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WO2010061240A1 - Procédé de formulation d’un produit de nettoyage ou un système de nettoyage de marque à teneur réduite en phosphore - Google Patents

Procédé de formulation d’un produit de nettoyage ou un système de nettoyage de marque à teneur réduite en phosphore Download PDF

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Publication number
WO2010061240A1
WO2010061240A1 PCT/IB2008/054569 IB2008054569W WO2010061240A1 WO 2010061240 A1 WO2010061240 A1 WO 2010061240A1 IB 2008054569 W IB2008054569 W IB 2008054569W WO 2010061240 A1 WO2010061240 A1 WO 2010061240A1
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WIPO (PCT)
Prior art keywords
magnesium
cleaning product
substitute
water
substitute cleaning
Prior art date
Legal status (The legal status 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 status listed.)
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PCT/IB2008/054569
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English (en)
Inventor
Kim R. Smith
Keith E. Olson
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Ecolab Inc
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Ecolab Inc
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Publication date
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Priority to PCT/IB2008/054569 priority Critical patent/WO2010061240A1/fr
Publication of WO2010061240A1 publication Critical patent/WO2010061240A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof

Definitions

  • This invention relates to cleaning products, including ware washing compositions, laundry detergents, hard surface cleaners, rinse aids and other compositions for cleaning hard or soft surfaces.
  • Cleaning products typically contain a large number of carefully chosen ingredients.
  • the individual ingredients normally each serve some specialized function, for example breaking down or solvating soils (e.g., by providing one or both of a source of alkalinity or enzymes), disinfecting, bleaching, preventing color loss, optical brightening, preventing foaming, offsetting the effects of hard water, aiding rinsing or drying, or making the product safer or more pleasant to use.
  • Large-selling cleaning products typically are manufactured and sold under a brand. A single brand is often employed to identify and unify a family of related cleaning products, with appropriate additional text or graphics being added as need be to designate individual family members.
  • a single unifying brand might be employed on powder, liquid, enzyme-containing, bleach-containing and scented product versions of a laundry detergent, with added text or graphics (serving in some instances as a further trademark or service mark) being used to distinguish the various family members.
  • the brand serves to identify one or more of the product source, quality or performance, and assists a consumer or other end-user in repurchasing the desired product, selecting an appropriate new product when improved or altered variants within the brand family appear in a marketplace, or selecting an appropriate substitute product from the same or a different source when for any reason the desired product is not repurchased.
  • Cleaning product formulations sometimes have to be changed, for reasons including changes in raw material cost, raw material availability, regulatory requirements, product performance requirements, or the manner in which a product might be used.
  • the formulation change involves a branded cleaning product, it normally will be necessary to maintain or at least not significantly decrease the product performance characteristics which consumers associate with products sold under the brand name, so as to avoid loss of goodwill for the changed product, for other related products sold under the brand, or even for products manufactured or sold in association with other brands by the same supplier.
  • Considerable effort and testing may be required in order to make some formulation changes, since there usually is a very wide assortment of potential ingredients which might be used to address each desired product performance characteristic, and because ingredients selected to address one product performance characteristic may adversely affect another ingredient or another product performance characteristic.
  • Most cleaning products contain one or more ingredients whose presence offsets the effects of hard water.
  • ingredients include phosphorus-containing and especially phosphate-containing acids (or more commonly salts thereof, including sodium or potassium salts) such as sodium tripolyphosphate (STPP) and sodium etidronate.
  • Other such ingredients include aminocarboxylates (for example, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA) and their salts) and polycarboxylates (for example, polyacrylates, polymethacrylates and olefin/maleic acid copolymers).
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • NTA nitrilotriacetic acid
  • polycarboxylates for example, polyacrylates, polymethacrylates and olefin/maleic acid copolymers.
  • the present invention provides, in one aspect, a method for formulating a cleaning product, which method comprises: (a) manufacturing or selling, in association with a brand, a cleaning product containing sufficient phosphorus-containing compound to provide commercially acceptable cleaning performance when the cleaning product contains or is used with hard water;
  • the invention provides, in another aspect, a method for formulating a cleaning system, which method comprises: (a) manufacturing or selling, in association with a brand, a cleaning product containing sufficient phosphorus-containing compound to provide commercially acceptable cleaning performance when the cleaning product contains or is used with hard water;
  • the disclosed methods enable reduction or elimination of ingredients that may be or may become commercially unacceptable for environmental, cost or other reasons, while substantially preserving or even increasing the cleaning performance levels associated with a branded cleaning product.
  • FIG. 1 is a schematic drawing of a family of branded cleaning products
  • Fig. 2 is a photograph of glasses treated with varying ratios of magnesium oxide to calcite
  • Fig. 3 is a photograph of glasses rinsed with either treated or untreated water
  • Fig. 4 is a photograph of glasses washed with either a chelating agent- free detergent and treated water, or with a conventional detergent and untreated water
  • Fig. 5 is a photograph of glasses washed with either a chelating agent- free detergent, treated water and a rinse aid, or with a conventional detergent, untreated water and a rinse aid
  • Fig. 6 is a photograph of soiled glasses washed with either a chelating agent-free detergent and treated water, or with a conventional detergent and untreated water;
  • Fig. 7 is a photograph of a control glass rinsed using hard water alone and five glasses rinsed using a rinse agent that provided 1:1, 1.5:1, 2:1, 2.5:1, or 3:1 molar ratios of magnesium to calcium.
  • a cleaning product that contains “a” magnesium compound may include “one or more” magnesium compounds.
  • the term “about” modifying the quantity of an ingredient in a composition or mixture or employed in the disclosed methods refers to variations such as may occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term about also encompasses amounts that differ due to different equilibrium conditions for a composition made from a particular initial mixture.
  • antiredeposition agent refers to a compound that helps keep water hardness ions suspended in water instead of depositing or redepositing onto an object being cleaned.
  • brand refers to a name, symbol, logo, slogan, design or other indicia, including trademarks, service marks and portions thereof, whether or not registered, that a potential purchaser or user of a product or service perceives as representing an expected level of quality or performance for products or services manufactured or sold in association with the brand.
  • chelating agent and “sequestrant” refer to a compound that forms a complex (soluble or not) with water hardness ions (e.g., from water already present in a cleaning composition, water added to a cleaning composition, wash water, rinse water, soil or a substrate being cleaned) in a specific molar ratio.
  • water hardness ions e.g., from water already present in a cleaning composition, water added to a cleaning composition, wash water, rinse water, soil or a substrate being cleaned
  • chelating agent and “sequestrant” normally are synonyms, and the term chelating agent will be used to refer to both chelating agents and sequestrants in the remainder of this application.
  • Chelating agents that can form a water soluble complex include acids (or more commonly salts thereof, including sodium or potassium salts) such as sodium tripolyphosphate, EDTA, DTPA, NTA, citric acid, and the like, as well as other materials such as zeolites.
  • the term "free of chelating agent” refers to a composition, mixture, or ingredient that does not contain a chelating agent or to which a chelating agent has not deliberately been added. This term encompasses however the presence of chelating agents as unintended or unavoidable impurities, e.g., through the formulation by a manufacturer or dilution by an end user of a cleaning composition using water containing one or more chelating agents in trace amounts.
  • EDTA metal- EDTA complexes have been found in amounts of 0.52 to 1120 ⁇ g/L in European surface waters, see Oviedo et al., EDTA: the chelating agent under environmental scrutiny, Quimica Nova, 26, 6, Nov/Dec 2003, and the use of such surface waters or similar EDTA-containing surface waters to manufacture or dilute a composition, mixture, or ingredient to which no other chelating agent had been added would still represent a composition, mixture or ingredient free of chelating agent.
  • substantially free of chelating agent refers to a composition, mixture, or ingredient containing less than 0.2 wt. % chelating agent.
  • lacking an effective amount of chelating agent refers to a composition, mixture, or ingredient containing too little chelating agent to affect measurably the hardness of water present in or employed with such composition, mixture or ingredient.
  • cleaning refers to performing or aiding in soil removal, bleaching, microbial population reduction, rinsing, or combination thereof.
  • cleaning product refers to a composition for cleaning hard or soft surfaces, including ware washing compositions, laundry detergents, hard surface cleaners and rinse aids.
  • cleaning system refers to a cleaning product and a water treatment product used together to clean hard or soft surfaces.
  • the cleaning system components may be used contemporaneously, consecutively or combinations thereof.
  • a water treatment product may be used to treat water (e.g., in a water inlet line) which is then combined with the cleaning product and used to clean a hard or soft surface; by employing both the cleaning product and water treatment product at the same time (e.g., by adding both a cleaning product and a water treatment product to a ware wash or laundry cycle, or by applying both to a hard surface); or by using the cleaning product followed by rinsing, before the cleaned surface has had a chance to dry, using water treated with the water treatment product.
  • the term "commercially acceptable cleaning performance” refers generally to the degree of cleanliness, extent of effort, or both that a typical consumer would expect to achieve or expend when using a cleaning product or cleaning system to address a typical soiling condition on a typical substrate. This degree of cleanliness may, depending on the particular cleaning product and particular substrate, correspond to a general absence of visible soils, or to some lesser degree of cleanliness. For example, a shower cleaner or toilet bowl cleaner would be expected by a typical consumer to achieve an absence of visible soils when used on a moderately soiled but relatively new hard surface, but would not be expected to achieve an absence of visible soils when used on an old hard surface which already bears permanent stains such as heavy calcite deposits or iron discoloration.
  • Cleanliness may be evaluated in a variety of ways depending on the particular cleaning product being used (e.g., ware or laundry detergent, rinse aid, hard surface cleaner, vehicular wash or rinse agent, or the like) and the particular hard or soft surface being cleaned (e.g., ware, laundry, fabrics, vehicles, and the like), and normally may be determined using generally agreed industry standard tests or localized variations of such tests. In the absence of such agreed industry standard tests, cleanliness may be evaluated using the test or tests already employed by a manufacturer or seller to evaluate the cleaning performance of its phosphorus- containing cleaning products sold in association with its brand.
  • ware or laundry detergent, rinse aid, hard surface cleaner, vehicular wash or rinse agent, or the like e.g., ware, laundry, fabrics, vehicles, and the like
  • the term "comparable cleaning performance” refers generally to achievement by a substitute cleaning product or substitute cleaning system of generally the same degree (or at least not a significantly lesser degree) of cleanliness or with generally the same expenditure (or at least not a significantly lesser expenditure) of effort, or both, when using the substitute cleaning product or substitute cleaning system rather than a branded phosphorus-containing cleaning to address a typical soiling condition on a typical substrate.
  • This degree of cleanliness may, depending on the particular cleaning product and particular substrate, correspond to a general absence of visible soils, or to some lesser degree of cleanliness, as explained in the prior paragraph.
  • hard surface refers to a non-resilient cleanable substrate, for example materials made from ceramic, stone, glass or hard plastics including showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, walls, wooden or tile floors, patient-care equipment (for example diagnostic equipment, shunts, body scopes, wheel chairs, bed frames, etc.), surgical equipment and the like.
  • the term "improved cleaning performance” refers generally to achievement by a substitute cleaning product or substitute cleaning system of a generally greater degree of cleanliness or with generally a reduced expenditure of effort, or both, when using the substitute cleaning product or substitute cleaning system rather than a branded phosphorus-containing cleaning product to address a typical soiling condition on a typical substrate. This degree of cleanliness may, depending on the particular cleaning product and particular substrate, correspond to a general absence of visible soils, or to some lesser degree of cleanliness, as explained above. [0030] The term "in association with” refers to use on a product or service, on product packaging, or in product or service advertizing or instructions.
  • phosphorus -free refers to a composition, mixture, or ingredients that do not contain phosphorus-containing compounds or to which phosphorus or phosphorus-containing compounds have not deliberately been added. This term encompasses however the presence of phosphorus-containing compounds as unintended or unavoidable impurities, e.g., through the formulation by a manufacturer or dilution by an end user of a cleaning composition using water containing trace amounts of phosphorus -containing compounds.
  • substantially free of phosphorus refers to a composition, mixture, or ingredients containing less than 0.2 wt.
  • % phosphorus-containing compounds % phosphorus-containing compounds.
  • lacking an effective amount of phosphorus refers to a composition, mixture, or ingredients containing too little phosphorus-containing compounds to affect measurably the hardness of water present in or employed with such composition, mixture or ingredient.
  • phosphate-free and substantially free of phosphate are defined similarly, with “phosphate” being substituted for ""phosphorus" in the above definitions.
  • the term "soft surface” refers to a resilient cleanable substrate, for example materials made from woven, nonwoven or knit textiles, leather, rubber or flexible plastics including fabrics (for example surgical garments, draperies, bed linens, bandages, etc.), carpet, transportation vehicle seating and interior components and the like.
  • solid refers to a composition in a generally shape-stable form under expected storage conditions, for example a powder, particle, agglomerate, flake, granule, pellet, tablet, lozenge, puck, briquette, brick or block, and whether in a unit dose or a portion from which measured unit doses may be withdrawn.
  • a solid may have varying degrees of shape stability, but typically will not flow perceptibly and will substantially retain its shape under moderate stress, pressure or mere gravity, as for example, when a molded solid is removed from a mold, when an extruded solid exits an extruder, and the like.
  • a solid may have varying degrees of surface hardness, and for example may range from that of a fused solid block whose surface is relatively dense and hard, resembling concrete, to a consistency characterized as being malleable and sponge-like, resembling a cured caulking material.
  • substitute cleaning product refers to a product that is intended to be or may be used in place of a cleaning product containing a phosphorus-containing compound.
  • threshold agent refers to a compound that inhibits or alters crystallization of water hardness ions from solution, but that need not form a specific complex with the water hardness ion and thereby may be distinguished from a chelating agent.
  • Threshold agents include polycarboxylates, for example polymers and copolymers of acrylic acid, methacrylic acid, maleic acid and olefins.
  • free of threshold agent refers to a composition, mixture, or ingredient that does not contain a threshold agent or to which a threshold agent has not deliberately been added.
  • threshold agents as unintended or unavoidable impurities, e.g., through the formulation by a manufacturer or dilution by an end user of a cleaning composition using water containing one or more threshold agents in trace amount, and the use of such water to manufacture or dilute a composition, mixture, or ingredient to which no other threshold agent had been added would still represent a composition, mixture or ingredient free of threshold agent.
  • substantially free of threshold agent refers to a composition, mixture, or ingredient containing less than 0.2 wt. % threshold agent.
  • the term "lacking an effective amount of threshold agent” refers to a composition, mixture, or ingredient containing too little threshold agent to inhibit measurably the precipitation of water hardness present in or employed with such composition, mixture or ingredient.
  • ware refers to items used for cooking or eating, for example pots, pans, cooking utensils, plates, cups, glasses and eating utensils.
  • warewashing refers to washing, rinsing or otherwise cleaning ware.
  • water soluble refers to a compound that can be dissolved in water at a concentration of more than 1 wt. %.
  • sparingly soluble or “sparingly water soluble” refer to a compound that can be dissolved in water only to a concentration of 0.1 to 1.0 wt. %.
  • water insoluble refers to a compound that can be dissolved in water only to a concentration of less than 0.1 wt. %.
  • Fig. 1 shows a family 100 of cleaning products sold under a unifying brand (in this case, APEXTM as well as the additional unifying brand ECOLABTM, both from Ecolab, Inc.,).
  • the family includes a solid detergent block 102 sold under the trademark APEX POWER, a solid detergent block 104 sold under the trademark APEX POWER PLUS, a solid detergent block 106 sold under the trademark APEX ULTRA, a solid detergent block 108 sold under the trademark APEX METAL PROTECTION, a solid presoaking detergent block 110 sold under the trademark APEX PRESOAK and a solid manual detergent block 112 sold under the trademark APEX MANUAL DETERGENT.
  • the various family members share similar labels and other trade dress, and provide at least a minimum level of expected cleaning performance for members manufactured or sold as a part of the brand family.
  • Block 102 includes a shaped solid detergent portion 114 surrounded by wrapping 116 (shown partially cut away) made of plastic, paper or other suitable material.
  • Label 118 provides a place on which the brands 120, 122 may be printed together with a further trademark designation 124 and information for consumers (for example, graphical indicia 126 or text) concerning the manner in which block 102 may be stored and used.
  • Weakened tear line or fracture line 128 incorporated in wrapping 116 facilitates removal of detergent 114 from wrapping 116.
  • Block 102 may be shaped into any suitable profile using casting, extrusion or other suitable shaping techniques.
  • Block 102 (and blocks 104 through 110) may for example have a generally elliptical profile with a pinched waist portion 130 whose shape desirably matches that of a corresponding receptacle in a suitable dispenser (not shown in Fig. 1).
  • Detergent 112 has a sufficiently different shape to reduce the likelihood that detergent 112 will inadvertently be placed in the dispenser intended for detergents 102 through 110, and may be mated with its own unique dispenser (also not shown in Fig. 1).
  • a variety of dispensers and a variety of detergent shapes may be employed for cleaning products such as detergents 102 through 112, for example those shown in U.S. Patent Nos. 4,687,121, 4,826,661, 5,086,952, 5,389,344, 6,143,257 and 6,489,278.
  • the disclosed methods may be used to formulate a wide variety of substitute cleaning products that are free of or substantially free of phosphorus- containing compounds and especially phosphate-containing compounds (or more commonly salts thereof, including sodium or potassium salts) such as sodium tripolyphosphate (STPP) and sodium etidronate.
  • phosphate-containing compounds or more commonly salts thereof, including sodium or potassium salts
  • STPP sodium tripolyphosphate
  • STPP sodium tripolyphosphate
  • etidronate sodium tripolyphosphate
  • additional chelating agents have undesirable environmental disadvantages (e.g., phosphates) or high cost, and their role may safely, effectively or inexpensively be replaced by the disclosed magnesium compounds.
  • Zeolites capable of complexing calcium salts without complexing magnesium compounds may be retained if desired. However, zeolites desirably are also reduced, substantially eliminated or eliminated to the extent their role may effectively or inexpensively be replaced by the disclosed magnesium compounds.
  • Other cleaning product ingredients that are sometimes used together with phosphorus-containing compounds and whose use may also be reduced, substantially eliminated or eliminated include chelating agents, threshold agents, or both chelating agents and threshold agents. It generally will be desirable to reduce, substantially eliminate or eliminate such chelating agents and threshold agents because their presence may compromise the performance of the magnesium compound, and they may effectively and inexpensively be replaced by the magnesium compound.
  • Representative aminocarboxylates include acids (or more commonly salts thereof, including sodium or potassium salts) such as EDTA, DTPA, NTA, methylglycinediacetic acid trisodium salt (MGDA), 1,3- diaminopropanetetraacetic acid (1,3-PDTA), 2-hydroxyethyliminodiacetic acid disodium salt (HEIDA), ethylene diamine disuccinic acid trisodium salt (EDDS), tetrasodium iminodisuccinate, tetrasodium 3-hydroxy-2,2'-iminodisuccinate (HIDS) and tetrasodium glutamate diacetate.
  • acids or more commonly salts thereof, including sodium or potassium salts
  • aminocarboxylates include various DISSOL VINETM chelating agents from Akzo Nobel Functional Chemicals bv; BAYPURETM and TRILONTM chelating agents from BASF; VERSENETM, VERSENEXTM and VERSENOLTM chelating agents from Dow Chemical Company; OCTA QUESTTM chelating agents from Octel Performance Chemicals and HIDS chelating agent from Nippon Shokubai.
  • Other chelating agents whose use may also be reduced, substantially eliminated or eliminated include sodium citrate and sodium gluconate.
  • Representative polycarboxylates include acrylate, methacrylate and olefin/maleic acid polymers and copolymers.
  • Other threshold agents whose use may also be reduced, substantially eliminated or eliminated include polyethers, polyethylenimines, polyvinylpyrrolidones, vinly imidazoles and naphthalene sulfonic acid-formaldehyde condensation products.
  • Exemplary polycarboxylates and additional threshold agents include the SOKALANTM, TAMOLTM and LUPASOLTM polymers available from BASF; GANTREZTM polymers from ISP Performance Chemicals and ACUSOLTM polymers from Rohm & Haas.
  • a variety of magnesium compounds may be employed in the disclosed method.
  • the magnesium compound may offset the effect of solubilized water hardness ions (e.g., Ca ++ ions) and prevent lime scale (calcite) formation.
  • the magnesium compound may be water soluble or water insoluble, and may be inorganic or organic.
  • Exemplary water soluble magnesium compounds include magnesium acetate, magnesium benzoate, magnesium bromide, magnesium bromate, magnesium chlorate, magnesium chloride, magnesium citrate, magnesium formate, magnesium hexafluorosilicate, magnesium iodate, magnesium iodide, magnesium lactate, magnesium molybdate, magnesium nitrate, magnesium perchlorate, magnesium phosphinate, magnesium salicylate, magnesium sulfate, magnesium sulfite, magnesium tartrate, magnesium thiosulfate and mixture thereof.
  • Exemplary water insoluble magnesium compounds include magnesium carbonate, magnesium chromate, magnesium hydroxide and magnesium oxide.
  • Magnesium chloride may be preferred for cleaning products in which clarity is important.
  • Magnesium sulphate may be preferred for cleaning products in which exposure to metals and the avoidance of corrosion are important.
  • a water insoluble magnesium compound may advantageously be combined with a water soluble magnesium compound (for example, at a ratio of water soluble to water insoluble magnesium compound of about 1:10 to about 10:1, about 1:5 to about 5:1, or about 1:3 to about 3:1) to slow the speed at which the water soluble magnesium compound dissolves.
  • Magnesium compounds in the form of magnesium salts may be employed, and may be provided as hydrated salts or anhydrous salts.
  • An exemplary subclass of magnesium compounds includes magnesium salts with an anion that also forms a soluble salt with calcium.
  • Exemplary such salts include magnesium acetate, magnesium benzoate, magnesium bromide, magnesium bromate, magnesium chlorate, magnesium chloride, magnesium formate, magnesium iodide, magnesium lactate, magnesium nitrate, magnesium perchlorate, magnesium phosphinate, magnesium salicylate and mixtures thereof.
  • Another exemplary subclass of magnesium compounds includes those approved as Generally Recognized As Safe (GRAS) for direct food contact, including magnesium chloride and magnesium sulfate.
  • GRAS Generally Recognized As Safe
  • the disclosed methods employ sufficient magnesium compound to provide comparable or improved cleaning performance when the substitute cleaning product contains or is used with hard water.
  • the magnesium compound amount may vary based on factors including the expected source water hardness and expected ratio of magnesium to calcium in such source water, the presence or absence of other substances in the water, in the cleaning product or in a companion product which might be used together with the cleaning product (e.g., substances including chelating agents, threshold agents and other ingredients which might complex, consume or otherwise compromise the performance of the magnesium compound and which may be present in trace or deliberately increased amounts), the cleaning task or tasks to be performed and the site in which they will be performed, and on the chosen magnesium compound and its degree of hydration if any.
  • a water soluble magnesium compound desirably is present in an amount sufficient to provide a 1 : 1 or greater molar ratio of magnesium ions to calcium ions at the cleaning site, for example Mg: Ca molar ratios greater than or equal to 1:1, 1.2, 1.3, 1.4, 1.5 or 2.0.
  • the Mg:Ca molar ratio may for example also be less than or equal to 5:1, 4:1 or 3:1.
  • Mg:Ca molar ratios between about 2:1 and 3:1 will provide very desirable results. Ratios above 3:1 and even above 5:1 may also provide very desirable results, but may represent a waste of superfluous magnesium compound.
  • a water insoluble magnesium compound may for example be about 1 to about 50 wt. % of a solid cleaning compound.
  • the expected source water hardness, expected ratio of magnesium to calcium in such source water, chosen magnesium compound and its degree of hydration if any are of particular interest when selecting a magnesium compound amount.
  • magnesium chloride hexahydrate MgCl 2 -OH 2 O, M.W. 203.3
  • the following amounts of the hydrated salt may be employed to obtain a 2:1 Mg:Ca molar ratio at the cleaning site:
  • the amounts shown above may readily be adjusted for other source water Mg:Ca molar ratios, source water hardness levels, magnesium compounds, degrees of hydration, and target Mg:Ca ratios at the cleaning site.
  • the magnesium compound may be incorporated into the substitute cleaning compound, employed in a water treatment product, or both. Further details regarding use of the magnesium compound in a cleaning product may be found in the above-mentioned U.S. Patent Application Serial Number 12/114,327 filed May 2, 2008, and in U.S. Patent Application Serial Number 12/114,486, filed May 2, 2008 and entitled "Cleaning Compositions with Water Insoluble Conversion Agents and Methods of Making and Using Them". Further details regarding use of the magnesium compound in a water treatment product may be found, for example, in U.S. Patent Application Serial Number 12/114,448, filed May 2, 2008 and entitled "Water Treatment System and Downstream Cleaning Methods".
  • the disclosed substitute cleaning product or cleaning system may be manufactured, packaged or sold forms in a variety of forms including liquids, gels and solids, and in ready-to-use (RTU) or concentrated forms intended to be diluted with water prior to use.
  • the substitute cleaning product or cleaning system may include a variety of ingredients which serve to maintain or improve cleaning performance, including sources of alkalinity, surfactants or surfactant systems (including anionic, nonionic, cationic and zwitterionic surfactants and surfactant systems), pH modifiers (e.g., organic or inorganic sources of alkalinity or pH buffering agents), builders (e.g., inorganic builders such as silicates, carbonates, sulfates, salts or acid forms thereof), processing aids, active oxygen compounds, glass or metal corrosion inhibitors, activators, rinse aids, functional materials, bleaching agents, defoaming agents, anti- redeposition agents, stabilizing agents, enzymes, detersive polymers, softeners, sources of acidity,
  • Additional adjuvants include antimicrobial agents, secondary hardening (viz-, solidification) agents, detergent fillers, aesthetic enhancing agents (e.g., dyes, odorants and perfumes), lubricants, dispersants and preservatives.
  • antimicrobial agents include antimicrobial agents, secondary hardening (viz-, solidification) agents, detergent fillers, aesthetic enhancing agents (e.g
  • the substitute cleaning product or cleaning system desirably has one or more of the following product attributes, including being free of phosphorus, free of NTA, useable in a pH range of about 9-13, effective in less than 3 minutes after the start of use, stable when formulated with soda ash or sodium hydroxide whether in liquid, gel or solid formulations, low in toxicity (including low in aquatic toxicity, biodegradable, and in compliance with all current and announced regulatory requirements in the country or region of sale.
  • the substitute cleaning product or cleaning system may also contain or be mixed with water.
  • the water may be treated, untreated or softened water including municipal or well water, deionized water, distilled water or water in any other suitable form. Water may represent for example at least 5 wt.
  • Water may for example also represent less than 80 wt. %, less than 70 wt. %. less than 60 wt. %, less than 55 wt. %, less than 50 wt. %, less than 40 wt. %, less than 30 wt. % or less than 20 wt. % of the substitute cleaning product, cleaning system or diluted solution thereof.
  • the substitute cleaning product or cleaning system may also be substantially water-free, for example in solid form.
  • RTU or diluted use solutions of the substitute cleaning composition or cleaning system may be clear, translucent or opaque, may be homogenous or may have more than one phase, and may be solutions, dispersions or emulsions. Diluted use solutions may for example be made at concentrate: water ratios of about 1:500 - 1:10, or about 1:250 - 1:1.
  • the desired use concentration may for example vary somewhat depending on the desired application method (manual spray, soak, washing machine, instrument washer, etc.).
  • the substitute cleaning composition or cleaning system desirably retains such solid form when exposed to elevated temperatures, e.g., temperatures of up to about 38° C or up to about 50° C.
  • the substitute cleaning composition and cleaning system may be used on a variety of hard and soft surfaces including those mentioned above and other surfaces including food-related surfaces, health care surfaces and transportation surfaces.
  • Exemplary food-related surfaces include production, processing, cooking and serving surfaces.
  • Exemplary health care surfaces include surfaces employed as part of a health care activity (including human and animal care), for example surfaces of instruments, devices, carts, cages, furniture, structures, buildings and the like.
  • Exemplary transportation surfaces include vehicles, service facilities, wash facilities and the like.
  • Example 1 Water Treatment using Low Water Solubility Magnesium Media
  • a Hobart AM- 14 automatic ware washing machine was supplied with water having 17 grains hardness in its untreated state.
  • the water was optionally passed through a treatment tank containing magnesium oxide but no calcite.
  • the untreated or treated water was supplied directly to the machine sump so that it would affect both the wash and rinse cycles. No detergent or rinse aid was employed.
  • drinking glasses washed with untreated or treated water were evaluated for spotting and filming.
  • the washed glasses are shown in Fig. 3.
  • the glass washed with water treated in the MgO bed exhibited little or no spotting, whereas the glass washed with untreated water exhibited substantial filming and spotting.
  • APEX POWERTM a branded product manufactured and sold to the institutional cleaning market by Ecolab Inc.
  • the APEX POWER detergent contained about 7% tripolyphosphate and about 16% phosphonate chelants.
  • the detergent was added to the ware washing machine in an amount sufficient to provide about 1000 ppm detergent in the wash cycle, and was used with untreated water and a standard rinse aid (RINSE-DRYTM, from Ecolab, Inc.) added after the wash cycle.
  • the second detergent was a substitute formulation completely free of chelating agents and containing 32 parts NaOH, 35 parts RU SILICATETM sodium silicate (available from Philadelphia Quartz), 1 part poly ether siloxane, 2 parts PLURONICTM N3 ethylene oxide/propylene oxide block copolymer (a nonionic surfactant and rinse aid available from BASF), 1 part of a nonionic defoaming agent, 10 parts soda ash, 12 parts sodium sulfate, 1 part sodium metasilicate and 6 parts water.
  • the chelating agent-free substitute formulation was added to the warewashing machine in an amount sufficient to provide about 650 ppm detergent in the wash cycle, and was used with treated water and without additional rinse aid. The glasses were washed for 100 cycles.
  • the washed glasses are shown in Fig. 4 after completion of the 100 cycle test.
  • the glass washed using the substitute formulation and treated water exhibited significantly less filming and spotting than the glass washed with the APEX POWER detergent, untreated water and a rinse aid.
  • the inside of the ware washing machine employing the substitute formulation and treated water had a much cleaner appearance, with no visible scale, compared to the ware washing machine employing the APEX POWER detergent, untreated water and a rinse aid.
  • the fourth experiment was repeated but about 2.33 mL of the rinse aid was added after each wash cycle for both detergents.
  • the washed glasses are shown in Fig. 5 after 100 wash cycles.
  • both glasses had an improved visual appearance.
  • the glass washed using the substitute formulation, treated water and the rinse aid had substantially less spotting and filming than the glass washed with APEX POWER detergent, untreated water and the rinse aid.
  • drinking glasses were soiled by dipping them in whole milk, drying the glasses, then washing them in wash water containing 2,000 ppm of a synthetic soil made from a mixture of milk, starch and grease.
  • the wash water also contained either APEX POWER detergent and untreated water, or the substitute formulation and treated water.
  • APEX POWER detergent and untreated water or the substitute formulation and treated water.
  • a rinse aid was added after the wash cycle.
  • the glasses were dipped in milk and dried between each cleaning cycle, and fresh synthetic soil was added to the next wash water cycle. These steps were repeated for 10 cycles in all.
  • the washed glasses are shown in Fig. 6.
  • the glasses washed with the substitute formulation and treated water had significantly less spotting and filming than those washed using APEX POWER detergent and untreated water.
  • the latter glasses also had a slightly bluish tint, whereas those washed using the substitute formulation and treated water had no visual blue spotting.
  • Glass C is a control glass (from the first experiment) washed and rinsed using hard water alone.
  • the remaining glasses are from the third experiment and are labeled to show the molar ratio of magnesium to calcium. These ratios are based on the total amount of magnesium present including that present in the incoming water.
  • Glass C has a severely clouded appearance, and looks like it had been frosted or etched.
  • Glass 1:1 is even cloudier or more frosted than glass C.
  • Glasses 1.5:1 through glass 3:1 are increasingly clearer in appearance than the previous (lower ratio) glasses.
  • Glass 3:1 has substantially no filming, spotting, cloudiness, or etched appearance and looked essentially like a brand new glass.
  • Example 2 experiments indicate that a cleaning system employing the Example 1 substitute formulation could be manufactured and sold under the APEX POWER brand for use with untreated water (viz-, without the disclosed magnesium compound water treatment) and with a rinse aid containing a water- soluble magnesium compound, to provide at least comparable and likely improved cleaning performance compared to that obtained using APEX POWER detergent and untreated water.
  • the Example 1 and Example 2 experiments also indicate that the Example 1 substitute formulation could be further altered to provide a further substitute cleaning product which could be used with treated or untreated water, by including about 5 to about 50 wt. % of a water soluble magnesium compound (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness).
  • Limonene [0069] The Table 3 ingredients are believed to be listed in descending order from the largest to the smallest concentrations. Some ingredients (e.g., perfume and colorant) appear more than once due in all likelihood to the use of different types of each of these ingredients.
  • a substitute cleaning product could be formulated by reducing or eliminating the tetrasodium etidronate, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation could contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride or magnesium sulfate.
  • the amounts of one or more and preferably each of the sodium acrylic acid/methacrylic acid copolymer, citric acid, trisodium ethylenediamine disuccinate and sodium polyacrylate desirably also would be reduced or eliminated, as they may otherwise compromise the performance of the added magnesium compound.
  • the sodium silicoaluminate (Zeolite) could be left in the formulation if it does not complex magnesium ions, but desirably would also be reduced or eliminated since its function could effectively and inexpensively be performed by the added magnesium compound.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus -containing compound, preferably laundry detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the ARIEL brand without loss of brand value.
  • Example 4 Substitute Powdered Laundry Detergent Formulations
  • BOLDTM 2inl Crushed Silk & Jasmine laundry detergent powder is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain the ingredients shown in Table 4:
  • the Table 4 ingredients are believed to be listed in descending concentration order as was done for the ingredients in Table 3.
  • Sodium dodecylbenzenesulfonate is listed more than once, due possibly to an error or because it may have been added in more than one form or at different stages during manufacture of the cleaning product.
  • the formulation also includes some magnesium sulfate, believed to be present in order to substitute for sodium ion in the surfactant sodium dodecylbenzenesulfonate and thereby alter the surfactant performance or solution characteristics.
  • a substitute cleaning product could be formulated by reducing or eliminating the tetrasodium etidronate and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride or magnesium sulfate (in the case of magnesium sulfate, beyond the amount already present).
  • the amounts of one or more and preferably each of the sodium acrylic acid/methacrylic acid copolymer, citric acid, trisodium ethylenediamine disuccinate and sodium polyacrylate desirably also would be reduced or eliminated, as they may otherwise compromise the performance of the added magnesium compound.
  • the sodium silicoaluminate (Zeolite) could be left in the formulation if it does not complex magnesium ions, but desirably would also be reduced or eliminated since its function could effectively and inexpensively be performed by the added magnesium compound.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus -containing compound, preferably laundry detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the BOLD brand without loss of brand value.
  • ARIELTM Color & Style liquid laundry detergent is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain the ingredients shown in Table 5:
  • a substitute cleaning product could be formulated by reducing or eliminating the sodium diethylenetriamine pentamethylene phosphonate, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus -containing compound, preferably laundry detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the ARIEL brand without loss of brand value.
  • BOLDTM Apple Blossom Lime Zest liquid laundry detergent is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain ingredients similar but not in all cases identical to those used in the ARIEL product, including sodium citrate and sodium diethylenetriamine pentamethylene phosphonate.
  • a substitute cleaning product could be formulated by reducing or eliminating the sodium diethylenetriamine pentamethylene phosphonate and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the sodium citrate desirably also would be reduced or eliminated, as it may otherwise compromise the performance of the added magnesium compound.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus-containing compound, preferably laundry detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the BOLD brand without loss of brand value.
  • FAIRYTM Active Burst Lemon dishwashing detergent powder is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain the ingredients shown in Table 6:
  • a substitute cleaning product could be formulated by reducing or eliminating the pentasodium triphosphonate, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride (where optimal clarity is desired) or magnesium sulfate (where clarity is of lesser concern and where the added amount is in addition to the amount already present).
  • the acrylic/sulphonic copolymer desirably also would be reduced or eliminated, as it is expensive and may compromise the performance of the added magnesium compound.
  • the resulting substitute formulations should provide dishwashing detergents containing less phosphorus, preferably dishwashing detergents that are free of or substantially free of phosphorus, and most preferably dishwashing detergents that are free of or substantially free of phosphorus, chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the FAIRY brand without loss of brand value.
  • Example 7 Substitute Liquitab Dishwashing Formulations
  • FAIRYTM Non-Bio Liquitabs dishwashing detergent is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain the ingredients shown in Table 7:
  • the Table 7 ingredients are believed to be listed in descending concentration order as was done for the ingredients in Table 3.
  • the formulation includes some magnesium chloride, believed to be present in order to substitute for sodium ion in the surfactant sodium dodecylbenzenesulfonate and thereby alter the surfactant performance or solution characteristics.
  • a substitute cleaning product could be formulated by reducing or eliminating the disodium etidronate and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride or magnesium sulfate (in the case of magnesium chloride, beyond the amount already present).
  • the sodium citrate desirably also would be reduced or eliminated, as it may otherwise compromise the performance of the added magnesium compound.
  • the resulting substitute formulations should provide dishwashing detergents containing less phosphorus-containing compound, preferably dishwashing detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably dishwashing detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the FAIRY brand without loss of brand value.
  • ARIELTM Regular/Biological Liquitabs dishwashing detergent is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain ingredients similar but not in all cases identical to those used in the FAIRY product, including MEA-dodecylbenzenesulfonate, disodium etidronate, sodium citrate and magnesium chloride.
  • a substitute cleaning product could be formulated by reducing or eliminating the disodium etidronate and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the sodium citrate desirably also would be reduced or eliminated, as it may otherwise compromise the performance of the added magnesium compound.
  • the resulting substitute formulations should provide dishwashing detergents containing less phosphorus-containing compound, preferably dishwashing detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably dishwashing detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the ARIEL brand without loss of brand value.
  • PERSILTM Gel Tablets Bio laundry detergent is said by its U.K. supplier (Unilever, see http :// www . unile v er. com/PIQTI/HN/P 1. asp) to contain ingredients having the functions shown in Table 8:
  • a substitute cleaning product could be formulated by reducing or eliminating either and preferably both of the pentasodium triphosphate and ethylene diamine tetra methylene phosphonic acid Ca/Na salt, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt.
  • a water soluble magnesium compound such as magnesium chloride or magnesium sulfate.
  • the amounts of one or more and preferably each of the sodium citrate, sodium acrylic acid/methacrylic acid copolymer and sodium polyacrylate desirably also would be reduced or eliminated, as they may otherwise compromise the performance of the added magnesium compound.
  • the sodium silicoaluminate (Zeolite) could be left in the formulation if it does not complex magnesium ions, but desirably would also be reduced or eliminated since its function could effectively and inexpensively be performed by the added magnesium compound.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus-containing compound, preferably laundry detergents that are free of or substantially free of phosphorus -containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the PERSIL brand without loss of brand value.
  • Example 9 Substitute Powdered Laundry Detergent Formulations
  • PERSILTM Universal-Pulver laundry detergent powder is said by its German supplier (Henkel AG & Co.) to contain the ingredients shown in Table 9: Table 9
  • a substitute cleaning product could be formulated by reducing or eliminating the tetrasodium etidronate, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride or magnesium sulfate.
  • the sodium acrylic acid/methacrylic acid copolymer desirably also would be reduced or eliminated, as it may otherwise compromise the performance of the added magnesium compound.
  • the Zeolite could be left in the formulation if it does not complex magnesium ions, but desirably would also be reduced or eliminated since its function could effectively and inexpensively be performed by the added magnesium compound.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus -containing compound, preferably laundry detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the PERSIL brand without loss of brand value.
  • a substitute cleaning product could be formulated by reducing or eliminating either or preferably both of the tetrasodium etidronate and ethylenediaminetetramethylene phosphonic acid Ca/Na salt, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt.
  • a water soluble magnesium compound such as magnesium chloride or magnesium sulfate.
  • the amounts of one or more and preferably each of the citric acid, sodium acrylic acid/methacrylic acid copolymer and sodium polyacrylate desirably also would be reduced or eliminated, as they may otherwise compromise the performance of the added magnesium compound.
  • the sodium silicoaluminate (Zeolite) could be left in the formulation if it does not complex magnesium ions, but desirably would also be reduced or eliminated since its function could effectively and inexpensively be performed by the added magnesium compound.
  • the resulting substitute formulations should provide laundry detergents containing less phosphorus -containing compound, preferably laundry detergents that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry detergents that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the PERSIL brand without loss of brand value.
  • DOVETM Cream Bar hand soap is said by its U.K. supplier (Unilever, see http ://www .unilev cr.com/1'IOTI/EN/P 1. asp) to contain ingredients having the functions shown in Table 11 :
  • a substitute cleaning product could be formulated by reducing or eliminating the tetrasodium etidronate, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride or magnesium sulfate.
  • the amounts of either and preferably both of the citric acid and tetrasodium EDTA desirably also would be reduced or eliminated, as they may otherwise compromise the performance of the added magnesium compound.
  • the sodium lauroyl isethionate and sodium isethionate are both lime scale dispersants which could be left in the formulation, reduced in amount or removed, as they may no longer be needed.
  • the resulting substitute formulations should provide hand soaps containing less phosphorus-containing compound, preferably hand soaps that are free of or substantially free of phosphorus-containing compounds, and most preferably hand soaps that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the DOVE brand without loss of brand value.
  • ACETM Gentle Stain Remover laundry stain remover is said by its manufacturer (Proctor & Gamble Co., see www.scienceinthebox.com) to contain the ingredients shown in Table 12: Table 12
  • a substitute cleaning product could be formulated by reducing or eliminating the dipotassium etidronate, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride (where optimal clarity is desired) or magnesium sulfate (where clarity is of lesser concern).
  • the resulting substitute formulations should provide laundry stain removers containing less phosphorus-containing compound, preferably laundry stain removers that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry stain removers that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the ACE brand without loss of brand value.
  • Example 13
  • a substitute cleaning product could be formulated by reducing or eliminating the complex sodium polyphosphates, and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt. % (measured on an anhydrous basis, with the desired amount depending in part on the expected water hardness) of a water soluble magnesium compound such as magnesium chloride or magnesium sulfate.
  • the resulting substitute formulations should provide dishwasher detergents containing less phosphorus-containing compound, preferably laundry stain removers that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry stain removers that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the CASCADE brand without loss of brand value.
  • dishwasher detergents containing less phosphorus-containing compound preferably laundry stain removers that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry stain removers that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the CASCADE brand without loss of brand value.
  • a professional version in the same brand family is available as
  • a substitute cleaning product could be formulated by reducing or eliminating the phosphate-containing compound(s), and adding to the formulation sufficient water soluble magnesium compound to overcome the presence of water hardness ions in water used to manufacture or used with such substitute cleaning product.
  • the substitute formulation may contain about 2 to about 50 wt. %, about 5 to about 40 wt. % or about 11 to about 30 wt.
  • the resulting substitute formulations should provide dishwasher detergents containing less phosphate-containing compound, preferably laundry stain removers that are free of or substantially free of phosphorus-containing compounds, and most preferably laundry stain removers that are free of or substantially free of chelating agents and threshold agents, while providing comparable or improved cleaning performance sufficient to enable the manufacture or sale of the substitute cleaning product under the CASCADE brand in the professional market segment without loss of brand value.

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Abstract

La présente invention concerne un produit de nettoyage contenant du phosphore fabriqué ou vendu en association avec une marque, pouvant être remplacé par un produit de nettoyage ou un système de nettoyage de substitution de marque identique contenant un composé à teneur réduite en phosphore, et contenant (ou utilisé avec un produit de traitement de l’eau) un composé de magnésium en quantité suffisante pour assurer une performance commercialement acceptable lorsque le produit de nettoyage de substitution contient ou est utilisé avec de l’eau dure
PCT/IB2008/054569 2008-11-03 2008-11-03 Procédé de formulation d’un produit de nettoyage ou un système de nettoyage de marque à teneur réduite en phosphore Ceased WO2010061240A1 (fr)

Priority Applications (1)

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PCT/IB2008/054569 WO2010061240A1 (fr) 2008-11-03 2008-11-03 Procédé de formulation d’un produit de nettoyage ou un système de nettoyage de marque à teneur réduite en phosphore

Applications Claiming Priority (1)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2592134B1 (fr) 2011-11-13 2022-11-02 Compad Consulting GmbH Détersifs et nettoyants durables

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6303556B1 (en) * 1999-01-20 2001-10-16 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkybenzene sulfonates
US6342473B1 (en) * 1999-01-20 2002-01-29 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkylbenzene sulfonates
US6387864B1 (en) * 2000-12-15 2002-05-14 Ecolab Inc. Composition and method for prevention of discoloration of detergents using nonionic surfactants and an alkaline source

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6303556B1 (en) * 1999-01-20 2001-10-16 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkybenzene sulfonates
US6342473B1 (en) * 1999-01-20 2002-01-29 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkylbenzene sulfonates
US6387864B1 (en) * 2000-12-15 2002-05-14 Ecolab Inc. Composition and method for prevention of discoloration of detergents using nonionic surfactants and an alkaline source

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2592134B1 (fr) 2011-11-13 2022-11-02 Compad Consulting GmbH Détersifs et nettoyants durables

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