005068598A9 (fr
Inventor
Werner Strothoff
Winfried Troll
Helmut Maier
John Furber
Bryan Maser
Michael Besse
Original Assignee
Ecolab Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/740,371 external-priority patent/US8092613B2/en
Application filed by Ecolab Inc. filed Critical Ecolab Inc.
Publication of WO2005068598A1 publication Critical patent/WO2005068598A1/fr
Publication of WO2005068598A9 publication Critical patent/WO2005068598A9/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0002—Washing processes, i.e. machine working principles characterised by phases or operational steps
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0076—Washing or rinsing machines for crockery or tableware of non-domestic use type, e.g. commercial dishwashers for bars, hotels, restaurants, canteens or hospitals
    • A47L15/0078—Washing or rinsing machines for crockery or tableware of non-domestic use type, e.g. commercial dishwashers for bars, hotels, restaurants, canteens or hospitals with a plurality of fluid recirculation arrangements, e.g. with separated washing liquid and rinsing liquid recirculation circuits
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0076—Washing or rinsing machines for crockery or tableware of non-domestic use type, e.g. commercial dishwashers for bars, hotels, restaurants, canteens or hospitals
    • A47L15/0081—Washing or rinsing machines for crockery or tableware of non-domestic use type, e.g. commercial dishwashers for bars, hotels, restaurants, canteens or hospitals with vertical sliding closing doors, e.g. hood-type dishwashers
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L2601/00—Washing methods characterised by the use of a particular treatment
    • A47L2601/20—Other treatments, e.g. dry cleaning
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the invention is related to a method of warewashing to remove starch.
  • the method includes a first alkaline step, a first acidic step, and a second alkaline step.
  • the method may include additional steps, as well as pauses and rinse steps.
  • the method may be carried out in a variety of dish machines, including consumer and institutional dish machines.
  • BACKGROUND Starchy soils are known to accumulate on dishes including for example eating utensils, plates, pots, pans, glassware, and the like. Such soils are particularly difficult to remove using conventional warewashing compositions and methods.
  • starch deposits may accumulate on a dish.
  • starchy soils and starch buildup have been removed by subjecting the dish to a "thorough cleaning," also referred to as processing, or by manually scrubbing the dish.
  • a thorough cleaning involves occasionally applying to the dish a cleaning composition having a substantially higher concentration than a typical cleaning composition. Both the "thorough cleaning" and manually scrubbing a dish are costly and time consuming.
  • compositions and methods that prevent the buildup of starch on dishes and remove existing starch buildup on dishes in an efficient and cost effective manner.
  • starchy soils and starch buildup may be removed using a method comprising at least a first alkaline step, a first acidic step, and a second alkaline step.
  • the method may include additional alkaline and acidic steps.
  • the method may also include pauses between steps as well as rinses.
  • the method may be carried out using a variety of alkaline and acidic compositions.
  • dish machines include consumer and institutional dish machines.
  • Figure 1 shows a door dish machine where the acid is applied through the rinse arm of the dish machine.
  • Figure 2 shows a door dish machine where the acid is applied through spray nozzles mounted on the top and bottom of the dish machine.
  • Figure 3 shows a door dish machine where the ac'id is applied through a separate rinse arm.
  • Figure 4 shows a door dish machine where the acid is applied through additional nozzles in the rinse arm.
  • the invention generally relates to a method of removing starchy soils and starch buildup from dishes.
  • the method comprises at least a first alkaline step, a first acidic step, and a second alkaline step.
  • the method may include additional alkaline or acidic steps.
  • the composition may include pauses between steps, as well as rinses between or after steps.
  • the method may use a variety of alkaline and acidic compositions.
  • the compositions may include additional functional ingredients that improve the effectiveness of the composition or provide an additional benefit.
  • the method may be carried out in a variety of dish machines, including consumer and institutional dish machines.
  • the present method has two additional benefits.
  • the invention generally relates to a method of removing starchy soils and starch buildup from dishes using at least a first alkaline step, a first acidic step, and a second alkaline step.
  • the method may include additional alkaline and acidic steps.
  • the additional alkaline and acidic steps preferably alternate to provide an alkaline-acidic-alkaline-acidic-alkaline pattern. While it is understood that the method may include as many alkaline and acidic steps as desired, the method preferably includes at least three steps, and not more than eight steps. In another embodiment, the method may include pauses between the alkaline and acidic steps.
  • the method may proceed according to the following: first alkaline step, first pause, first acidic step, second pause, second alkaline step, third pause, and so on. During a pause, no further cleaning agent is applied to the dish and the existing cleaning agent is allowed to stand on the dish for a period of time.
  • the method may include rinses.
  • the method may proceed according to the following: first alkaline step, first acidic step, second alkaline step, rinse.
  • the method may proceed according to the following: first alkaline step, first pause, first acidic step, second pause, second alkaline step, third pause, rinse.
  • the method may include an optional prewash step prior to the first alkaline step.
  • the time for each step in the method may vary depending on the dish machine, for example if the dish machine is a consumer dish machine or an institutional dish machine.
  • the time required for a cleaning step in consumer dish machines is typically about 10 minutes to about 60 minutes.
  • the time required for the cleaning cycle in a U.S. or Asian institutional dish machine is typically about 45 seconds to about 2 minutes, depending on the type of machine.
  • Each method step preferably lasts from about 2 seconds to about 30 minutes.
  • the temperature of the cleaning solutions in each step may also vary depending on the dish machine, for example if the dish machine is a consumer dish machine or an institutional dish machine.
  • the temperature of the cleaning solution in a consumer dish machine is typically about 110 °F (43 °C) to about 150 °F (66 °C) with a rinse up to about 160 °F (71 °C).
  • the temperature of the cleaning solution in a high temperature institutional dish machine in the U.S. is about typically about 150 °F (66 °C) to about 165 °F (74 °C) with a rinse from about 180 °F (82 °C) to about 195 °F (91 °C).
  • the temperature in a low temperature institutional dish machine in the U.S. is typically about 120 °F (49 °C) to about 140 °F (60 °C).
  • Low temperature dish machines usually include at least a seven minute rinse with a sanitizing solution.
  • the temperature in a high temperature institutional dish machine in Asia is typically from about 131 °F (55 °C) to about 136 °F (58 °C) with a final rinse at 180 °F (82 °C).
  • the temperature of the cleaning solutions is preferably from about 95 °F (35 °C) to about 176 °F (80 °C).
  • Compositions may be either a concentrate or a diluted solution.
  • the concentrate refers to the composition that is diluted to form the use solution.
  • the concentrate is preferably a solid.
  • the diluted solution refers to a diluted form of the concentrate.
  • compositions may be formed as a concentrate and dilute it to a diluted solution on- site.
  • the concentrate is often easier and less expensive to ship than the use solution.
  • a concentrate that is diluted in a dish machine to form the diluted solution during the cleaning process.
  • a composition may be formed as a solid and placed in the dish machine dispenser as a solid and sprayed with water during the cleaning cycle to form a diluted solution.
  • the compositions applied to the dish during cleaning are diluted solutions and not concentrates.
  • the compositions may be a liquid, thickened liquid, gelled liquid, paste, granular or pelletized solid material, solid block, cast solid block, powder, tablet, or the like.
  • Liquid compositions can typically be made by forming the ingredients in an aqueous liquid or aqueous liquid solvent system. Such systems are typically made by dissolving or suspending the active ingredients in water or in compatible solvent and then diluting the product to an appropriate concentration, either to form a concentrate or a use solution thereof. Gelled compositions can be made similarly by dissolving or suspending the active ingredients in a compatible aqueous, aqueous liquid or mixed aqueous organic system including a gelling agent at an appropriate concentration. Solid particulate materials can be made by merely blending the dry solid ingredients in appropriate ratios or agglomerating the materials in appropriate agglomeration systems.
  • Pelletized materials can be manufactured by compressing the solid granular or agglomerated materials in appropriate pelletizing equipment to result in appropriately sized pelletized materials.
  • Solid block and cast solid block materials can be made by introducing into a container either a prehardened block of material or a castable liquid that hardens into a solid block within a container.
  • the compositions may be provided in bulk or in unit dose.
  • the compositions may be provided in a large solid block that may be used for many cleaning cycles.
  • the compositions may be provided in unit dose form wherein a new composition is provided for each new cleaning cycle.
  • the compositions may be packaged in a variety of materials including a water soluble film, disposable plastic container, flexible bag, shrink wrap, and the like.
  • compositions may be packaged in such a way as to allow for multiple forms of product in one package, for example, a liquid and a solid in one unit dose package.
  • the alkaline, acidic, and rinse compositions may be either provided or packaged separately or together.
  • the alkaline composition may be provided and packaged completely separate from the acidic composition.
  • the alkaline, acidic, and rinse compositions may be provided together in one package.
  • the alkaline, acidic, and rinse compositions may be provided in a layered block or tablet wherein the first layer is the first alkaline composition, the second layer is the first acidic composition, the third layer is the second alkaline composition, and optionally, the fourth layer is the rinse composition.
  • this layered arrangement may be adjusted to provide for more alkaline and acidic steps as contemplated by the invention or to include additional rinses or no rinses.
  • the individual layers preferably have different characteristics that allow them to dissolve at the appropriate time. For example, the individual layers may dissolve at different temperatures that correspond to different wash cycles; the layers may take a certain amount of time to dissolve so that they dissolve at the appropriate time during the wash cycle; or the layers may be divided by a physical barrier that allows them to dissolve at the appropriate time, such as a paraffin layer, a water soluble film, or a chemical coating.
  • the alkaline and acidic compositions may also be in separate domains.
  • the alkaline and acidic compositions may be in separate domains in a solid composition wherein each domain is dissolved by a separate spray when the particular composition is desired.
  • Alkaline Composition The method of the present invention includes at least two alkaline steps wherein an alkaline composition is brought into contact with a dish during the alkaline step of the cleaning process.
  • the alkaline composition includes one or more alkaline carriers.
  • suitable alkaline carriers include the following: a hydroxide such as sodium hydroxide, or potassium hydroxide; an alkali silicate; an ethanolamine such as triethanolamine, diethanolamine, and monoethanolamine; an alkali carbonate; and mixtures thereof.
  • the alkaline carrier is preferably a hydroxide or a mixture of hydroxides, or an alkali carbonate.
  • the alkaline carrier is preferably present in the diluted, ready to use, alkaline composition from about 125 ppm to about 5000 ppm, more preferably from about 250 ppm to about 3000 ppm and most preferably from about 500 ppm to about 2000 ppm.
  • the alkaline composition preferably creates a diluted solution having a pH from about 7 to about 14, more preferably from about 9 to about 13, and most preferably from about 10 to about 12.
  • the particular alkaline carrier selected is not as important as the resulting pH. Any alkaline carrier that achieves the desired pH may be used in the alkaline composition of the invention.
  • the first alkaline cleaning step and the second alkaline cleaning step may use the same alkaline composition or different alkaline compositions.
  • the alkaline composition may include additional ingredients.
  • the alkaline composition may include a water conditioning agent, an enzyme, an enzyme stabilizing system, a surfactant, a binding agent, an antimicrobial agent, a bleaching agent, a defoaming agent/foam inhibitor, an antiredeposition agent, a dye or odorant, a carrier, a hydrotrope and mixtures thereof.
  • Water Conditioning Agent can be referred to as a detergent builder and/or chelating agent and generally provides cleaning properties and chelating properties.
  • Exemplary detergent builders include sodium sulphate, sodium chloride, starch, sugars, C1-C 1 0 alkylene glycols such as propylene glycol, and the like.
  • Exemplary chelating agents include phosphates, phosphonates, and amino-acetates.
  • Exemplary phosphates include sodium orthophosphate, potassium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate (STPP), and sodium hexametaphosphate.
  • Exemplary phosphonates include l-hydroxyethane-l,l-diphosphonic acid, aminotrimethylene phosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), 1- hydroxyethane-l,l-diphosphonic acid CH. 3 C(OH)[PO(OH) 2 ] 2 , aminotri(methylenephosphonic acid) N[CH PO(OH) 2 ] 3 , aminotri(methylenephosphonate), sodium salt ONa. +
  • amino-acetates include aminocarboxylic acids such as N- hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NT A), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl- ethylenediaminetriacetic acid (HEDTA), and diethylenetriaminepentaacetic acid (DTP A).
  • Enzyme The present composition may include one or more enzymes, which can provide desirable activity for removal of protein-based, carbohydrate- based, or triglyceride-based soils from substrates such as flatware, cups and bowls, and pots and pans.
  • Enzymes suitable for the inventive composition can act by degrading or altering one or more types of soil residues encountered on a surface thus removing the soil or making the soil more removable by a surfactant or other component of the cleaning composition. Both degradation and alteration of soil residues can improve detergency by reducing the physicochemical forces which bind the soil to the surface being cleaned, i.e. the soil becomes more water soluble.
  • one or more proteases can cleave complex, macromolecular protein structures present in soil residues into simpler short chain molecules which are, of themselves, more readily desorbed from surfaces, solubilized, or otherwise more easily removed by detersive solutions containing said proteases.
  • Suitable enzymes include a protease, an amylase, a lipase, a gluconase, a cellulase, a peroxidase, or a mixture thereof of any suitable origin, such as vegetable, animal, bacterial, fungal or yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • the enzyme is a protease, a lipase, an amylase, or a combination thereof.
  • protease suitable for the present invention can be derived from a plant, an animal, or a microorganism.
  • the protease is derived from a microorganism, such as a yeast, a mold, or a bacterium.
  • Preferred proteases include serine proteases active at alkaline pH, preferably derived from a strain of Bacillus such as Bacillus subtilis or Bacillus licheniformis; these preferred proteases include native and recombinant subtilisins.
  • the protease can be purified or a component of a microbial extract, and either wild type or variant (either chemical or recombinant).
  • proteolytic enzymes which can be employed in the present invention include (with trade names) Savinase ® ; a protease derived from Bacillus lentus type, such as Maxacal ® , Opticlean ® , Durazym ® , and Properase ® ; a protease derived from Bacillus licheniformis, such as Alcalase ® and
  • Maxatase ® and a protease derived from Bacillus amyloliquefaciens, such as Primase' .
  • Preferred commercially available protease enzymes include those sold under the trade names Alcalase ® , Savinase ® , Primase ® , Durazym ® , or Esperase ® by Novo Industries A/S (Denmark); those sold under the trade names Maxatase ® , Maxacal ® , or Maxapem ® by Gist- Brocades (Netherlands); those sold under the trade names Purafect ® , Purafect OX, and Properase by Genencor International; those sold under the trade names Opticlean ® or Optimase ® by Solvay Enzymes; and the like.
  • Purafect ® is a preferred alkaline protease (a subtilisin) for use in detergent compositions of this invention having application in lower temperature cleaning programs, from about 30 °C to about 65 °C; whereas, Esperase ® is an alkaline protease of choice for higher temperature detersive solutions, from about 50 °C to about 85 °C.
  • Suitable detersive proteases are described in patent publications including: GB 1,243,784, WO 9203529 A (enzyme/inhibitor system), WO 9318140 A, and WO 9425583 (recombinant trypsin-like protease) to Novo; WO 9510591 A, WO 9507791 (a protease having decreased adsorption and increased hydrolysis), WO 95/30010, WO 95/30011, WO 95/29979, to Procter & Gamble; WO 95/10615 (Bacillus amyloliquefaciens subtilisin) to Genencor International; EP 130,756 A (protease A); EP 303,761 A (protease B); and EP 130,756 A.
  • a variant protease employed in the present stabilized enzyme cleaning compositions is preferably at least 80% homologous, preferably having at least 80% sequence identity, with the amino acid sequences of the proteases in these references.
  • proteolytic enzymes may be incorporated into this invention. While various specific enzymes have been described above, it is to be understood that any protease which can confer the desired proteolytic activity to the composition may be used and this embodiment of this invention is not limited in any way by specific choice of proteolytic enzyme.
  • Amylase An amylase suitable for the composition of the present invention can be derived from a plant, an animal, or a microorganism.
  • the amylase is derived from a microorganism, such as a yeast, a mold, or a bacterium.
  • Preferred amylases include those derived from a Bacillus, such as B. licheniformis, B. amyloliquefaciens, B. subtilis, or B. stearothermophilus.
  • the amylase can be purified or a component of a microbial extract, and either wild type or variant (either chemical or recombinant), preferably a variant that is more stable under washing or presoak conditions than a wild type amylase.
  • Preferred commercially available amylase enzymes include the stability enhanced variant amylase sold under the trade name Duramyl ® by Novo. A mixture of amylases can also be used.
  • Amylases suitable for the present invention include: I-amylases described in WO 95/26397, PCT/DK96/00056, and GB 1,296,839 to Novo; and stability enhanced amylases described in J. Biol. Chem., 260(11):6518- 6521 (1985); WO 9510603 A, WO 9509909 A and WO 9402597 to Novo; references disclosed in WO 9402597; and WO 9418314 to Genencor International.
  • a variant I-amylase employed in the present stabilized enzyme cleaning compositions is preferably at least 80% homologous, preferably having at least 80% sequence identity, with the amino acid sequences of the proteins of these references.
  • a cellulase suitable for the present invention can be derived from a plant, an animal, or a microorganism.
  • the cellulase is derived from a microorganism, such as a fungus or a bacterium.
  • Preferred cellulases include those derived from a fungus, such as Humicola insolens, Humicola strain DSM1800, or a cellulase 212-producing fungus belonging to the genus Aeromonas and those extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • the cellulase can be purified or a component of an extract, and either wild type or variant (either chemical or recombinant).
  • Examples of cellulase enzymes that can be employed in the stabilized enzyme cleaning composition of the invention include those sold under the trade names Carezyme ® or Celluzyme ® by Novo, or Cellulase by Genencor; and the like.
  • a mixture of cellulases can also be used. Suitable cellulases are described in patent documents including: U.S. Pat. No. 4,435,307, GB-A-2.075.028, GB-A-2.095.275, DE-OS-2.247.832, WO 9117243, and WO 9414951 A (stabilized cellulases) to Novo. Naturally, mixtures of different cellulase enzymes can be incorporated into this invention. While various specific enzymes have been described above, it is to be understood that any cellulase which can confer the desired cellulase activity to the composition can be used and this embodiment of this invention is not limited in any way by specific choice of cellulase enzyme.
  • a lipase suitable for the present invention can be derived from a plant, an animal, or a microorganism.
  • the lipase is derived from a microorganism, such as a fungus or a bacterium.
  • Preferred lipases include those derived from a Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, or from a Humicola, such as Humicola lanuginosa (typically produced recombinantly in Aspergillus oryzae).
  • the lipase can be purified or a component of an extract, and either wild type or variant (either chemical or recombinant).
  • Other commercially available lipases that can be employed in the present compositions include Amano-CES, lipases derived from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A.
  • lipases derived from Pseudomonas gladioli or from Humicola lanuginosa.
  • a preferred lipase is sold under the trade name Lipolase ® by Novo.
  • Suitable lipases are described in patent documents including: WO 9414951 A (stabilized lipases) to Novo, WO 9205249, RD 94359044, GB 1,372,034, Japanese Patent Application 53,20487, laid open Feb. 24, 1978 to Amano Pharmaceutical Co. Ltd., and EP 341,947.
  • WO 9414951 A stabilizedionas gladioli
  • RD 94359044 GB 1,372,034
  • Japanese Patent Application 53,20487 laid open Feb. 24, 1978 to Amano Pharmaceutical Co. Ltd.
  • EP 341,947 Naturally, mixtures of different lipase enzymes can be incorporated into this invention.
  • any lipase which can confer the desired lipase activity to the composition can be used and this embodiment of this invention is not limited in any way by specific choice of lipase enzyme.
  • Additional Enzymes Additional enzymes suitable for use in the present stabilized enzyme cleaning compositions include a cutinase, a peroxidase, a gluconase, and the like. Suitable cutinase enzymes are described in WO 8809367 A to Genencor. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase.
  • Peroxidases suitable for stabilized enzyme cleaning compositions are disclosed in WO 89099813 A and WO 8909813 A to Novo.
  • Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, and the like.
  • Additional enzymes suitable for incorporation into the present stabilized enzyme cleaning composition are disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. Pat. No. 3,553,139 to McCarty et al., U.S. Pat. No. 4,101,457 to Place et al, U.S. Pat. No. 4,507,219 to Hughes and U.S. Pat. No.
  • An additional enzyme such as a cutinase or peroxidase, suitable for the stabilized enzyme cleaning composition of the present invention can be derived from a plant, an animal, or a microorganism. Preferably the enzyme is derived from a microorganism.
  • the enzyme can be purified or a component of an extract, and either wild type or variant (either chemical or recombinant). Naturally, mixtures of different additional enzymes can be incorporated into this invention. While various specific enzymes have been described above, it is to be understood that any additional enzyme which can confer the desired enzyme activity to the composition can be used and this embodiment of this invention is not limited in any way by specific choice of enzyme.
  • the enzyme stabilizing system of the present invention includes a mixture of carbonate and bicarbonate.
  • the enzyme stabilizing system can also include other ingredients to stabilize certain enzymes or to enhance or maintain the effect of the mixture of carbonate and bicarbonate.
  • Stabilizing systems of certain cleaning compositions for example medical or dental instrument or device stabilized enzyme cleaning compositions, may further include from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during warewashing, can be relatively large; accordingly, enzyme stability to chlorine in-use can be problematic.
  • percarbonate or percarbonate which have the ability to react with chlorine bleach, may be present in certain of the instant compositions in amounts accounted for separately from the stabilizing system, the use of additional stabilizers against chlorine, may, most generally, not be essential, though improved results may be obtainable from their use.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (ME A), and mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • ME A monoethanolamine
  • special enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility.
  • scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium percarbonate tetrahydrate, sodium percarbonate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
  • sources of hydrogen peroxide such as sodium percarbonate tetrahydrate, sodium percarbonate monohydrate and sodium percarbonate
  • phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
  • the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, there is no requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme- containing embodiment of the invention; even
  • the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer that is unacceptably incompatible, as formulated, with other reactive ingredients.
  • ammonium salts such salts can be simply admixed with the stabilized enzyme cleaning composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Pat. No. 4,652,392, Baginski et al.
  • surfactant or surfactant mixture of the present invention can be selected from water soluble or water dispersible nonionic, semi-polar nonionic, anionic, cationic, amphoteric, or zwitterionic surface-active agents; or any combination thereof.
  • Nonionic surfactants useful in the invention are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol.
  • any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent.
  • hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties.
  • Useful nonionic surfactants in the present invention include: 1. Block polyoxypropylene-polyoxyethylene polymeric compounds based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. Examples of polymeric compounds made from a sequential propoxylation and ethoxylation of initiator are commercially available under the trade names Pluronic ® and Tetronic ® manufactured by BASF Corp.
  • Pluronic ® compounds are difunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from 1,000 to 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10%) by weight to about 80% by weight of the final molecule.
  • Tetronic ® compounds are tetra-f ⁇ nctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine.
  • the molecular weight of the propylene oxide hydrotype ranges from 500 to 7,000; and, the hydrophile, ethylene oxide, is added to constitute from 10% by weight to 80% by weight of the molecule.
  • the alkyl group can, for example, be represented by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl.
  • These surfactants can be polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. Examples of commercial compounds of this chemistry are available on the market under the trade names Igepal manufactured by Rhone-Poulenc and Triton manufactured by Union Carbide. 3. Condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from 6 to 24 carbon atoms with from 3 to 50 moles of ethylene oxide. The alcohol moiety can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specific number of carbon atoms within this range. Examples of like commercial surfactant are available under the trade names Neodol ® manufactured by Shell Chemical Co.
  • the acid moiety can consist of mixtures of acids in the above defined carbon atoms range or it can consist of an acid having a specific number of carbon atoms within the range. Examples of commercial compounds of this chemistry are available on the market under the trade names Nopalcol ® manufactured by Henkel Corporation and Lipopeg ® manufactured by Lipo Chemicals, Inc.
  • ethoxylated carboxylic acids commonly called polyethylene glycol esters
  • other alkanoic acid esters formed by reaction with glycerides, glycerin, and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in this invention. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these substances. Care must be exercised when adding these fatty ester or acylated carbohydrates to compositions of the present invention containing amylase and/or lipase enzymes because of potential incompatibility.
  • nonionic low foaming surfactants include: 5.
  • reactants such as thionyl chloride which convert terminal hydroxy groups to a chloride group.
  • Such modifications to the terminal hydroxy group may lead to all-block, block-heteric, heteric-block or all-heteric nonionics.
  • Additional examples of effective low foaming nonionics include: 7. The alkylphenoxypolyethoxyalkanols of U.S. Pat No. 2,903,486 issued September 8, 1959 to Brown et al. and represented by the formula
  • R is an alkyl group of 8 to 9 carbon atoms
  • A is an alkylene chain of 3 to 4 carbon atoms
  • n is an integer of 7 to 16
  • m is an integer of 1 to 10.
  • Y is the residue of organic compound having from 1 to 6 carbon atoms and one reactive hydrogen atom
  • n has an average value of at least 6.4, as determined by hydroxyl number
  • m has a value such that the oxyethylene portion constitutes 10% to 90% by weight of the molecule.
  • Y is the residue of an organic compound having from 2 to 6 carbon atoms and containing x reactive hydrogen atoms in which x has a value of at least 2, n has a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least 900 and m has value such that the oxyethylene content of the molecule is from 10% to 90% by weight.
  • Compounds falling within the scope of the definition for Y include, for example, propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine and the like.
  • the oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of propylene oxide.
  • Additional conjugated polyoxyalkylene surface-active agents which are advantageously used in the compositions of this invention correspond to the formula: P[(C 3 H 6 O) n (C 2 H O) m H] x wherein P is the residue of an organic compound having from 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least 44 and m has a value such that the oxypropylene content of the molecule is from 10% to 90% by weight.
  • polyhydroxy fatty acid amide surfactants suitable for use in the present compositions include those having the structural formula R 2 CONR 1 Z in which: R 1 is H, C C 4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R 2 is a C 5 - C 3 ⁇ hydrocarbyl, which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z can be derived from a reducing sugar in a reductive amination reaction; such as a glycityl moiety.
  • the alkyl ethoxylate condensation products of aliphatic alcohols with from 0 to 25 moles of ethylene oxide are suitable for use in the present compositions.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • the ethoxylated C 6 -Ci 8 fatty alcohols and C 6 -C ⁇ 8 mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the present compositions, particularly those that are water soluble.
  • Suitable ethoxylated fatty alcohols include the C ⁇ o-C ⁇ 8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50. 11.
  • Suitable nonionic alkylpolysaccharide surfactants particularly for use in the present compositions include those disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units. 12.
  • Fatty acid amide surfactants suitable for use in the present compositions include those having the formula: R CON(R ) 2 in which R is an alkyl group containing from 7 to 21 carbon atoms and each R is independently hydrogen, C ⁇ -C 4 alkyl, C 1 -C 4 hydroxyalkyl, or -(C 2 H O) x H, where x is in the range of from 1 to 3. 13.
  • R CON(R ) 2 in which R is an alkyl group containing from 7 to 21 carbon atoms and each R is independently hydrogen, C ⁇ -C 4 alkyl, C 1 -C 4 hydroxyalkyl, or -(C 2 H O) x H, where x is in the range of from 1 to 3. 13.
  • a useful class of non-ionic surfactants includes the class defined as alkoxylated amines or, most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants.
  • non-ionic surfactants may be at least in part represented by the general formulae: R 20 -(PO) s N-(EO) t H, R 20 -(PO) s N-(EO) t H(EO) t H, and R 20 -N(EO) t H; in which R 20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably 2-5.
  • w and z are independently 1-10, preferably 2-5.
  • These compounds are represented commercially by a line of products sold by Huntsman Chemicals as nonionic surfactants.
  • a preferred chemical of this class includes SurfonicTM PEA 25 Amine Alkoxylate.
  • the treatise Nonionic Surfactants, edited by Schick, M.J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety of nonionic compounds generally employed in the practice of the present invention.
  • a typical listing of nonionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.
  • Semi-Polar Nonionic Surfactants are another class of nonionic surfactant useful in compositions of the present invention.
  • semi-polar nonionics are high foamers and foam stabilizers, which can limit their application in CIP systems.
  • semi-polar nonionics would have immediate utility.
  • the semi-polar nonionic surfactants include the amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives. 14.
  • Amine oxides are tertiary amine oxides corresponding to the general formula:
  • R 1 is an alkyl radical of from 8 to 24 carbon atoms; R and R are alkyl or hydroxyalkyl of 1-3 carbon atoms or a mixture thereof; R and R can be attached to each other, e.g. through an oxygen or nitrogen atom, to form a ring structure; R 4 is an alkaline or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges from 0 to 20.
  • Useful water soluble amine oxide surfactants are selected from the coconut or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2- hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3 -dodecoxy- 1 - hydroxypropyl
  • R 1 is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to 24 carbon atoms in chain length; and R 2 and R 3 are each alkyl moieties separately selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.
  • useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2- hydroxyethyl)dodecylphosphine oxide, and bis(hydroxymethyl)tetradecylphosphine oxide.
  • Semi-polar nonionic surfactants useful herein also include the water soluble sulf oxide compounds which have the structure:
  • R 1 is an alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, from 0 to 5 ether linkages and from 0 to 2 hydroxyl substituents; and R 2 is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.
  • sulfoxides include dodecyl methyl sulfoxide; 3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
  • Anionic Surfactants Also useful in the present invention are surface active substances which are categorized as anionics because the charge on the hydrophobe is negative; or surfactants in which the hydrophobic section of the molecule carries no charge unless the pH is elevated to neutrality or above (e.g. carboxylic acids).
  • Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic) solubilizing groups found in anionic surfactants.
  • sodium, lithium and potassium impart water solubility; ammonium and substituted ammonium ions provide both water and oil solubility; and, calcium, barium, and magnesium promote oil solubility.
  • anionics are excellent detersive surfactants and are therefore favored additions to heavy duty detergent compositions.
  • anionics have high foam profiles which limit their use alone or at high concentration levels in cleaning systems such as CIP circuits that require strict foam control.
  • Anionic surface active compounds are useful to impart special chemical or physical properties other than detergency within the composition.
  • Anionics can be employed as gelling agents or as part of a gelling or thickening system.
  • Anionics are excellent solubilizers and can be used for hydrotropic effect and cloud point control.
  • the majority of large volume commercial anionic surfactants can be subdivided into five major chemical classes and additional sub-groups known to those of skill in the art and described in "Surfactant Encyclopedia," Cosmetics & Toiletries, Vol. 104 (2) 71-86 (1989).
  • the first class includes acylamino acids (and salts), such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride), and the like.
  • the second class includes carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g.
  • the third class includes phosphoric acid esters and their salts.
  • the fourth class includes sulfonic acids (and salts), such as isethionates (e.g. acyl isethionates), alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates (e.g. monoesters and diesters of sulfosuccinate), and the like.
  • the fifth class includes sulfuric acid esters (and salts), such as alkyl ether sulfates, alkyl sulfates, and the like.
  • Anionic sulfate surfactants suitable for use in the present compositions include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C ⁇ 7 acyl-N-(C ⁇ -C alkyl) and -N-(C ⁇ - C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Suitable synthetic, water soluble anionic detergent compounds include the ammonium and substituted ammonium (such as mono-, di- and triethanolamine) and alkali metal (such as sodium, lithium and potassium) salts of the alkyl mononuclear aromatic sulfonates such as the alkyl benzene sulfonates containing from 5 to 18 carbon atoms in the alkyl group in a straight or branched chain, e.g., the salts of alkyl benzene sulfonates or of alkyl toluene, xylene, cumene and phenol sulfonates; alkyl naphthalene sulfonate, dia yl naphthalene sulfonate, and dinonyl naphthalene sulfonate and alkoxylated derivatives.
  • ammonium and substituted ammonium such as mono-, di- and triethanolamine
  • alkali metal such as sodium,
  • Anionic carboxylate surfactants suitable for use in the present compositions include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps (e.g. alkyl carboxyls).
  • Secondary soap surfactants (e.g. alkyl carboxyl surfactants) useful in the present compositions include those which contain a carboxyl unit connected to a secondary carbon.
  • the secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates.
  • the secondary soap surfactants typically contain no ether linkages, no ester linkages and no hydroxyl groups.
  • Suitable secondary soap surfactants typically contain 11-13 total carbon atoms, although more carbons atoms (e.g., up to 16) can be present.
  • Other anionic detergents suitable for use in the present compositions include olefin sulfonates, such as long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkane-sulfonates.
  • alkyl sulfates alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy) sulfates such as the sulfates or condensation products of ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylene groups per molecule).
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • the particular salts will be suitably selected depending upon the particular formulation and the needs therein.
  • suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in
  • Cationic Surfactants Surface active substances are classified as cationic if the charge on the hydrotrope portion of the molecule is positive. Surfactants in which the hydrotrope carries no charge unless the pH is lowered close to neutrality or lower, but which are then cationic (e.g. alkyl amines), are also included in this group. In theory, cationic surfactants may be synthesized from any combination of elements containing an "onium" structure RnX+Y- and could include compounds other than nitrogen (ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium).
  • Cationic surfactants preferably include, more preferably refer to, compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen.
  • the long carbon chain group may be attached directly to the nitrogen atom by simple substitution; or more preferably indirectly by a bridging functional group or groups in so- called interrupted alkylamines and amido amines.
  • Such functional groups can make the molecule more hydrophilic and/or more water dispersible, more easily water solubilized by co-surfactant mixtures, and/or water soluble.
  • additional primary, secondary or tertiary amino groups can be introduced or the amino nitrogen can be quatemized with low molecular weight alkyl groups.
  • the nitrogen can be a part of branched or straight chain moiety of varying degrees of unsaturation or of a saturated or unsaturated heterocyclic ring.
  • cationic surfactants may contain complex linkages having more than one cationic nitrogen atom.
  • the surfactant compounds classified as amine oxides, amphoterics and zwitterions are themselves typically cationic in near neutral to acidic pH solutions and can overlap surfactant classifications.
  • Polyoxyethylated cationic surfactants generally behave like nonionic surfactants in alkaline solution and like cationic surfactants in acidic solution.
  • the simplest cationic amines, amine salts and quaternary ammonium compounds can be schematically drawn thus:
  • R represents a long alkyl chain
  • R, R" and R" may be either long alkyl chains or smaller alkyl or aryl groups or hydrogen and X represents an anion.
  • the amine salts and quaternary ammonium compounds are preferred for practical use in this invention due to their high degree of water solubility.
  • the majority of large volume commercial cationic surfactants can be subdivided into four major classes and additional sub-groups known to those of skill in the art and described in "Surfactant Encyclopedia,"
  • the first class includes alkylamines and their salts.
  • the second class includes alkyl imidazolines.
  • the third class includes ethoxylated amines.
  • the fourth class includes quaternaries, such as alkylbenzyldimethylammonium salts, alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammonium salts, and the like.
  • Cationic surfactants are known to have a variety of properties that can be beneficial in the present compositions. These desirable properties can include detergency in compositions of or below neutral pH, antimicrobial efficacy, thickening or gelling in cooperation with other agents, and the like.
  • Cationic surfactants useful in the compositions of the present 1 1 invention include those having the formula R m R X Y L Z wherein each R is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four of the following structures:
  • the R 1 groups can additionally contain up to 12 ethoxy groups, m is a number from 1 to 3. Preferably, no more than one R 1 group in a molecule has 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3.
  • Each R 2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 2 in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group are filled by hydrogens.
  • Y can be a group including, but not limited to:
  • L is 1 or 2
  • Y groups being separated by a moiety selected from R 1 and R 2 analogs (preferably alkylene or alkenylene) having from 1 to 22 carbon atoms and two free carbon single bonds when L is 2.
  • Z is a water soluble anion, such as sulfate, methylsulfate, hydroxide, or nitrate anion, particularly preferred being sulfate or methyl sulfate anions, in a number to give electrical neutrality of the cationic component.
  • Amphoteric Surfactants Amphoteric, or ampholytic, surfactants contain both a basic and an acidic hydrophilic group and an organic hydrophobic group.
  • ionic entities may be any of the anionic or cationic groups described herein for other types of surfactants.
  • a basic nitrogen and an acidic carboxylate group are the typical functional groups employed as the basic and acidic hydrophilic groups.
  • surfactants sulfonate, sulfate, phosphonate or phosphate provide the negative charge.
  • Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
  • Amphoteric surfactants are subdivided into two major classes known to those of skill in the art and described in "Surfactant Encyclopedia," Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989). The first class includes acyl/dialkyl ethylenediamine derivatives (e.g.
  • 2-alkyl hydroxyethyl imidazoline derivatives and their salts.
  • the second class includes N- alkylamino acids and their salts.
  • Some amphoteric surfactants can be envisioned as fitting into both classes.
  • Amphoteric surfactants can be synthesized by methods known to those of skill in the art. For example, 2-alkyl hydroxyethyl imidazoline is synthesized by condensation and ring closure of a long chain carboxylic acid (or a derivative) with dialkyl ethylenediamine.
  • Commercial amphoteric surfactants are derivatized by subsequent hydrolysis and ring- opening of the imidazoline ring by alkylation ⁇ for example with ethyl acetate.
  • Long chain imidazole derivatives having application in the present invention generally have the general formula: (MONO)ACETATE (DI)PROPIONATE AMPHOTERIC SULFONATE
  • R is an acyclic hydrophobic group containing from 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion, generally sodium.
  • M is a cation to neutralize the charge of the anion, generally sodium.
  • imidazoline-derived amphoterics that can be employed in the present compositions include for example:
  • Cocoamphopropionate Cocoamphocarboxy-propionate
  • Cocoamphoglycinate Cocoamphocarboxy-glycinate, Cocoamphopropyl- sulfonate, and Cocoamphocarboxy-propionic acid.
  • Preferred amphocarboxylic acids are produced from fatty imidazolines in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • the carboxymethylated compounds (glycinates) described herein above frequently are called betaines.
  • Betaines are a special class of amphoteric discussed herein below in the section entitled, Zwitterion
  • Most commercial N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl) alanine.
  • Examples of commercial N-alkylamino acid ampholytes having application in this invention include alkyl beta-amino dipropionates, RN(C 2 H 4 COOM) 2 and RNHC 2 H 4 COOM.
  • R is preferably an acyclic hydrophobic group containing from 8 to 18 carbon atoms
  • M is a cation to neutralize the charge of the anion.
  • Preferred amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acid. The more preferred of these coconut derived surfactants include as part of their structure an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, preferably glycine, or a combination thereof; and an aliphatic substituent of from 8 to 18 (preferably 12) carbon atoms. Such a surfactant can also be considered an alkyl amphodicarboxylic acid.
  • Disodium cocoampho dipropionate is one most preferred amphoteric surfactant and is commercially available under the tradename MiranolTM FBS from Rhodia Inc., Cranbury, N. J. Another most preferred coconut derived amphoteric surfactant with the chemical name disodium cocoampho diacetate is sold under the tradename MiranolTM C2M-SF Cone, also from Rhodia Inc., Cranbury, NJ.
  • MiranolTM C2M-SF Cone also from Rhodia Inc., Cranbury, NJ.
  • a typical listing of amphoteric classes, and species of these surfactants is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
  • Zwitterionic surfactants can be thought of as a subset of the amphoteric surfactants. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Typically, a zwitterionic surfactant includes a positive charged quaternary ammonium or, in some cases, a sulfonium or phosphonium ion, a negative charged carboxyl group, and an alkyl group.
  • Zwitterionics generally contain cationic and anionic groups which ionize to a nearly equal degree in the isoelectric region of the molecule and which can develop strong "inner-salt" attraction between positive-negative charge centers.
  • Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. A general formula for these compounds is:
  • R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8 to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety;
  • Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms;
  • R is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon atoms;
  • x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom,
  • R 3 is an alkylene or hydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • Examples of zwitterionic surfactants having the structures listed above include : 4- [N,N-di(2-hydroxyethyl)-N-octadecylammonio] -butane- 1 -carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3- hydroxypentane-1 -sulfate; 3-[P,P-diethyl-P-3,6,9- trioxatetracosanephosphonio]-2-hydroxypropane-l -phosphate; 3-[N,N- dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-l- phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane- 1 - sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy
  • betaines typically do not exhibit strong cationic or anionic characters at pH extremes nor do they show reduced water solubility in their isoelectric range. Unlike “external" quaternary ammonium salts, betaines are compatible with anionics.
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12 -i 4 acylamidopropylbetaine; C 8- ⁇ 4 acylamidohexyldiethyl betaine; 4-C ⁇ 4- ⁇ 6 acylmethylamidodiethylammonio-1-carboxybutane; C ⁇ 6- ⁇ 8 acylamidodimethylbetaine; C 12 -.i 6 acylamidopentanediethylbetaine; and C12- 16 acylmethylamidodimethylbetaine .
  • Sultaines useful in the present invention include those compounds having the formula (R(R J ) 2 N* R 2 SO 3" , in which R is a C 6 -C ⁇ 8 hydrocarbyl group, each R 1 is typically independently C ⁇ -C 3 alkyl, e.g. methyl, and R 2 is a C ⁇ -C 6 hydrocarbyl group, e.g. a C ⁇ -C 3 alkylene or hydroxyalkylene group.
  • R is a C 6 -C ⁇ 8 hydrocarbyl group
  • each R 1 is typically independently C ⁇ -C 3 alkyl, e.g. methyl
  • R 2 is a C ⁇ -C 6 hydrocarbyl group, e.g. a C ⁇ -C 3 alkylene or hydroxyalkylene group.
  • a typical listing of zwitterionic classes, and species of these surfactants is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in
  • the composition may optionally include a binding agent to bind the detergent composition together to provide a solid detergent composition.
  • the binding agent may be formed by mixing alkali metal carbonate, alkali metal bicarbonate, and water.
  • the binding agent may also be urea or polyethylene glycol.
  • Antimicrobial Agent are chemical compositions that can be used in the composition to prevent microbial contamination and deterioration of commercial products material systems, surfaces, etc.
  • microbes typically refer primarily to bacteria and fungus microorganisms.
  • the antimicrobial agents are formed into the final product that when diluted and dispensed using an aqueous stream forms an aqueous disinfectant or sanitizer composition that can be contacted with a variety of surfaces resulting in prevention of growth or the killing of a substantial proportion of the microbial population.
  • Common antimicrobial agents include phenolic antimicrobials such as pentachlorophenol, orthophenylphenol.
  • Halogen containing antibacterial agents include sodium trichloroisocyanurate, sodium dichloroisocyanurate (anhydrous or dihydrate), iodine-poly(vinylpyrolidin- onen) complexes, bromine compounds such as 2-bromo-2-nitropropane-l,3-diol quaternary antimicrobial agents such as benzalconium chloride, cetylpyridiniumchloride, amine and nitro containing antimicrobial compositions such as hexahydro-l,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates such as sodium dimethyldithiocarbamate, and a variety of other materials known in the art for their microbial properties.
  • Antimicrobial agents may be encapsulated to improve stability and/or to reduce reactivity with other materials in the detergent composition.
  • Bleaching Agent Bleaching agents for use in inventive formulations for lightening or whitening a substrate include bleaching compounds capable of liberating an active halogen species, such as Cl 2 , Br 2 , -OCI " and/or -OB , under conditions typically encountered during the cleansing process.
  • Suitable bleaching agents for use in the present cleaning compositions include, for example, chlorine-containing compounds such as a chlorine, a hypochlorite, chloramine.
  • Preferred halogen-releasing compounds include the alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochlorarrine and dichloramine, and the like.
  • Encapsulated bleaching sources may also be used to enhance the stability of the bleaching source in the composition (see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773, the disclosure of which is incorporated by reference herein).
  • a bleaching agent may also be a peroxygen or active oxygen source such as hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrates, potassium permonosulfate, and sodium perborate mono and tetrahydrate, with and without activators such as tetraacetylethylene diamine, and the like.
  • a cleaning composition may include a minor but effective amount of a bleaching agent, preferably about 0.1 - 10 wt. %, preferably about 1-6 wt. %.
  • Defoaming Agent/ Foam Inhibitor The composition of the invention may include a defoaming agent or a foam inhibitor. A defoaming agent or foam inhibitor may be included for reducing the stability of any foam that is formed.
  • foam inhibitors include silicon compounds such as silica dispersed in polydimethylsiloxane, fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, polyoxyethylene-polyoxypropylene block copolymers, alkyl phosphate esters such as monostearyl phosphate and the like.
  • foam inhibitors may be found, for example, in U.S. Pat. No. 3,048,548 to Martin et al., U.S. Pat. No. 3,334,147 to Brunelle et al, and U.S. Pat. No.
  • the composition may also include an antiredeposition agent capable of facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned.
  • an antiredeposition agent capable of facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned.
  • suitable antiredeposition agents include fatty acid amides, complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.
  • Dye or Odorant Various dyes, odorants including perfumes, and other aesthetic enhancing agents may also be included in the composition.
  • Dyes may be included to alter the appearance of the composition, as for example, Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and
  • Fragrances or perfumes that may be included in the compositions include, for example, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as CIS-jasmine or jasmal, vanillin, and the like.
  • compositions of the invention may optionally include a hydrotrope, coupling agent, or solubilizer that aides in compositional stability, and aqueous formulation.
  • a hydrotrope e.g., a hydrotrope, coupling agent, or solubilizer that aides in compositional stability, and aqueous formulation.
  • the suitable couplers which can be employed are non-toxic and retain the active ingredients in aqueous solution throughout the temperature range and concentration to which a concentrate or any use solution is exposed. Any hydrotrope coupler may be used provided it does not react with the other components of the composition or negatively affect the performance properties of the composition.
  • hydrotropic coupling agents or solubilizers which can be employed include anionic surfactants such as alkyl sulfates and alkane sulfonates, linear alkyl benzene or naphthalene sulfonates, secondary alkane sulfonates, alkyl ether sulfates or sulfonates, alkyl phosphates or phosphonates, dialkyl sulfosuccinic acid esters, sugar esters (e.g., sorbitan esters), amine oxides (mono-, di-, or tri-alkyl) and C 8 -C ⁇ 0 alkyl glucosides.
  • anionic surfactants such as alkyl sulfates and alkane sulfonates, linear alkyl benzene or naphthalene sulfonates, secondary alkane sulfonates, alkyl ether sulfates or sulfonates,
  • Preferred coupling agents for use in the present invention include n-octanesulfonate, available as NAS 8D from Ecolab Inc., n-octyl dimethylamine oxide, and the commonly available aromatic sulfonates such as the alkyl benzene sulfonates (e.g. xylene sulfonates) or naphthalene sulfonates, aryl or af aryl phosphate esters or their alkoxylated analogues having 1 to about 40 ethylene, propylene or butylene oxide units or mixtures thereof.
  • Nonionic surfactants of C 6 -C 2 4 alcohol alkoxylates (alkoxylate means ethoxylates, propoxylates, butoxylates, and co-or-terpolymer mixtures thereof) (preferably C 6 -Cj 4 alcohol alkoxylates) having 1 to about 15 alkylene oxide groups (preferably about 4 to about 10 alkylene oxide groups); C 6 -C 24 alkylphenol alkoxylates (preferably C 8 -C ⁇ o alkylphenol alkoxylates) having 1 to about 15 alkylene oxide groups (preferably about 4 to about 10 alkylene oxide groups); C 6 -C 2 alkylpolyglycosides (preferably C 6 -C 20 alkylpolyglycosides) having 1 to about 15 glycoside groups (preferably about 4 to about 10 glycoside groups); C 6 -C 2 fatty acid ester ethoxylates, propoxylates or glycerides; and C 4 -C 12 mono or dialkanol
  • Carrier may optionally include a carrier or solvent.
  • the carrier may be water or other solvent such as an alcohol or polyol.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups (e.g. propylene glycol, ethylene glycol, glycerine, and 1,2- propanediol) can also be used.
  • Acidic Composition The method of the present invention includes at least one acidic step wherein an acidic composition is brought into contact with a dish during the acidic step of the cleaning process.
  • the acidic composition includes one or more acids. Both organic and inorganic acids have been found to be generally useful in the present composition.
  • Organic acids useful in accordance with the invention include hydroxyacetic (glycolic) acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid, among others.
  • Organic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid among others are also useful in accordance with the invention.
  • organic acids may also be used intermixed or with other organic acids which allow adequate formation of the composition of the invention.
  • Inorganic acids useful in accordance with the invention include phosphoric acid, sulfuric acid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitric acid among others. These acids may also be used in combination with other inorganic acids or with those organic acids mentioned above.
  • An acid generator may also be used in the composition to form a suitable acid.
  • suitable generators include calcium phosphate, potassium fluoride, sodium fluoride, lithium fluoride, ammonium fluoride, ammonium bifiuoride, sodium silicofluoride, etc.
  • the acid is preferably phosphoric. In another embodiment, the acid is preferably a mixture of citric acid and sulfamic acid. A mixture of citric acid and sulfamic acid is especially good when hard water is used because it does not create precipitates.
  • the acid is preferably present in the diluted, ready to use, acidic composition from about 0.01 wt.% to about 1 wt.%, more preferably from about 0.25 wt.% to about 0.5 wt.% and most preferably from about 0.05 wt.% to about 0.05 wt.%).
  • the acidic composition preferably creates a diluted solution having a pH from about 0 to about 7, more preferably from about 1 to about 5, and most preferably from about 2 to about 4.
  • the particular acid selected is not as important as the resulting pH. Any acid that achieves the desired pH may be used in the acidic composition of the invention.
  • the acidic composition may include additional ingredients.
  • the acidic composition may include an anticorrosion agent, a water conditioning agent, a surfactant, an enzyme, an enzyme stabilizing system, a foam inhibitor/defoaming agents, an anti-etch agent, a bleaching agent, a dye or odorant, an antimicrobial agent, a hydrotrope, a binding agent, a carrier and mixtures thereof.
  • the water conditioning agent, enzyme, enzyme stabilizing system, surfactant, bleaching agent, dye or odorant, antimicrobial agent, hydrotrope, antiredeposition agent, binding agent, and carrier may be selected from any those compositions previously described herein.
  • Surfactant In addition to the surfactants previously described, it has been discovered that it is advantageous to put a nonionic surfactant and/or a cationic surfactant into the acidic composition.
  • a nonionic surfactant when included in the acidic composition and used in the method of the invention has been found to assist in preventing the formation of spots as well as assisting in the prevention of redeposition soils. The nonionic surfactant also helps in the removal or soils.
  • a preferred nonionic surfactant is a low foaming nonionic surfactant such as Pluronic N-3, commercially available from BASF.
  • a cationic surfactant when included in the acidic composition and used in the method of the invention has been found to assist in the removal of protein. Examples of preferred cationic surfactants are found in U.S. Pat. No. 6,218,349, which is hereby incorporated by reference in its entirety.
  • the cationic surfactant is preferably diethylammonium chloride, commercially available as Glensurf 42 from Glenn Chemical (St. Paul, MN).
  • Anti-Etch Agent The composition may also include an anti-etch agent capable of preventing etching in glass.
  • anti-etch agents include adding metal ions to the composition such as zinc, zinc chloride, zinc gluconate, aluminum, and beryllium.
  • the composition may optionally include an anticorrosion agent.
  • Anticorrosion agents provide compositions that generate surfaces that are shiner and less prone to biofilm buildup than surfaces that are not treated with compositions having anticorrosion agents.
  • Preferred anticorrosion agents which can be used according to the invention include phosphonates, phosphonic acids, triazoles, organic amines, sorbitan esters, carboxylic acid derivatives, sarcosinates, phosphate esters, zinc, nitrates, chromium, molybdate containing components, and borate containing components.
  • Exemplary phosphates or phosphonic acids are available under the name Dequest (i.e., Dequest 2000, Dequest 2006, Dequest 2010, Dequest 2016, Dequest 2054, Dequest 2060, and Dequest 2066) from Solutia, Inc. of St. Louis, MO.
  • Exemplary triazoles are available under the name Cobratec (i.e., Cobratec 100, Cobratec TT-50-S, and Cobratec 99) from PMC Specialties Group, Inc. of Cincinnati, Ohio.
  • Exemplary organic amines include aliphatic amines, aromatic amines, monoamines, diamines, triamines, polyamines, and their salts.
  • Exemplary amines are available under the names Amp (i.e.
  • sorbitan esters are available under the name Calgene (LA-series) from Calgene Chemical Inc. of Skokie, Illinois.
  • Exemplary carboxylic acid derivatives are available under the name Recor (i.e., Recor 12) from Ciba- Geigy Corp. of Tarrytown, N.Y.
  • Exemplary sarcosinates are available under the names Hamposyl from Hampshire Chemical Corp. of Lexington, Massachusetts; and Sarkosyl from Ciba-Geigy Corp. of Tarrytown, New York.
  • the composition optionally includes an anticorrosion agent for providing enhanced luster to the metallic portions of a dish machine.
  • Rinse As previously discussed, the method may optionally include a rinse step. The rinse step may take place at any time during the cleaning process and at more than one time during the cleaning process. The method preferably includes one rinse at the end of the cleaning process.
  • the rinse composition may comrpise a formulated rinse aid composition containing a wetting or sheeting agent combined with other optional ingredients.
  • the rinse aid components is a water soluble or dispersible low foaming organic material capable of reducing the surface tension of the rinse water to promote sheeting action and to prevent spotting or streaking caused by beaded water after rinsing is complete in warewashing processes.
  • Such sheeting agents are typically organic surfactant like materials having a characteristic cloud point.
  • the cloud point of the surfactant rinse or sheeting agent is defined as the temperature at which a 1 wt. % aqueous solution of the surfactant turns cloudy when warmed.
  • a first type generally considered a sanitizing rinse cycle uses rinse water at a temperature of about 180. degree. F., about 80. degree. C. or higher.
  • a second type of non-sanitizing machines uses a lower temperature non-sanitizing rinse, typically at a temperature of about 125.degree. F., about 50. degree. C. or higher.
  • Surfactants useful in these applications are aqueous rinses having a cloud point greater than the available hot service water. Accordingly, the lowest useful cloud point measured for the surfactants of the invention is approximately 40. degree. C.
  • the cloud point can also be ⁇ O.degree. C. or higher, 70. degree. C. or higher, 80. degree. C.
  • Preferred sheeting agents typically comprise a polyether compound prepared from ethylene oxide, propylene oxide, or a mixture in a homopolymer or block or heteric copolymer structure.
  • Such polyether compounds are known as polyalkylene oxide polymers, polyoxyalkylene polymers or polyalkylene glycol polymers.
  • Such sheeting agents require a region of relative hydrophobicity and a region of relative hydrophilicity to provide surfactant properties to the molecule.
  • Such sheeting agents have a molecular weight in the range of about 500 to 15,000.
  • Certain types of (PO)(EO) polymeric rinse aids have been found to be useful containing at least one block of poly(PO) and at least one block of poly(EO) in the polymer molecule. Additional blocks of poly(EO), poly PO or random polymerized regions can be formed in the molecule.
  • Particularly useful polyoxypropylene polyoxyethylene block copolymers are those comprising a center block of polyoxypropylene units and blocks of polyoxyethylene units to each side of the center block. Such polymers have the formula shown below: (EO)n -(PO)m -(EO)n wherein n is an integer of 20 to 60, each end is independently an integer of 10 to 130.
  • block copolymer having a center block of polyoxyethylene units and blocks of polyoxypropylene to each side of the center block.
  • Such copolymers have the formula: (PO)n -(EO)m -(PO)n wherein m is an integer of 15 to 175 and each end are independently integers of about 10 to 30.
  • the solid functional materials of the invention can often use a hydrotrope to aid in maintaining the solubility of sheeting or wetting agents. Hydrotropes can be used to modify the aqueous solution creating increased solubility for the organic material.
  • Preferred hydrotropes are low molecular weight aromatic sulfonate materials such as xylene sulfonates and dialkyldiphenyl oxide sulfonate materials.
  • Bleaching agents for use in inventive formulations for lightening or whitening a substrate include bleaching compounds capable of liberating an active halogen species, such as C12, Br2, --OC1- and/or —OBr-, under conditions typically encountered during the cleansing process.
  • Suitable bleaching agents for use in the present cleaning compositions include, for example, chlorine-containing compounds such as a chlorine, a hypochlorite, chloramine.
  • Preferred halogen-releasing compounds include the alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochloramine and dichloroamine, and the like. Encapsulated chlorine sources may also be used to enhance the stability of the chlorine source in the composition (see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773, the disclosure of which is incorporated by reference herein).
  • a bleaching agent may also be a peroxygen or active oxygen source such as hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrates, potassium permonosulfate, and sodium perborate mono and tetrahydrate, with and without activators such as tetraacetylethylene diamine, and the like.
  • Dish Machines The method of the invention may be carried out in any consumer or institutional dish machine. Some non-limiting examples of dish machines include door machines or hood machines, conveyor machines, undercounter machines, glasswashers, flight machines, pot and pan machines, utensil washers, and consumer dish machines.
  • the dish machines may be either single tank or multi-tank machines.
  • the dish machine is made out of acid resistant material, especially when the portions of the dish machine that contact the acidic composition do not also contact the alkaline composition.
  • a door dish machine also called a hood dish machine, refers to a commercial dish machine " wherein the soiled dishes are placed on a rack and the rack is then moved into the dish machine.
  • Door dish machines clean one or two racks at a time. In such machines, the rack is stationary and the wash and rinse arms move.
  • a door machine includes two sets arms, a set of wash arms and a rinse arm, or a set of rinse arms.
  • Door machines may be a high temperature or low temperature machine. In a high temperature machine the dishes are sanitized by hot water.
  • the dishes are sanitized by the chemical sanitizer.
  • the door machine may either be a recirculation machine or a dump and fill machine.
  • the detergent solution is reused, or "recirculated" between wash cycles.
  • the concentration of the detergent solution is adjusted between wash cycles so that an adequate concentration is maintained.
  • the wash solution is not reused between wash cycles. New detergent solution is added before the next wash cycle.
  • door machines include the Ecolab Omega HT, the Hobart AM- 14, the Ecolab ES-2000, the Hobart LT-1, the CMA EVA-200, American Dish Service L-3DW and HT-25, the Autochlor A5, the Champion D-HB, and the Jackson Tempstar.
  • the method of the invention may be used in conjunction with any of the door machines described above.
  • the door machine may need to be modified to accommodate the acidic step.
  • the door machine may be modified in one of several ways.
  • the acidic composition may be applied to the dishes using the rinse spray arm of the door machine.
  • the rinse spray arm is connected to a reservoir for the acidic composition.
  • the acidic composition may be applied using the original nozzles of the rinse arm.
  • additional nozzles may be added to the rinse arm for the acidic composition.
  • an additional rinse arm may be added to the door machine for the acidic composition.
  • spray nozzles may be installed in the door machine for the acidic composition.
  • the nozzles are installed inside the door machine in such a way as to provide full coverage to the dish rack.
  • Figure 1 shows a door dish machine modified to provide the acid through the rinse arm of the dish machine.
  • the dish machine (1) consists of a housing frame (3) provided with support legs (2).
  • a first tank (4) for an alkaline cleaning solution In the housing frame (3) there is arranged a first tank (4) for an alkaline cleaning solution.
  • This alkaline cleaning solution is sucked out of the tank (4) using a pump (not shown) fed by means of pipe ducts (5) under pressure to spray nozzles (6) of an upper spray arm (17) and a lower spray arm (18) and sprayed onto the dishes disposed in the upper part of the door dish machine (1).
  • heated rinse water from boiler (13) is sprayed over an upper rinse arm (10) and a lower rinse arm (12).
  • the dish machine (1) has in its upper part a door pivotable in the direction of the arrow (7) or a pivotable housing part (8).
  • This pivotable housing part (8) is to be pivoted by means of a handgrip (9) by the user upwardly for opening and downwardly again for closing into the position illustrated in the figures.
  • the pivotable housing part (8) overlaps the housing frame part (3) in closed position.
  • the boiler (13) is connected to the rinse arm (10) and (1 ) by additional pipe ducts (14). Acid from a container (not shown) can be pumped with a pump (15). Via this pipe ducts (14) and the pump
  • FIG 3 shows a door dish machine where the acid is applied through a separate rinse arm.
  • the boiler (13) is connected to rinse arms (10) and (12) and to additional rinse arms (10a) and (12a).
  • the additional upper rinse arm (10a) is arranged close to the rinse arm (10) and the additional lower rinse arm (12a) close to the lower rinse arm (12).
  • Additional rinse arms (10a) and (12a) are connected with the boiler (13) and the pump (not shown) for the acid.
  • the alkaline cleaning solution from tanlc (4) is sprayed over the spray arms (17) and (18) whereby the acidic cleaning solution is sprayed over the additional rinse arms (10a) and (12a) and the rinse solution over the rinse arms (10) and (12).
  • Figure 4 shows a door dish machine where the acid is applied through additional nozzles (6a) in the rinse arm.
  • the additional nozzles (6a) are comiected with a water supply and a pump (15) for dosing the acid.
  • the other nozzles (6) are connected with the boiler (13).
  • the door machine is modified by applying the acidic composition through the rinse arm of the door machine. This embodiment is advantageous because it requires less installation than if additional nozzles are added to the rinse arm or if spray nozzles are added to the interior of the door machine. In another preferred embodiment, the door machine if modified by adding spray nozzles to the interior of the door machine. This embodiment is advantageous because it requires less water than when the acidic composition is applied through the rinse arm. In addition to modifying the door machine, the door machine controller will also need to be modified to include the acidic step.
  • the method of the invention may also be used in a pot and pan and a utensil washer.
  • the pot and pan and utensil washer are modified the same as the door machine.
  • a conveyor machine refers to a commercial dish machine, wherein the soiled dishes are placed on a rack that moves through a dish machine on a conveyor.
  • a conveyor machine continuously cleans racks of soiled dishes instead of one rack at a time.
  • the manifolds are typically stationary or oscillating and the rack moves through the machine.
  • a conveyor machine may be a single tank or multi-tank machine.
  • the conveyor machine may include a prewash section.
  • a conveyor machine may be a high temperature or low temperature machine.
  • conveyor machines primarily recirculate the detergent solution.
  • conveyor machines include the Ecolab ES-4400, the Jackson AJ-100, the Stero SCT-44, and the Hobart C-44, and C-66
  • the method of the invention may be used in conjunction with any of the conveyor machines described above.
  • the conveyor machine may need to be modified to accommodate the acidic step.
  • the conveyor machine may be modified by adding spray nozzles for the acidic step between tanks for the alkaline steps.
  • the nozzles for the acidic step are connected to an acidic composition source.
  • the placement of the nozzles in the conveyor machine may be adjusted to provide for the application of the acidic composition at the desired time.
  • the acidic composition may also be applied by running the acid through a wash arm.
  • An undercounter machine refers to a dish machine similar to most consumer dish machines, wherein the dish machine is located underneath a counter and the dishes are cleaned one rack at a time. In an undercounter dish machine, the rack is stationary and the wash/rinse arms are moving. Undercounter machines may be a high temperature or low temperature machine. The undercounter machine may either be a recirculation machine or a dump and fill machine. Some non-limiting examples of undercounter machines include the Ecolab ES-1000, the Jackson JP-24, and the Hobart LX-40H. The method of the invention may be used in conjunction with any of the undercounter machines described above.
  • the undercounter machine may need to be modified to accommodate the acidic step, or the cleaning compositions be modified.
  • the undercounter machine may be modified to discard the washing water between steps and refill with fresh water. In this case the amount of cleaning agent can be lower because less will be needed to achieve the desired pH. When the washing water is not discarded between steps, the amount of cleaning agent necessary will increase because more will be needed to bring the pH to the desired level.
  • the undercounter machine may also be modified by adding additional dosing chambers that may either be time or pressure activated. Consumer dish machine may be modified in a way similar to the undercounter machines. Undercounter and consumer machines are especially suited to use with a tablet. Glasswashers may also be used with the method of the invention.
  • Undercounter glasswashers will be modified like an undercounter dish machine. Bar glass washers that utilize a rotary drive may be modified by incorporating additional spray nozzles and detergent reservoirs for the acid step and the second alkaline step. In addition, the wash cycle may be slowed down to accommodate the method of the invention.
  • a flight machine refers to a commercial dish machine, wherein the soiled dishes are placed on pegs that move through a dish machine on a conveyor. A flight machine continuously cleans soiled dishes and racks are not used. Here the manifolds are typically stationary or oscillating and the conveyor moves through the machine.
  • a flight machine is typically a multi-tank machine. The flight machine may include a prewash section.
  • a flight machine is typically a high temperature machine.
  • flight machines typically recirculate the detergent solution.
  • Some non-limiting examples of flight machines include the Meiko BA Series and the Hobart FT-900.
  • the method of the invention may be used in conjunction with any of the flight machines described above.
  • the flight machine may also need to be modified to accommodate the acidic step.
  • the flight machine may be modified by adding spray nozzles for the acidic step between tanks for the alkaline steps.
  • the nozzles for the acidic step are connected to an acidic composition source.
  • the placement of the nozzles in the flight machine may be adjusted to provide for the application of the acidic composition at the desired time.
  • the acidic composition may also be applied by running the acid through a wash arm.
  • the above described dish machines include dispensers for dispensing the alkaline cleaning agent and the acidic cleaning agent.
  • the dispenser may be selected from a variety of dispensers depending on the physical form of the composition.
  • a liquid composition may be dispensed using a pump, either peristaltic or bellows for example, syringe/plunger injection, gravity feed, siphon feed, aspirators, unit dose, for example using a water soluble packet such as polyvinyl alcohol or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface.
  • the composition may be dispensed using a pump such as a peristaltic or bellows pump, syringe/plunger injection, caulk gun, unit dose, for example, using a water soluble packet such as polyvinyl alcohol or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface.
  • a pump such as a peristaltic or bellows pump, syringe/plunger injection, caulk gun
  • unit dose for example, using a water soluble packet such as polyvinyl alcohol or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface.
  • the composition may be dispensed using a spray, flood, auger, shaker, tablet-type dispenser, unit dose using a water soluble packet such as polyvinyl alcohol or foil pouch, or diffusion through a membrane or permeable surface.
  • the dispenser may also be a dual dispenser in which the alkaline cleaning agent is dispensed on one side, and the acidic cleaning agent is dispensed on the other side. These dispensers may be located in the dish machine, outside of the dish machine, or remote from the dish machine. Finally, a single dispenser may feed one or more dish machines. It is understood that the dish machines described herein may be used in conjunction with the method of the invention. Additionally, the dish machines may be modified as described and used with a different method of cleaning. For example, instead of using the method of the invention in a dish machine modified according to this invention, a different detergent, for example, a special surfactant package, rinse aid, or the like, may be run through the modified dish machine, for example through the additional wash or rinse arms, or spray nozzles.
  • a different detergent for example, a special surfactant package, rinse aid, or the like, may be run through the modified dish machine, for example through the additional wash or rinse arms, or spray nozzles.
  • the first alkaline wash causes the starch soil to swell and partially dissolve.
  • the addition of the acidic composition hydro lyzes the glycosidic linkages and depolymerizes the starch.
  • the second alkaline wash loosens any remaining soil.
  • Corn Starch Soiling Procedure Some of the following examples tested cleaning performance on plates soiled with com starch. To prepare the plates, 30 grams of corn starch and 1 ml of Luconyl black dye were added to 500 grams of water while stirring. The corn starch solution was brought to boiling and then cooled to 75 °C. Approximately 4 grams of the com starch solution was applied to a plate using a brush. The plates were allowed to cure, either overnight, or using an oven. When the plates were cured in an oven, the resulting starch soil was harder than if the plates were cured overnight. Cleaning performance was evaluated visually by examining the amount of gross soils, or heavy black solids, and gray film removed.
  • Example 1 tested the impact on starch removal of an acidic composition versus other non-acidic compositions when used according to the method of the invention.
  • plates were prepared according to the com starch soiling procedure. The plates were put through a cleaning process in a Krefft® single- tank dish machine according to the following method: (1) the plates were cleaned for one minute with a 0.3 wt.% aqueous solution of a standard alkaline detergent (approximately 17 wt.% alkali metal hydroxide, 14 wt.% tripolyphosphate, 1.5 wt.% alkali metal hypochlorite, 1 wt.% alkali silicate, and the remainder water); (2) the plates were then sprayed with one of the six solutions described in Table 2; (3) the sprayed on solution was allowed to sit for 30 seconds; and (4) the alkaline detergent in step (1) was applied again for two minutes.
  • a standard alkaline detergent approximately 17 wt.% alkali metal hydroxide, 14 wt.
  • Table 2 shows that the best cleaning results were achieved in tests 3-5 where a solution of methanesulfonic acid was used as the spray-on solution.
  • Tests 3-5 altered the pH from alkaline to acid and back to alkaline, whereas test 1 used an alkaline composition, test 2 used an enzyme, and test 6 used water. Table 2 also shows that a high acid concentration is not necessary in order to achieve results.
  • an acidic composition of 0.4 wt.% is effective at removing starch when used according to the method described in this invention.
  • Example 2 tested the ability of the method of the invention to perform in a modified door dish machine. For this example, a standard door dish machine (Krefft® Professional Plus) was modified by adding an additional injection point.
  • the dish machine's program was altered from an alkaline cleaning — pause — rinse step to alkaline cleaning — pause — acidic rinse — pause — alkaline cleaning.
  • plates were prepared according to the corn starch soiling procedure.
  • the alkaline detergent used in this example for the first alkaline step and the second alkaline step was 3 g/1 of Perclin Intensive Flussig.
  • the plates were evaluated on a visual scale of 0 to 10 where 0 stands for no visible sign of cleaning and 10 stands for complete removal of soil.
  • Table 3 shows that including an acidic step in the method of the invention is more effective at removing starch than when water is used instead of the acid. Also, Table 3 shows that the method of the invention is effective at removing starch when used in a door dish machine. Tests 1 and 6 used water instead of the acid. When water was used in the long cleaning process (Test 1) and the short, two cycle cleaning process (Test 6), the starch was not effectively removed. Example 3 Example 3 tested the performance of a tablet in a consumer dish machine. A glass tube was filled with six different layers to form the "tablet.” The first layer was 5.3 grams of NaOH. The second layer was a paraffin layer with a melting point from 134 °F (57 °C) to 140 °F (60 °C).
  • the third layer contained 10.0 grams of amidosulfonic acid.
  • the fourth layer was another paraffin layer with a melting point from 124 °F (51 °C) to 127 °F (53 °C).
  • the fifth layer was 1.0 grams of NaOH.
  • the sixth layer contained a paraffin layer with a melting point of 95 °F (35 °C).
  • a polyethylene glycol having a molecular weight of about 8000 can be used to close the tube. This glass tube was placed in a Bosch SMS 2022 household dishwasher such that the polyalkylene glycol layer would dissolve first, and the 5.3 grams of NaOH would dissolve last.
  • the composition of the layers was designed to correspond to the temperature of the dish machine's wash cycle so that as the temperature of the wash cycle changed, the individual layers dissolved in the appropriate sequence to provide an alkaline cleaning step, then an acidic cleaning step, and then an alkaline cleaning step.
  • the machine was run using Program 3 and the program of the machine was not modified.
  • plates were prepared according to the corn starch soiling procedure.
  • the first alkaline cleaning step was at a temperature from about 68 °F (20 °C) to 127 °F (53 °C).
  • the 1.0 gram of NaOH was dissolved in 5.251 liters of water.
  • the pH of the solution was 11 at 68 °F (20 °C) and 10.5 at 127 °F (53 °C).
  • the first alkaline cleaning step lasted approximately seven minutes. During the acidic cleaning step, the temperature ranged from 127 °F (53 °C) to 140 °F (60 °C). The 10 grams of amidosulfonic acid was dissolved in 5.251 liters of water. The pH of the solution was 2. The acidic cleaning step lasted approximately 2 minutes. The second alkaline cleaning step had a temperature from 140 °F (60 °C) to 156 °F (69 °C). The 5.3 grams of NaOH was dissolved in 5.251 ml of water. The pH of the solution was 11 at 140 °F (60 °C) and 10.8 at 156 °F (69 °C). The second alkaline cleaning step lasted approximately 13 minutes.
  • the second alkaline cleaning step was followed by a regular rinse.
  • the performance of the glass tube compositions was tested against Topmat Tab.
  • the plate were evaluated on a visual scale of 0 to 10 where 0 stands for no visible sign of cleaning and 10 stands for complete removal of soil. The results are described in Table 4.
  • Example 4 tested the impact of an acidic composition versus other non-acidic compositions when used according to the method of the invention. For this test, plates were prepared according to the corn starch soiling procedure. The plates were put through a cleaning process in a Hobart AM-14 door dish machine. The cleaning temperature of the AM- 14 machine was 145 °F (63 °C).
  • Table 5 shows that the best cleaning results were achieved in tests 2 and 4 where hydrochloric acid was used.
  • the concentrated NaOH spray (test 5) improved detergent performance from just Solid Power® (tests 1 and 3) but was not nearly as effective as the acid spray (tests 2 and 4).
  • the acid detergent alone (test 7) was less effective than water (test 6).
  • Example 4 shows that the method of the invention is effective at removing starch soils and starch film.
  • Example 5 examined preferred amount of alkaline detergent necessary to achieve the best results. For this test, plates were prepared according to corn starch soiling procedure.
  • the temperature of the cleaning solution was 145 °F.
  • Example 6 shows that an alkaline composition concentration of 1000 ppm (test 1) provided the best results in terms of soil removal. A 500 ppm concentration (test 2) and a 750 ppm concentration (test 3) did not differ significantly.
  • Example 6 Example 6 tested the method of the invention in a low temperature cleaning process. Plates were prepared according to the corn starch soiling procedure. An Ecolab ES 2000 door dish machine was operated in "delime" mode (a continuous wash with no rinse and no drain) at 130 °F (54 °C). A detergent was added manually at the beginning of the wash sequence. The cleaning process used for this example was the following: (1) a 60 second wash; (2) a 30 second pause or acid spray; and (3) a 60 second wash. The acidic composition was manually sprayed on the dishes. Table 7 Impact of Low Temperature Cleaning on Cleaning Performance
  • Example 7 tested the method of the invention in a high temperature dish machine. Plates were prepared according to the com starch soiling procedure. A Hobart AM- 14 door dish machine was operated manually. The temperature ranged from 160-165 °F (71 °C - 74 °C). The cleaning procedure used for the example was the following: (1) a 30 second alkaline wash; (2) a 30 second pause or a 30 second acid spray; and (3) a 30 second alkaline wash. Table 8 Impact of High Temperature Cleaning on Cleaning Performance
  • Tests 3 and 4 using Solid Fusion had better results than tests 1 and 2 using Solid Power.
  • Tests 2 and 4 included the acidic composition.
  • Tests 2 and 4 were cleaner than tests 1 and 3 that did not use the acidic composition.
  • the plates that were cleaned using the high temperature cleaning method were cleaner than the plates cleaned using the low temperature cleaning method.
  • Example 8 Example 8 tested various concentrations of acid to determine the minimum concentration necessary to effectively remove starch. Plates were prepared according to the com starch soiling procedure. The following method was used: (1) 25 second alkaline wash; (2) 30 second pause or acid spray; and (3) 20 second alkaline wash.
  • the test was conducted in a Hobart AM- 14 door dish machine at 160 °F-165 °F (71 °C • 74 °C).
  • Table 9 shows that including an acid in between the alkaline wash steps (tests 3, 4, 5 and 7) is more effective at removing starch than where there is not an acid between the alkaline steps (tests 1, 2, and 6).
  • a 0.05% concentration of sulfamic acid (test 4) is more effective at removing starch than no acid (tests 1, 2, and 6).
  • the 0.10% concentration of the sulfamic acid (test 3, 5, and 7) was more effective at removing the starch soil and the gray film than the 0.05%> concentration sulfamic acid (test 4).
  • Example 9 tested the impact of applying the acidic detergent through a separate wash arm, for example in a flight machine or a conveyor machine, on cleaning performance.
  • plates were prepared according to the com starch soiling procedure. Two Hobart AM- 14 door dish machines were run side by side in order to simulate two sumps and two wash arms. The first AM-14 machine applied a 250 ppm solution of Solid Fusion to the plates at a pH of 10.07.
  • the second AM-14 machine applied a 1000 ppm solution of sulfamic acid to the plates at a pH of 2.20.
  • the following method was used in this example: (1) a 20 second alkaline wash at 150 °F (66 °C); (2) a 20 second acidic wash at 160 °F (71 °C); and (3) a 20 second alkaline wash at 150 °F (66 °C).
  • This example should be compared with Tests 6 and 7 in example 8.
  • test 6 a 250 ppm solution of Solid Fusion was applied to the dishes without an acid spray (control).
  • test 7 a 250 ppm solution of Solid Fusion was applied along with a 1000 ppm solution of sulfamic acid that was sprayed on. the dishes.
  • Example 10 tested the threshold concentration of acid and alkaline detergents necessary to effectively remove starch. For this test, plates were prepared according to the com starch soiling procedure. A Hobart AM-14 door dish machine was used and operated manually. The acid spray was sprayed on the dishes using a spray bottle. The temperature of the solution was 160 °F (71 °C).
  • Table 11 shows that the method of the invention is necessary to achieve effective removal of the starch soil and the gray film.
  • the water control no alkaline, no acid
  • Including only acid and not alkaline 0.10% sulfamic acid
  • Including only an alkaline detergent at a concentration of 125 ppm 3 250 ppm, and 500 ppm, without the acid spray, only provided some gross soil removal but no removal of the gray film. Only when the concentration of the alkaline detergent was increased to 750 ppm was there significant gross soil removal without an acid spray, however, the gray film remained.
  • Table 11 also shows the minimum concentration of alkaline detergent and acidic detergent in order to achieve effective starch removal.
  • An acid concentration of 0.025% provided moderate removal of the gross starch soil as well as partially dissolving the gray film at alkaline concentrations of 125 ppm and 250 ppm . This is an improvement over not including an acid at all, which only provided some gross soil removal and no removal of the gray film.
  • a 0.025% concentration of acid removed the majority of the gross starch soil when the alkaline concentration was increased to 500 ppm. The starch removal increased when the concentration of the acid was increased from 0.025% to 0.05%. The majority of the gross starch soil was removed when the alkaline concentration was 125 ppm. At 125 ppm, the gray film still remained.
  • Example 11 tested a mixture of sulfamic acid and citric acid in the method of the invention.
  • plates were prepared according to the com starch soiling procedure.
  • a Hobart AM-14 door dish machine was used.
  • a 500 ppm solution of Solid Fusion was used as the alkaline detergent.
  • a control was run without an acid against a 0.10% solution of FX-3 and a 0.50% solution of FX-3.
  • the following method was used: (1) 20 second alkaline wash; (2) 20 second pause/acid spray; (3) 20 second alkaline wash.
  • the temperature of the solutions was 160 °F (71 °C).
  • Table 12 shows that the 0.10% solution of FX-3 did not improve cleaning over the control (Test 1 - no acid).
  • the 0.50% solution of FX-3 (Test 3) did improve starch removal over both the control (Test 1) and the 0.10% FX-3 solution (Test 2).
  • Example 12 tested the impact of different acids on cleaning performance. This test was carried out in a Hobart AM-14 door dish machine with a 15 gallon tank. The temperature of the solution was 150 °F (66 °C). The following method was used for this example: (1) 20 second alkaline wash; (2) 20 second acid spray; and (3) 20 second alkaline wash. Table 13 Impact of Different Acids on Cleaning Performance
  • Table 13 shows that tests with sulfamic acid (tests 1, 7, and 9) and urea hydrochloride (Nitech BJS-1) (tests 2, 6, and 10) performed better than tests 3, 4, 5, 8, and 11 where no acid was included with the exception of test 8 where 1000 ppm of Solid Power was used without an acid.
  • the urea hydrochloride in tests 2, 6, and 10 worked better than the sulfamic acid in similar tests (tests 1, 7, and 9).
  • Example 13 tested discoloration or corrosion on aluminum strips caused by citric acid, sulfamic acid, and urea hydrochloride. For this test, 1.0% and 0.1% solutions of citric acid, sulfamic acid, and Vitech BJS-1 were prepared. l"x 3" aluminum strips were placed in a glass jar. The jar was filled approximately 3 A full with the test solution. The jars were then placed in a 180 °F (82 °C) water bath for six hours. Table 14 Impact of Citric Acid, Sulfamic Acid, and Urea Hydrochloride on Corrosion
  • Table 14 shows that the urea hydrochloride, citric acid, and sulfamic acid performed equally at a 0.1%) concentration. However, when the same three acids were increased to 1.0% concentrations, the citric acid provided the least discoloration on the aluminum strips.
  • Example 14 tested the method of the invention on the removal of protein, as well as spotting and filming. Example 14 also tested the impact of various surfactants on cleaning performance. Finally, Example 14 looked at the impact of the method of the invention on redeposition soils. For this example, ten formulas were prepared and tested. The formulas are listed in Table 15.
  • the acid was pumped into the dish machine by a peristaltic pump at a rate of 9 mis per 5 seconds.
  • the 9 mis of acid was diluted in 200 mis of water to achieve an acid concentration of 1100 ppm and a pH of 2.4.
  • the temperature of the wash was 140 °F to 155 °F .
  • the rinse temperature was 180 °F - 195 °F.
  • Table 17 shows the results of Formulas 1-10 after being cleaned according to this example. Table 17 Results of Glass Testing
  • Example 14 shows that the addition of a nonionic and/or a cationic surfactant improves the effectiveness of the acidic composition and the method of the invention.
  • Test 3 included the nonionic surfactant Plurafac N3. The addition of the nonionic surfactant was found to reduce the spotting on the glasses.
  • the spot rating for the control (Test 1 - no acid or surfactant) was 4 for both the milk glasses and the redeposit glasses.
  • the spot rating for just the acid, no surfactant (Test 2) was 3 for the milk glasses and 2 for the redeposit glasses.
  • Test 3 included the nonionic surfactant Pluronic N3.
  • the spot rating in test 3 was 2 for the milk glasses and 2 for the redeposit glasses.
  • Tests 4 and 6 included only a cationic surfactant, Glensurf 42, without acid, at two concentrations.
  • Tests 4 had a protein level of 4 for the milk glasses and 1.5 for the redeposit glasses.
  • Test 6 the more concentrated cationic surfactant, had protein levels of 4 for the milk glasses and 2 for the redeposit glasses.
  • Test 2 included only the acid without the cationic surfactant.
  • Test 2 had protein levels of 4 for the milk glasses and 2 for the redeposit glasses.
  • Example 15 looked at a solid acid product formula to determine if it would dispense evenly enough to be included with the method of the invention.
  • the formula included 54.6 wt.% citric acid, 5.5 wt.% maleic acid, 14.3 wt.% Pluronic N3, 0.695 Glensurf 42, 13.8 pulverized urea, and 11.0 water.
  • the Pluronic N3, water, and Glensurf 42 were heated to approximately 150 °F . Then the citric acid and maleic acid were added. Finally, the urea was added.
  • composition solidified quickly when it cooled.
  • the sample was placed in a Ecolab Distributor 3000 dispenser and dispensed to a 10% concentration. Random samples were pulled at various times where a 10 ml sample wad diluted into 200 mis of water and analyzed for pH. Table 19 describes the results. Table 19 pH of Diluted Solid Acid Samples
  • Tests 1, 2, and 3 showed excellent results. No significant difference was seen between tests 1, 2, and 3 except that test 1 may have been slightly better. Control tests 4, 5, and 6 did not effectively remove either the starch soil or the gray film.
  • Example 17 tested the ability of a modified Jackson 2018 door dish machine to remove starch using the method of the invention.
  • a Jackson 2018 machine was modified by installing four nozzles in the wash chamber. Two nozzles were on the top of the dish machine in the front comers. Those nozzles used 60 ° nozzles. The other nozzles were in the center of the bottom of the dish machine. Those nozzles were 120 ° nozzles. The nozzles were Spraying Systems 1/8 G-SS 1.5W (120°) and 1/8 G-SS 2 (60°).
  • a Rinse Max dispenser commercially available from Ecolab Inc. was used to inject the acid concentrate into a fresh water source that supplies the nozzles at a pumping rate of 82 cc/min.
  • a Dema solenoid was used to control the fresh water flow. All components were 24VAC operated by a single switch that sent power to both the solenoid and the Rinse Max simultaneously. Plates were prepared according to the com starch soiling procedure and cleaned in the modified Jackson 2018 machine using a 500 ppm solution of Solid Fusion as the alkaline detergent. The temperature of the solution was 150 °F. The method used for this example was as follows: (1) 20 second alkaline wash with 500 ppm Solid Fusion; (2) Acid Spray or Pause; (3) 20 second alkaline wash with 500 ppm Solid Fusion. Table 21 Impact of Modified Door Machine on Cleaning Performance Using the Method of the Invention
  • Table 21 shows that the modified door machine is effective at removing starch when using the method of the invention.
  • Test 1 did not include the acid and the starch was not effectively removed.
  • Test 2 did include the acid, but only for a 10 second spray. Some of the gross soil and gray film were removed.
  • Test 3 included the acid for a 20 second spray and removed most of the gross soil and gray film.

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Abstract

Un procédé de lavage pour l'élimination d'amidon consistant à appliquer une composition alcaline sur un plat, puis à appliquer une composition acide sur un plat, et appliquer une seconde composition alcaline sur le plat. Le procédé peut comporter des étapes supplémentaires. Des compositions d'utilisation avec le procédé et des machines lave-vaisselle que l'on peut utiliser avec le procédé.
PCT/US2004/034477 2003-12-18 2004-10-18 Procedes et compositions pour l'elimination d'amidon WO2005068598A1 (fr)

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WO2010102861A1 (fr) 2009-03-12 2010-09-16 Unilever Plc Formulations de polymères colorants
WO2012155986A1 (fr) * 2011-05-19 2012-11-22 Ecolab Inc. Procédé de lavage de vaisselle comprenant une étape de nettoyage basique et une étape de nettoyage acide
WO2012155976A1 (fr) * 2011-05-19 2012-11-22 Ecolab Inc. Procédé de nettoyage pour un lave-vaisselle
CN109759402A (zh) * 2018-12-13 2019-05-17 林伟 一种化学教学实验用多根试管清洗设备

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WO2002100993A1 (fr) * 2001-06-08 2002-12-19 Ecolab Inc. Procede d'epuration destine a l'elimination d'amidon
WO2004052564A1 (fr) * 2002-12-06 2004-06-24 Ecolab Inc. Procede de nettoyage acide pour lavage de vaisselle en machine
US20040194810A1 (en) * 2002-05-31 2004-10-07 Werner Strothoff Methods and compositions for the removal of starch
EP1477552A1 (fr) * 2003-05-13 2004-11-17 Ecolab Inc. Procédé de nettoyage d'articles au moyen d'un lave-vaisselle

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DE3326459A1 (de) * 1983-07-22 1985-01-31 Etol-Werk GmbH & Co KG Chemische Fabrik, 7603 Oppenau Verfahren zur herstellung eines geschirrspuelmittels und vorrichtung zur verarbeitung desselben
WO1992018047A1 (fr) * 1991-04-20 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Procede pour le lavage en machine de vaisselle ordinaire
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EP1477552A1 (fr) * 2003-05-13 2004-11-17 Ecolab Inc. Procédé de nettoyage d'articles au moyen d'un lave-vaisselle

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WO2010102861A1 (fr) 2009-03-12 2010-09-16 Unilever Plc Formulations de polymères colorants
WO2012155986A1 (fr) * 2011-05-19 2012-11-22 Ecolab Inc. Procédé de lavage de vaisselle comprenant une étape de nettoyage basique et une étape de nettoyage acide
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WO2012155976A1 (fr) * 2011-05-19 2012-11-22 Ecolab Inc. Procédé de nettoyage pour un lave-vaisselle
CN103547203A (zh) * 2011-05-19 2014-01-29 艺康股份有限公司 机器清洗餐具的清洁方法
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CN109759402A (zh) * 2018-12-13 2019-05-17 林伟 一种化学教学实验用多根试管清洗设备

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