US3701736A - Means to inhibit overglaze damage by automatic dishwashing detergents - Google Patents

Means to inhibit overglaze damage by automatic dishwashing detergents Download PDF

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Publication number
US3701736A
US3701736A US133340A US3701736DA US3701736A US 3701736 A US3701736 A US 3701736A US 133340 A US133340 A US 133340A US 3701736D A US3701736D A US 3701736DA US 3701736 A US3701736 A US 3701736A
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Prior art keywords
aluminum
overglaze
detergent
composition
sodium
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Expired - Lifetime
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US133340A
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English (en)
Inventor
Amory Earl Austin
Charles L Bechtold
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Colgate Palmolive Co
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Colgate Palmolive Co
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3958—Bleaching agents combined with phosphates
    • 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
    • C11D3/1206—Water-insoluble compounds free metals, e.g. aluminium grit or flakes
    • 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
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3953—Inorganic bleaching agents
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents

Definitions

  • the present invention relates in general to cleaning compositions and in particular to the provision of cleaning compositions beneficially adapted for use in connection with the cleaning of substrates such as dishware and the like having a glazed surface.
  • the overall advantage realized is often marginal in view of concomitant problems having as their genesis the objectionable tendency of the cleaning composition and more particularly, the inhibitor compound, to yield unsightly deposits or precipitates on the surface of the substrate treated, not to mention the contacting surfaces of the washing receptable.
  • the fugitive behavior of the inhibitor material may be such as to substantially vitiate any advantage which might otherwise accrue from its use thereby detracting from commercial feasibility.
  • cleaning compositions capable of providing superior cleaning activity, eg bleaching, washing, etc.
  • a watersoluble alkaline detergent composition for automatic dishwashing comprises a major amount of water soluble organic and/or inorganic builder salts; and metallic aluminum as a protector against overglaze attack.
  • the metallic aluminum contemplated for use in the practice of the present invention and capable of inhibiting both overglaze attack and attack on aluminumware may be in the form of metal strips hung in the dishwasher during the washing cycles or in comminuted form as a direct additive to the detergent formulation.
  • the metallic aluminum may be sacrificial aluminum, aluminum alloys, or pure aluminum.
  • the preferred form of aluminum is in the form of a powder because of the ease with which it can be formulated into a dishwasher detergent, although any finely divided aluminum may be utilized herein.
  • metallic aluminum in lieu of aluminum compounds, heretofore utilized in dishwashing formulations, eliminates stability and solubility problems associated with said aluminum compounds under actual use conditions which may result in undesirable residues found in the cup receptacles and/or on the glassware and dishware.
  • the metallic aluminum additive which is readily soluble in acids or alkalis, permits greater freedom in the formulation of dishwasher cleaning products, capable of protecting the overglaze pattern on fine china and the aluminumware from attack by the alkaline washing solution, without adversely affecting the cleaning efiicacy of the detergent.
  • the superior protection afforded by metallic aluminum is illustrated by the following test, wherein a 4" x 1" x 3& strip of utensil grade aluminum was immersed in 3,000 mi.
  • the water soluble builder salts utilized in the instant detergent composition comprises one or more inorganic and/or organic basic and neutral water soluble salts.
  • the builder salts are employed in amounts ranging up to about 95%, i.e. 40-95% by weight with a range of from about 60% to about 90% by weight of the composition being preferred.
  • Suitable inorganic builders include without necessary limitation, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium tripolyphosphate hexahydrate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexameta phosphate, sodium silicates, SiO /Na O of 1/1 to 3.2/1, e.g.
  • Suitable organic builders include salts of organic acids and, in particular, the water soluble salts of aminopolycarboxylic acids and hydroxycarboxylic acids.
  • the acid portion of the salt can be derived from acids such as nitrilodiacetic; N-(2-hydroxyethyl) nitrilodiacetic acid, nitrilotriacetic acid (NTA), ethylenediamine tetracetic acid (EDTA); N-(2- hydroxyethyl) ethylenediamine triacetic acid; 2-hydroxyethyl iminodiacetic acid; 1,2-diaminocyclohexanediacetic acid; diethylenetriamine penta-acetic acid, citric acid and the like.
  • the builder salt is preferably employed in amounts sutficient to yield a pH in water of from 9.5 to 12 preferably from 10 to 11 in order to obtain optimum detergency performance.
  • the cleaning compositions described herein may further be provided with one or more bleaching agents which may in general be defined as encompassing compounds capable of liberating a hypohalite such as hypochlorite chlorine and/or hypobromite bromine on contact with aqueous media.
  • bleaching agents include the dry, particulate heterocyclic N-bromo and N-chloro imides such as trichloro-cyanuric, tribromocyanuric acid, dibromoand dichlorocy-anuric acid, the salts thereof with water-solubilizing cations such as potassium and sodium and mixtures thereof.
  • Particular compounds found useful are potassium dichloroisocyanurate and trichloroisocyanuric acids.
  • N-bromo and N-chloro imides may also be used, such as N-brominated and N-chlorinated succinimide, malonimide phthalimide and naphthalimide.
  • Other compounds include the hydantoins, such as 1,3-dibromo and 1,3-dich1oro 5,5-dimethylhydantoin; N-monochloro-5,5- dimethylhydantoin, methylene bis(N-bromo-5,5-dimethylhydantoin); 1,3-dibromo and 1,3-dichloro -isobutylhydantoin; 1,3-bromo and 1,3-dichloro, S-methyl-S-n-amylhydantoin, and the like.
  • hypohalite-liberating agents comprise tribromomelamine and trichloromelamine. Dry, particulate, water soluble anhydrous inorganic salts are likewise suitable for use such as lithium hypochlorite and hypobromite.
  • the hypohalite-liberating agent may, if desired, be provided in the form of a stable, solid complex or hydrate, such as sodium p-toluene-su lfo-bromamine-trihydrate, sodium benzene sulfo-chloramine-dihydrate, calcium hypobromine tetrahydrate, calcium hypochlorite tetrahydrate etc.
  • Brominated and chlorinated trisodium phosphate formed by the reaction of the corresponding sodium hypohalite solution with trisodium phosphate (and water as necessary) likewise comprise efiicacious materials.
  • the present invention contemplates as an additional embodiment the use of bleaching agents capable of liberating hypochlorite as Well as hypobromite such as, for example, the N-brominated, N'- chlorinated heterocyclic imides, as for example the N- bromo, N'-chlorocyanuric acids and salts thereof, e.g., N-monobromo-N, N-dichloro-cyanuric acid, N monobromo-N-monochlorocyanuric acid, sodium-N-monobromo-N monochlorocyanurate, potassium-N-monobromo- N-monochlorocyanuate; and the N-brominated, N-chlorinated hydantoins, e.g., N-bromo-
  • hypohalite-liberating compound is employed in an amount of from 0.5 to 5% by weight of the composition, and preferably in an amount of from about 0.5 to 3% by weight thereof.
  • hypohalide material should preferably be employed in amounts sufficient to yield from about 0.53% available chlorine, bromine etc. in order to assure optimum results.
  • efiicacious cleaning compositions may be formulated in accordance with the present invention by the use of metallic aluminum in amounts of about 0.06 to 3% by weight of total composition and up to about i.e. from 40% to 95% by weight of at least one compound selected from the group of water-soluble organic detergent, water soluble inorganic or organic neutral or alkaline builder salt, bleaching agent capable of liberating hypohalite on contact with aqueous media and caustic alkali.
  • the bleaching agent is essential to the implementation of those embodiments of the present invention directed to industrial bottle cleaning compositions.
  • Water soluble organic detergents i.e. surface active components may be employed, such materials being well known in the prior art, the term detergent comprehending species of the anionic, cationic, amphoteric and zwitterionic types.
  • alow foaming detergent such as the non-ionics.
  • Nonionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
  • nonionic surface active agents which may be used there may be noted the condensation prodnets of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of higher fatty alcohols of monoethers of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbital mono-oleate and mannitan monopalrnitate, and the condensation products of polypropylene glycol with ethylene oxide.
  • the condensation prodnets of alkyl phenols with ethylene oxide e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units
  • condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units condensation products of higher fatty alcohols of monoethers of hexahydric alcohols and inner ethers thereof such as sorbit
  • Suitable detergents are polyoxyalkene esters of organic acids, such as the higher fatty acids, rosin acids, tall oil, or acids from the oxidation of petroleum, and the like.
  • the polyglycol esters will usually contain from about 8 to about 30 moles of ethylene oxide or its equivalent and about 8 to 22 carbon atoms in the acyl group.
  • Suitable products are refined tall oil condensed with 16 or 20 ethylene oxide groups, or similar polyglycol esters of lauric, stearic, oleic and like acids.
  • Non-ionic detergents are the polyalkylene oxide condensates with higher fatty acid amides, such as the higher fatty acid primary amides and higher fatty acid monoand di-ethanol amides.
  • Suitable agents are coconut fatty acid amide condensed with about 10 to 30 moles of ethylene oxide.
  • the fatty acyl group will similarly have about 8 to 22 carbon atoms, and usually about 10 to 18 carbon atoms in each product.
  • the corresponding sulphonamides may also be used if desired.
  • polyether non-ionic detergents are the polyalkylene oxide ethers of higher aliphatic alcohols.
  • Suitable alcohols are those having a hydrophobic character, and preferably 8 to 22 carbon atoms. Examples thereof are iso-octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and oleyl alcohols which may be condensed with an appropriate amount of ethylene oxide, such as at least about 6, and preferably about 10-30 moles.
  • a typical product is tridecyl alcohol, produced by the Oxo process, condensed with about l2, 15 or 20 moles of ethylene oxide.
  • the corresponding higher alkyl mercaptan or thioalcohols condensed with ethylene oxide are also suitable for use in compositions of the present invention.
  • wetting agents examples include low foaming anionic materials usch as dodecyl hydrogen phosphate, methyl naphthalene sulfonate, sodium 2-acetamidohexadecane-l-sulfonae, and mixtures thereof. Mixtures of the foregoing wetting agents may also be employed, and, if desired, foam-reducing additive may be added as appropriate to minimize undesirable foaming tendencies of these wetting agents under conditions of use.
  • the detergent material is employed in concentrations ranging from about 0.5% to about by weight of total composition with a range of 1% to 3% being particularly preferred.
  • nonionic type detergent that is, about 2-4% is especially beneficial inasmuch as it acts as a foam depressant as well as detersive agent in an automatic dishwashing solution.
  • Minor amounts of other additives which do not interfere with the cleaning, anticorrosive, and overglaze protection properties of instant composition may be added such as pigments, dyes, perfume, fillers, extenders, suds builders, suds depressors, anti-redeposition agents, etc. In some instances it may be commercially feasible to add said ingredients to render them more attractive to the consumer.
  • test samples are immersed in deionized or distilled water maintained at a temperature of 211 F. and containing the indicated percent concentration of detergent for periods of 2, 4 and 6 hours.
  • the test samples are thereafter removed, hand-rubbed with cloth and compared with untreated samples of the same standard plate.
  • the treated samples are visually scrutinized to determine the extent of overglaze damage with numerical indicia being assigned to indicate the extent of overglaze damage involved.
  • the scale of 0, 1, 2, 3 and 4 correspond, in terms of damage, to none, slight, moderate, considerable and complete respectively.
  • EXAMPLE 1 This example illustrates the applicability of the present invention to the preparation and use of cleaning compositions specifically adapted for use in connection with dishwashing operations.
  • the following composition is prepared by dry-blending the specified ingredients to form a dry particulate composition.
  • the non-ionic detergent is the product obtained by the condensation of about three mols of propylene oxide with the condensation product of one mole of a. mixture of essentially straight chain, primary. fatty alcohols in the Cio-Cm range with about six mols of ethylene oxide.
  • Example 2 is repeated except that the concentration of the aluminum powder is reduced to 1.0% and the sodium sulfate is increased to 8.63%.
  • the results obtained are a CSMA rating of 0, a pH of about 10.4 before and a pH of about 10.2 after 6 hours immersion.
  • Example 2 is repeated except that the concentration of the aluminum powder is reduced to 0.5% and the sodium sulfate is increased to 9.13%. The results obtained is a CSMA rating of 0+ and an initial and final pH of about 10.4.
  • EXAMPLE 7 Ingredients: Percent Sodium citrate .2H O 45.0
  • Non-ionic detergent Ex. 1 2.0
  • the pH of a 1% solution of the above ingredients is about 10.4. Overglaze tests at 0.15% concentration gave a CSMA rating of 0+ after 6 hours immersion.
  • Example 7 is repeated but the boric acid and the boric oxide are omitted with an increase of the sodium sulfate content to 14.744%.
  • the pH of a 1% solution of these ingredients is about 11.4.
  • the CSMA rating of a 0.15 solution hereof is 0+.
  • compositions provided in accordance with the present invention are capable of superior cleaning activity i.e., displaying an outstanding capacity to readily remove stain deposits from a wide variety of glazed dishware.
  • Effective industrial bottle cleaning compositions may be provided in accordance with the present invention by merely admixing with caustic alkali whereby to provide a highly alkaline composition preferably having a pH of about 12.
  • Such compositions may be readily formulated in accordance with the parameters hereinbefore described.
  • the detergent composition of the present invention finds most efficacious utilization in connection with the washing of the dishes and the like in automatic dishwashers, naturally, the detergent may be utilized in other fashions as desired. Usually, however, the best mode of 8 use will be in connection with automatic dishwashers which have the ability of dispensing the detergent of the present invention in one or more separate wash cycles. Accordingly, the detergent compositions of the present invention is added to the two receptacles, if such are present, in an automatic dishwasher. When the dishwasher is set into operation, after the dishes have been suitably positioned therein, the automatic devices of the dishwasher permit the addition of sufficient water to produce a concentration of the detergent composition of approximately 0.15 to 0.5% by weight.
  • the operation of the dishwasher results in treating, that is, washing of the dishes with the aqueous solution of the detergent composition.
  • sequence of operation in utilizing an automatic dishwasher results in one or more rinsing steps following the one or more washing cycles.
  • the detergent composition of the present invention it will be noted that even after use in considerable number of washings there will be little or no attack on the overglaze on china or little or no attack on aluminum- Ware as a result of the use of the detergent composition.
  • any dishwasher detergent may be utilized in accordance with this invention by including within the confines of the dishwasher strips of aluminum or aluminum alloy which will supply metallic aluminum ions to said wash solution during operation.
  • a water-soluble alkaline detergent composition capable of inhibiting overglaze attack and providing an alkaline pH in water consisting essentially of about 40-95% by weight of at least one water-soluble organic and/or inorganic alkaline or neutral builder salt, and at least 3.25% by weight of metallic aluminum.
  • composition in accordance with claim 1 which also includes about 0.5% by weight of a bleaching agent capable of liberating hypochlorite or hypobromite in aqueous media.
  • a composition in accordance with claim 2 which also includes about 0.5% to 5% by weight of a watersoluble low-foaming non-ionic organic detergent.
  • a method for treating glasses, dishes and glazed surfaces to remove foreign bodies from the surfaces thereof without modifying the substrata comprising treating said substrata with a dilute aqueous solution of the composition defined in claim 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
US133340A 1971-04-12 1971-04-12 Means to inhibit overglaze damage by automatic dishwashing detergents Expired - Lifetime US3701736A (en)

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US13334071A 1971-04-12 1971-04-12

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US (1) US3701736A (OSRAM)
BE (1) BE781916A (OSRAM)
CA (1) CA969831A (OSRAM)
CH (1) CH568380A5 (OSRAM)
DE (1) DE2216657A1 (OSRAM)
DK (1) DK138604B (OSRAM)
FR (1) FR2132804B1 (OSRAM)
GB (1) GB1384456A (OSRAM)
IT (1) IT954417B (OSRAM)
NL (1) NL7204916A (OSRAM)
SE (1) SE393119B (OSRAM)
ZA (1) ZA721935B (OSRAM)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888781A (en) * 1972-09-05 1975-06-10 Procter & Gamble Process for preparing a granular automatic dishwashing detergent composition
US4908148A (en) * 1989-02-13 1990-03-13 The Procter & Gamble Company Rinse additive compositions providing glassware protection comprising insoluble zinc compounds
US4933101A (en) * 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
EP0385595A3 (en) * 1989-02-13 1991-01-23 The Procter & Gamble Company Liquid automatic dishwashing compositions having an optimized thickening system
WO1996036687A1 (en) * 1995-05-19 1996-11-21 Unilever N.V. Automatic dishwashing compositions containing aluminum salts
WO1998051769A1 (en) * 1997-05-13 1998-11-19 The Procter & Gamble Company Process for removing tarnish from tarnished silverware
US20050003979A1 (en) * 2003-07-02 2005-01-06 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US20050020464A1 (en) * 2003-07-02 2005-01-27 Smith Kim R. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20080020960A1 (en) * 2006-07-24 2008-01-24 Smith Kim R Warewashing composition for use in automatic dishwashing machines, and method for using

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888781A (en) * 1972-09-05 1975-06-10 Procter & Gamble Process for preparing a granular automatic dishwashing detergent composition
US4908148A (en) * 1989-02-13 1990-03-13 The Procter & Gamble Company Rinse additive compositions providing glassware protection comprising insoluble zinc compounds
US4933101A (en) * 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
EP0385595A3 (en) * 1989-02-13 1991-01-23 The Procter & Gamble Company Liquid automatic dishwashing compositions having an optimized thickening system
WO1996036687A1 (en) * 1995-05-19 1996-11-21 Unilever N.V. Automatic dishwashing compositions containing aluminum salts
WO1998051769A1 (en) * 1997-05-13 1998-11-19 The Procter & Gamble Company Process for removing tarnish from tarnished silverware
US7196044B2 (en) 2003-07-02 2007-03-27 Ecolab, Inc. Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor
US7524803B2 (en) 2003-07-02 2009-04-28 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines comprising an aluminum/zinc ion mixture
US7135448B2 (en) 2003-07-02 2006-11-14 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US20060270580A1 (en) * 2003-07-02 2006-11-30 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20050003979A1 (en) * 2003-07-02 2005-01-06 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US7196045B2 (en) 2003-07-02 2007-03-27 Ecolab Inc. Warewashing composition comprising a corrosion inhibitor with Al and Zn ions
US20070149431A1 (en) * 2003-07-02 2007-06-28 Lentsch Steven E Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7829516B2 (en) 2003-07-02 2010-11-09 Ecolab Usa Inc. Warewashing composition comprising a Zn/Al corrosion inhibitor for use in automatic dishwashing machines
US7452853B2 (en) 2003-07-02 2008-11-18 Ecolab Inc. Warewashing composition comprising zinc and aluminum ions for use in automatic dishwashing machines
US20090038649A1 (en) * 2003-07-02 2009-02-12 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20050020464A1 (en) * 2003-07-02 2005-01-27 Smith Kim R. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7638473B2 (en) 2003-07-02 2009-12-29 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7759299B2 (en) 2006-07-24 2010-07-20 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines
US20100242997A1 (en) * 2006-07-24 2010-09-30 Ecolab Usa Inc. Method for using warewashing composition in automatic dishwashing machines
US20080020960A1 (en) * 2006-07-24 2008-01-24 Smith Kim R Warewashing composition for use in automatic dishwashing machines, and method for using
US7858574B2 (en) 2006-07-24 2010-12-28 Ecolab Usa Inc. Method for using warewashing composition comprising AI and Ca or Mg IONS in automatic dishwashing machines

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GB1384456A (en) 1975-02-19
IT954417B (it) 1973-08-30
SE393119B (sv) 1977-05-02
CH568380A5 (OSRAM) 1975-10-31
DK138604B (da) 1978-10-02
BE781916A (fr) 1972-07-31
FR2132804B1 (OSRAM) 1977-04-01
FR2132804A1 (OSRAM) 1972-11-24
DE2216657A1 (de) 1972-10-19
ZA721935B (en) 1973-11-28
DK138604C (OSRAM) 1979-04-23
CA969831A (en) 1975-06-24
NL7204916A (OSRAM) 1972-10-16

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