EP0998548B1 - Maschinengeschirrspülmittel enthaltend wasserlösliche kationische oder amphotere polymere - Google Patents

Maschinengeschirrspülmittel enthaltend wasserlösliche kationische oder amphotere polymere Download PDF

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Publication number
EP0998548B1
EP0998548B1 EP98940267A EP98940267A EP0998548B1 EP 0998548 B1 EP0998548 B1 EP 0998548B1 EP 98940267 A EP98940267 A EP 98940267A EP 98940267 A EP98940267 A EP 98940267A EP 0998548 B1 EP0998548 B1 EP 0998548B1
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EP
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Prior art keywords
poly
cationic
vinyl
acid
alkyl
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French (fr)
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EP0998548A1 (de
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Alla Tartakovsky
Joseph Oreste Carnali
Richard Gerald Gary
John Robert Winters
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Unilever NV
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Unilever NV
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Priority claimed from US08/898,758 external-priority patent/US5981456A/en
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention is in the field of machine dishwashing. More specifically, the invention encompasses automatic dishwashing detergents in granular, liquid, gel, solid and tablet form which contain a cationic or amphoteric water soluble polymer for the purpose of reducing the fading or corrosion of dishware such as decorated glassware.
  • Machine dishwashing detergents constitute a generally recognized distinct class of detergent compositions.
  • machine dishwashing detergents are mixtures of ingredients whose purpose, in combination, is to breakdown and remove food soils; to inhibit foaming caused by certain food soils; to promote the wetting of wash articles in order to minimize or eliminate visually observable spotting and filming; to remove stains such as might be caused by beverages such as coffee and tea or by vegetable soils such as carotenoid soils; to prevent a buildup of soil films on wash ware surfaces; and to reduce or eliminate tarnishing of flatware.
  • An additional and critical characteristic which the machine dishwashing detergent must possess is the ability to perform all of the above tasks without substantially etching or corroding or otherwise damaging the surface of glasses or dishes. It is particularly critical that the fading and loss of luster from brightly colored decorations on glasses and dishes be prevented.
  • compositions suitable for use in machine dishwashing methods, having a reduced tendency to fade or otherwise corrode brightly patterned plates and glasses while at the same time maintaining good cleaning performance towards soiled articles.
  • UK Patent Application GB 2 295 625 A and WO 96/17051 disclose compositions for use in machine dishwashing comprising a mixture of disilicate and metasilicate in which the weight ratio of disilicate to metasilicate is from 50:1 to 3:2. The minor proportion of metasilicate is described to reduce glass pattern corrosion.
  • WO 96/20268 describes a copolymer of an organomineral siliconate, obtained by condensation polymerization of an alkali metal disilicate and an alkali metal siliconate, as an additive in a machine dishwashing formulation for the purpose of reducing weight loss and visible corrosion on glass.
  • WO 96/20129 discloses an alkali metal silicate partially substituted with calcium, magnesium, strontium or cerium as counterion. This modified silicate, when incorporated into a machine dishwashing composition, is described to reduce the weight loss and visible corrosion of washed glassware.
  • WO 96/12783 describes the inclusion of a crystalline layered silicate of the general formula Na 2 Si x O 2+1 .yH 2 O for preserving the color and luster of patterned glassware during machine dishwashing.
  • transition metal salts particularly of aluminum
  • U.S. Patent No. 5,698,506 for use in mitigating the fading of colors from decorated glassware.
  • aluminum complexes with such as citrate has been described in U.S. Patent No. 5,624,892.
  • EP-A-0 560 519, DE-A-19 532 542 and EP-A-0 077 588 disclose compositions for use in automatic dishwashing machines, which comprise water-soluble cationic or amphoteric polymers. However they are used in these documents to prevent spotting or filming, as rinse aids and to reduce foaming respectively. Their use to prevent fading or corrosion is not disclosed.
  • water soluble, cationic or amphoteric polymers provide an unexpected and superior level of protection to decorated glassware when incorporated into a machine dishwashing detergent. Such protection is illustrated by, but not limited to, the prevention of fading and loss in luster of colored decorations and the reduction in weight loss from washed glass articles.
  • the invention relates to a method for preventing fading or corrosion of dishware during the wash process in an automatic dishwashing machine by adding to the dishwashing machine a composition comprising a water soluble cationic or amphoteric polymer.
  • the present invention provides a further method for preventing fading or corrosion of dishware during the wash process in an automatic dishwashing machine by adding to the dishwashing machine a composition, comprising:
  • Water soluble polymers are, unless otherwise noted, here defined to include polymers which, because of their molecular weight or monomer composition, are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C.
  • “Cationic” polymers herein comprise polymers in which at least one of the monomer units making up the polymer contains a cationic charge over a portion of the wash pH range of pH 6 to pH 11, those monomer units not containing cationic charges being nonionic in nature.
  • Amphoteric polymers herein are defined as polymers in which at least one of the comprising monomer units contains a cationic charge over a portion of the pH range 6-11 and at least one of the comprising monomer units contains an anionic charge over the same portion of the pH range 6-11.
  • the overall composition of an amphoteric polymer can otherwise freely be chosen from among monomers containing cationic charge(s), monomers containing anionic charge(s), monomer units containing both cationic and anionic charge(s), and monomer units which are nonionic in nature - so long as the above definition is satisfied.
  • wash pH at which this invention would be employed would either naturally fall within the above mentioned portion of the pH range 6-11 or, optionally, would be buffered in that range.
  • Water soluble cationic or amphoteric polymers may be added to a rinse aid, in which case the pH at which the polymers should retain their charge would be as low as 2.
  • the present composition contains as essential components a water soluble cationic or amphoteric polymer and optionally a builder which may be a phosphate or nonphosphate builder.
  • compositions of the present invention which utilize a water-soluble phosphate builder typically contain this builder at a level of from 1 to 90% by weight, preferably from 10 to 80% by weight, most preferably from 20 to 70% by weight of the composition.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid. Sodium or potassium tripolyphosphate is most preferred.
  • compositions of the present invention which utilize a water-soluble nonphosphate builder typically contain this builder at a level of from 1 to 90% by weight, preferably from 10 to 80% by weight, most preferably from 20 to 70% by weight of the composition.
  • Suitable examples of non-phosphorus-containing inorganic builders include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, including layered silicates such as SKS-6 ex. Hoechst, metasilicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates including layered silicates and zeolites.
  • Organic detergent builders can also be used as nonphosphate builders in the present invention.
  • organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylate
  • Such carboxylates are described in U.S. Patent Nos. 4,144,226, 4,146,495 and 4,686,062.
  • Alkali metal citrates, nitrilotriacetates, oxydisuccinates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred nonphosphate builders.
  • a water soluble cationic or amphoteric polymer is here defined to include polymers which, because of their molecular weight or monomer composition, are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C.
  • Water soluble cationic or amphoteric polymers include polymers in which one or more of the constituent monomers are selected from the list of copolymerizable cationic monomers. These monomer units contain a positive charge over a portion of the pH range 6-11. A partial listing of such monomers is presented in "Water-Soluble Synthetic Polymers: Properties and Behavior, Volume II", by P. Molyneux, CRC Press, Boca Raton, 1983, ISBN 0-8493-6136- incorporated herein by reference.
  • monomers useful in this invention may be represented structurally as ethenically unsaturated compounds as in formula I.
  • R 1 is hydrogen, hydroxyl, or a C 1 to C 30 straight or branched alkyl radical
  • R 2 is hydrogen, or a C 1-30 straight or branched alkyl, a C 1-30 straight or branched alkyl substituted aryl, aryl substituted C 1-30 straight or branched alkyl radical, or a poly oxyalkene condensate of an aliphatic radical
  • R 3 is a heteroatomic alkyl or aromatic radical containing either one or more quaternerized nitrogen atoms or one or more amine groups which possess a positive charge over a portion of the pH interval pH 6 to 11.
  • Such amine groups can be further delineated as having a pK a of about 6 or greater, as defined by R. Laughlin in "Cationic Surfactants, Physical Chemistry", edited by D.N. Rubingh and P.M.Holland, Marcel Dekker, New York, 1991, ISBN 0-8247-8357-3.
  • cationic polymers include, but are not limited to, co-poly 2-vinyl pyridine and its co-poly 2-vinyl N-alkyl quaternary pyridinium salt derivatives; co-poly 4-vinyl pyridine and its co-poly 4-vinyl N-alkyl quaternary pyridinium salt derivatives; co-poly 4-vinylbenzyltrialkylammonium salts such as co-poly 4-vinylbenzyltrimethylammonium salt; co-poly 2-vinyl piperidine and co-poly 2-vinyl piperidinium salt; co-poly 4-vinylpiperidine and co-poly 4-vinyl piperidinium salt; co-poly 3-alkyl 1-vinyl imidazolium salts such as co-poly 3-methyl 1-vinyl imidazolium salt; acrylamido and methacrylamido derivatives such as co-poly dimethyl aminopropylmethacrylamide, co-
  • cationic polymers suitable for this invention are co-poly vinyl amine and co-polyvinylammonium salt; co-poly diallylamine, co-poly methyldiallylamine, and co-poly diallydimethylammonium salt; and the ionene class of internal cationic monomers as defined by D. R. Berger in "Cationic Surfactants, Organic Chemistry", edited by J.M. Richmond, Marcel Dekker, New York, 1990, ISBN 0-8247-8381-6, herein incorporated by reference.
  • This class includes co-poly ethylene imine, co-poly ethoxylated ethylene imine and co-poly quaternized ethoxylated ethylene imine; co-poly [(dimethylimino) trimethylene (dimethylimino) hexamethylene disalt], co-poly [(diethylimino) trimethylene (dimethylimino) trimethylene disalt]; co-poly [(dimethylimino) 2-hydroxypropyl salt]; as defined in the "International Cosmetic Ingredient Dictionary, 5th Edition", edited by J.A. Wenninger and G.N. McEwen.
  • Preferred, cationic polymers are the cationic co-poly amido-amine having the chemical structure of formula II. where n is a number from 1 to 10,000 and X is any suitable counter ion preferably CL , and the quaternized polyimidazoline having the chemical structure of formula III where X - is any suitable counter ion preferably CH 3 OSO 2 - .
  • An additional class of cationic polymers suitable for this invention are those arising from natural sources and include, but are not limited to, cocodimethylammonium hydroxypropyl oxyethyl cellulose, lauryldimethylammonium hydroxypropyl oxyethyl cellulose, stearyldimethylammonium hydroxypropyl oxyethyl cellulose, and stearyldimethylammonium hydroxyethyl cellulose; guar 2-hydroxy-3-(trimethylammonium) propyl ether salt; cellulose 2-hydroxyethyl 2-hydroxy 3-(trimethyl ammonio) propyl ether salt.
  • the counterion of the comprising cationic co-monomer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulfate, methyl sulfate, formate, and acetate.
  • Water soluble amphoteric polymers suitable for incorporation into the present invention can also include polymers in which one or more of the constituent monomers are selected from the list of copolymerizable, internally amphoteric monomers. These monomer units contain both one or more positive charges and one or more negative charges over a portion of the pH range 6-11.
  • Such internally amphoteric monomers include those species possessing formal anionic and cationic charges such as N,N-dimethyl, N-acetyl aminoethyl(meth)acrylate. Also included are monomers which, while not possessing formal charges, have one or more resonance forms which result in the occurrence of fractional cationic and anionic charges being separated within the monomer.
  • Monomers in this class are typified by vinyl pyrrolidone, as described in "Water-Soluble Synthetic Polymers: Properties and Behavior, Volume I", by P. Molyneux, CRC Press, Boca Ratan, 1983, ISBN 0-8493-6135-4. Further examples include vinyl oxazolidone; vinyl methyoxazolidone; and vinyl caprolactam.
  • the weight fraction of the cationic or amphoteric polymer which is composed of the above-described cationic or amphoteric monomer units can range from 1 to 100%, preferably from 10 to 100%, and most preferably from 15 to 80% of the entire polymer.
  • the remaining monomer units comprising the cationic or amphoteric polymer are chosen from the class of anionic monomers and the class of nonionic monomers or solely from the class of nonionic monomers.
  • the polymer is an amphoteric polymer while in the latter case it can be a cationic polymer, provided that no amphoteric co-monomers are present.
  • the anionic monomers comprise a class of monounsaturated compounds which possess a negative charge over the portion of the pH range from pH 6 to 11 in which the cationic monomers possess a positive charge.
  • the nonionic monomers comprise a class of monounsaturated compounds which are uncharged over the pH range from pH 6 to 11 in which the cationic monomers possess a positive charge. It is expected that the wash pH at which this invention would be employed would either naturally fall within the above mentioned portion of the pH range 6-11 or, optionally, would be buffered in that range.
  • a preferred class of both the anionic and the nonionic monomers are the vinyl (ethylenically unsaturated) substituted compounds corresponding to formula IV.
  • R 4 , R 5 , and R 6 are independently hydrogen, a C 1 to C 3 alkyl, a carboxylate group or a carboxylate group substituted with a C 1 to C 30 linear or branched heteroatomic alkyl or aromatic radical, a heteroatomic radical or a poly oxyalkene condensate of an aliphatic radical.
  • the class of anionic monomers are represented by the compound described by formula IV in which at least one of the R 4 , R 5 , or R 6 comprises a carboxylate, substituted carboxylate, phosphonate, substituted phosphonate, sulfate, substituted sulfate, sulfonate, or substituted sulfonate group.
  • Preferred monomers in this class include but are not limited to ⁇ -ethacrylic acid, ⁇ -cyano acrylic acid, ⁇ , ⁇ -dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, acrylic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, ⁇ -styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), citraconic acid, glutaconic acid, aconitic acid, ⁇ -phenylacrylic acid, ⁇ -acryloxy propionic acid, citraconic acid, vinyl benzoic acid, N-vinyl succinamidic acid, and mesaconic acid.
  • co-poly styrene sulfonic acid 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryloyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid and vinyl phosphoric acid.
  • Most preferred monomers include acrylic acid, methacrylic acid and maleic acid.
  • the polymers useful in this invention may contain the above monomers and the alkali metal, alkaline earth metal, and ammonium salts thereof.
  • the class of nonionic monomers are represented by the compounds of formula IV in which none of the R 4 , R 5 , or R 6 contain the above mentioned negative charge containing radicals.
  • Preferred monomers in this class include, but are not limited to, vinyl alcohol; vinyl acetate; vinyl methyl ether; vinyl ethyl ether; acrylamide, methacrylamide and other modified acrylamides; vinyl propionate; alkyl acrylates (esters of acrylic or methacrylic acid); and hydroxyalkyl acrylate esters.
  • a second class of nonionic monomers include co-poly ethylene oxide, co-poly propylene oxide, and co-poly oxymethylene.
  • a third class of nonionic monomers includes naturally derived materials such as hydroxyethylcellulose.
  • the average molecular weight of the polymers of this invention range from about 1000 to about 10 7 , with the preferred molecular weight range depending on the polymer composition.
  • An effective amount of said polymer is 0.1 to 20%, preferably 0.5 to 10%, most preferably 1 to 5%, all by weight, of the total detergent formulation.
  • compositions of the invention may be formulated as detergent compositions comprising conventional ingredients, preferably selected from enzymes, buffering systems, oxygen bleaching systems, surfactants, heavy metal ion sequestrants, antiscalants, corrosion inhibitors, and antifoams.
  • Enzymes capable of facilitating the removal of soils from a substrate may also be present in a combined amount of up to about 10% by weight of active enzyme.
  • Such enzymes include proteases, amylases, lipases, esterases, cellulases, pectinases, lactases and peroxidases as conventionally incorporated into detergent compositions.
  • Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase and Esperase from Novo Industries A/S (Denmark); and those sold by Genencor International under the tradename Purafect OxP.
  • Preferred commercially available amylases include those ⁇ -amylases sold under the tradenames Termamyl and Duramyl from Novo Industries and those sold by Genencor International under the tradename Purafect OxAm.
  • a preferred lipase is commercially available from Novo Industries under the trade name Lipolase.
  • the buffering system may be present in order to deliver a pH of about 6 to about 11 in the wash water.
  • Materials which may be selected for the buffering system include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, layered silicates such as SKS-6 ex Hoechst, metasilicates, phytic acid, citric acid, borate and crystalline and amorphous aluminosilicates and mixtures thereof.
  • Preferred examples include sodium and potassium carbonate, sodium and potassium bicarbonates, borates and silicates, including layered silicates.
  • the present invention may optionally contain an oxygen bleach source chosen from the following:
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as:
  • a typical diacylperoxide useful herein includes dibenzoylperoxide.
  • Inorganic peroxygen compounds are also suitable for the present invention.
  • these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
  • Preferred peroxy bleaching agents include epsilon-phthalimido-peroxyhexanoic acid, o-carboxybenzamidoperoxyhexanoic acid, and mixtures thereof.
  • the organic peroxy acid is present in the composition in an amount such that the level of organic peroxy acid in the wash solution is about 1 ppm to about 300 ppm AvOx, preferably about 2 ppm to about 200 ppm AvOx.
  • the oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques.
  • the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from about 40°C to 50°C.
  • the wax coating has a thickness of from 100 to 1500 microns.
  • Bleach Precursors - Suitable peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907;358; 907,950; 1,003,310 and 1,246,339; U.S. Patent Nos. 3,332,882 and 4,128,494.
  • Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N',N'-tetraacetylethylene diamine (TAED) and N,N,N',N'-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate.
  • SABS sodium acetyloxybenene sulfonate
  • SNOBS sodium nonanoyloxy benzene sulfonate
  • choline sulfophenyl carbonate choline sulfophenyl carbonate
  • Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988. Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
  • Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N',N'-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate.
  • the peroxygen bleach precursors are present in the composition in an amount from about 1 to about 20 weight percent, preferably from about 1 to about 15 wt. %, most preferably from about 2 to about 15 wt. %.
  • a source of hydrogen peroxide is required.
  • the hydrogen peroxide source is preferably a compound that delivers hydrogen peroxide on dissolution.
  • Preferred sources of hydrogen peroxide are sodium perborate, either as the mono- or tetrahydrate and sodium percarbonate.
  • the source of hydrogen peroxide, when included in these compositions is present at a level of about 1% to about 40% by weight, preferably from about 2% to about 30% by weight, most preferably from about 4% to about 25% by weight.
  • Bleach Catalyst - An effective amount of a bleach catalyst can also be present in the invention.
  • a number of organic catalysts are available such as the sulfonimines as described in U.S. Patents 5,041,232; 5,047,163 and 5,463,115.
  • Transition metal bleach catalysts are also useful, especially those based on manganese, iron, cobalt, titanium, molybdenum, nickel, chromium, copper, ruthenium, tungsten and mixtures thereof. These include simple water-soluble salts such as those of iron, manganese and cobalt as well as catalysts containing complex ligands.
  • Suitable examples of manganese catalysts containing organic ligands are described in U.S. Pat. 4,728,455, U.S. Pat. 5,114,606, U.S. Pat 5,153,161, U.S. Pat. 5,194,416, U.S. Pat. 5,227,084, U.S. Pat. 5,244,594, U.S. Pat.5,246,612, U.S. Pat. 5,246,621, U.S. Pat. 5,256,779, U.S. Pat. 5,274,147, U.S. Pat. 5,280,117 and European Pat. App. Pub. Nos. 544,440, 544,490, 549,271 and 549,272.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (CIO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (CIO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ), and mixtures thereof.
  • Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • Iron and manganese salts of aminocarboxylic acids in general are useful herein including iron and manganese aminocarboxylate salts disclosed for bleaching in the photographic color processing arts.
  • a particularly useful transition metal salt is derived from ethylenediaminedisuccinate and any complex of this ligand with iron or manganese.
  • Another type of bleach catalyst is a water soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, mesoerythritol, meso-inositol, lactose and mixtures thereof. Especially preferred is sorbitol.
  • U.S. Patent No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including manganese, cobalt, iron or copper with a non-(macro)-cyclic ligand.
  • transition metals including manganese, cobalt, iron or copper
  • Other examples include Mn gluconate, MN(CF 3 SO 3 ) 2 , and binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including [bipy 2 Mn III (u-O) 2 Mn IV bipy 2 ]-(CIO 4 ) 3 .
  • bleach catalysts are described, for example, in European Pat. App. Pub. Nos. 408,131 (cobalt complexes), 384,503 and 306,089 (metallo-porphyrins), U.S. Pat. 4,728,455 (manganese/multidenate ligand), U.S. Pat. 4,711,748 (absorbed manganese on aluminosilicate), U.S. Pat. 4,601,845 (aluminosilicate support with manganese, zinc or magnesium salt), U.S. Pat. 4,626,373 (manganese/ligand), U.S. Pat. 4,119,557 (ferric complex), U.S. Pat. 4,430.243 (Chelants with manganese cations and non-catalytic metal cations), and U.S. Pat. 4,728,455 (manganese gluconates).
  • WO 96/23860 describe cobalt catalysts of the type [Co n L m X p ] z Y z , where L is an organic ligand molecule containing more than one heteroatom selected from N, P, O and S; X is a co-ordinating species; n is preferably 1 or 2; m is preferably 1 to 5; p is preferably 0 to 4 and Y is a counterion.
  • transition-metal containing bleach catalysts can be prepared in the situ by the reaction of a transition-metal salt with a suitable chelating agent, for example, a mixture of manganese sulfate and ethylenediaminedisuccinate.
  • a suitable chelating agent for example, a mixture of manganese sulfate and ethylenediaminedisuccinate.
  • Highly colored transition metal-containing bleach catalysts may be co-processed with zeolites to reduce the color impact.
  • the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10% by wt., preferably about 0.001 to about 5% by weight.
  • a surfactant selected from the list including anionic, nonionic, cationic, amphoteric, and zwitteronic surfactants and mixtures of these surface active agents may be included in the machine dishwashing formulation.
  • Such surfactants are well known in the detergent arts and are described at length in "Surface Active Agents and Detergents", Vol. 2 by Schwartz, Perry and Birch, Interscience Publishers, Inc., 1959.
  • Preferred surfactants are one or a mixture of:
  • Anionic surfactants - Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups.
  • An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
  • R 7 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilizing cation.
  • the alkyl group R 7 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 7 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 7 is coconut alkyl, for example.
  • the solubilizing cation may be a range of cations which are in general monovalent and confer water solubility.
  • An alkali metal, notably sodium, is especially envisaged.
  • Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
  • Alkyl Ether Sulfates R 7 O(CH 2 CH 2 O) n SO 3 M where R 7 is a primary alkyl group of 8 to 18 carbon atoms, n has an average value in the range from 1 to 6 and M is a solubilizing cation.
  • the alkyl group R 7 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 7 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 7 is coconut alkyl, for example.
  • n has an average value of 2 to 5.
  • R 8 is an alkyl group of 6 to 16 atoms
  • R 9 is an alkyl group of 1 to 4 carbon atoms
  • M is a solubilizing cation.
  • the group R 8 may have a mixture of chain lengths. Preferably at least two-thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R 8 CH(-)CO 2 (-) is derived from a coconut source, for instance. It is preferred that R 9 is a straight chain alkyl, notably methyl or ethyl.
  • Alkyl Benzene Sulfonates R 10 ArSO 3 M where R 10 is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (C 6 H 4 ) and M is a solubilizing cation.
  • the group R 10 may be a mixture of chain lengths. Straight chains of 11 to 14 carbon atoms are preferred.
  • Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Celanese.
  • Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
  • U.S. Patent No. 3,332,880 contains a description of suitable olefin sulfonates.
  • Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
  • Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula: R 8 CH(SO 3 M)CO 2 R 9 where the moiety R 8 CH(-)CO 2 (-) is derived from a coconut source and R 9 is either methyl or ethyl; primary alkyl sulfates with the formula: R 7 OSO 3 M wherein R 7 is a primary alkyl group of 10 to 18 carbon atoms and M is a sodium cation; and paraffin sulfonates, preferably with 12 to 16 carbon atoms to the alkyl moiety.
  • Nonionic surfactants - Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents.
  • a major class of nonionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
  • Ethoxylated fatty alcohols may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above.
  • the average chain lengths of the alkyl group R 11 in the general formula: R 11 O(CH 2 CH 2 O) n H is from 6 to 20 carbon atoms.
  • the group R 11 may have chain lengths in a range from 9 to 18 carbon atoms.
  • the average value of n should be at least 2.
  • the numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation.
  • Particularly preferred ethoxylated fatty alcohols have a group R 11 which has 9 to 18 carbon atoms while n is from 2 to 8.
  • nonionic surfactants having a formula: wherein R 12 is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R 13 and R 14 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
  • One preferred nonionic surfactant of the above formula is Poly-Tergent SLF-18 a registered trademark of the Olin Corporation, New Haven, Conn. having a composition of the above formula where R 12 is a C 6 -C 10 linear alkyl mixture, R 13 and R 14 are methyl, x averages 3, y averages 12 and z averages 16.
  • R 15 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including mixtures thereof; and R 16 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; j is an integer having a value of from 1 to about 3; k is an integer having a value from 5 to about 30; and 1 is an integer having a value of from 1 to about 3.
  • Other preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U.S. 4,340,766 to BASF. Particularly preferred is Plurafac LF403 ex. BASF.
  • R 17 is a C 6 -C 24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R 17 is a C 8 -C 18 linear alkyl mixture and q is a number from 2 to 15.
  • the preferred polyoxyethylene derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbital tristearate, sorbitan monooleate, and sorbitan trioleate.
  • the polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 10 to 20.
  • the sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
  • polyoxyethylene-polyoxypropylene block copolymers having formula: HO(CH 2 CH 2 O) a (CH(CH 3 ) CH 2 O) b (CH 2 CH 2 O) c H or HO(CH(CH 3 )CH 2 O) d (CH 2 CH 2 O) e (CH(CH 3 )CH 2 O) f H wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer.
  • the polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer.
  • the material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art. They are available under the trademark "Pluronic” and "Pluronic R", a product of BASF Corporation.
  • Amine oxides having formula: R 18 R 19 R 20 N O wherein R 18 , R 19 and R 20 are saturated aliphatic radicals or substituted saturated aliphatic radicals.
  • Preferable amine oxides are those wherein R 18 is an alkyl chain of about 10 to about 20 carbon atoms and R 19 and R 20 are methyl or ethyl groups or both R 18 and R 19 are alkyl chains of about 6 to about 14 carbon atoms and R 20 is a methyl or ethyl group.
  • Amphoteric synthetic detergents - can be broadly described as derivatives of aliphatic tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • anionic water-solubilizing group i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
  • Zwitterionic synthetic detergents - can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
  • R 21 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about 13) carbon atoms; R 22 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R 22 O) n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Z 1 represents a moiety derived from a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated alipha
  • Examples of commercially available materials from Henkel Techandit GmbH Aktien of Dusseldorf, Germany include APG 300, 325 and 350 with R 21 being C 9 -C 11 , n is 0 and p is 1.3, 1.6 and 1.8-2.2 respectively; APG 500 and 550 with R 21 is C 12 -C 13 , n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG 600 with R 21 being C 12 -C 14 , n is 0 and p is 1.3.
  • esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
  • nonionic surfactants are polyoxyethylene and polyoxypropylene condensates of linear aliphatic alcohols.
  • the preferred range of surfactant is from about 0.5 to 30 % by wt., more preferably from about 0.5 to 15% by weight of the composition.
  • the detergent compositions herein may also optionally contain one or more transition metal chelating agents. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions.
  • Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, ethylenediamine disuccinate, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent No. 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 5.0% by weight of such composition.
  • Scale formation on dishes and machine parts can be a significant problem. It can arise from a number of sources but, primarily it results from precipitation of either alkaline earth metal carbonates, phosphates or silicates. Calcium carbonate and phosphates are the most significant problem. To reduce this problem, ingredients to minimize scale formation can be incorporated into the composition. These include polyacrylates of molecular weight from 1,000 to 400,000 examples of which are supplied by Rohm & Haas, BASF and Alco Corp. and polymers based on acrylic acid combined with other moieties.
  • acrylic acid combined with maleic acid, such as Sokalan CP5 and CP7 supplied by BASF or Acusol 479N supplied by Rohm & Haas; with methacrylic acid such as Colloid 226/35 supplied by Rhone-Poulenc; with phosphonate such as Casi 773 supplied by Buckman Laboratories; with maleic acid and vinyl acetate such as polymers supplied by H ⁇ ls; with acrylamide; with sulfophenol methallyl ether such as Aquatreat AR 540 supplied by Alco; with 2-acrylamido-2-methylpropane sulfonic acid such as Acumer 3100 supplied by Rohm & Haas or such as K-775 supplied by Goodrich; with 2-acrylamido-2-methylpropane sulfonic acid and sodium styrene sulfonate such as K-798 supplied by Goodrich; with methyl methacrylate, sodium methallyl sulfonate and sulfophenol methallyl
  • the composition my optionally contain corrosion inhibitors to reduce the tarnishing of silver flatware.
  • corrosion inhibitors include benzotriazole and other members of the azole family. Particularly preferred are azoles, including imidazoles.
  • Additional antitarnish additives include water-soluble bismuth compounds such as bismuth nitrate as taught in GB 2,297,096 A; heavy metal salts of copper, iron, manganese, zinc, or titanium (EP 0 636 688 A1, GB 2,283,494 A); paraffin oil; and non-paraffin oil organic agents such as fatty esters of mono or polyhydridic alcohols as claimed in EP 0 690 122 A2.
  • compositions of the present invention when formulated for use in machine dishwashing compositions, preferably comprise an antifoam system.
  • Suitable antifoam systems for use herein may comprise essentially any known antifoam compound, including, for example, silicone antifoams, silicone oil, mono- and distearyl acid phosphates, mineral oil, and 2-alkyl and alcanol antifoam compounds. Even if the machine dishwashing composition contains only defoaming surfactants, the antifoam assists to minimize foam which food soils can generate.
  • the compositions may include 0.02 to 2% by weight of antifoam, preferably, 0.05 to 1.0%.
  • Preferred antifoam systems are described in Angevaare et al.; U.S. Serial No. 08/539,923 (WO-A-97/13833).
  • the machine dishwashing compositions of the present invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels, solids or tablets.
  • the process of preparing a granulate may involve preparing a slurry of the ingredients identified above and drying the mixture by means of suitable equipment such as a turbine dryer (Turbogranulation dryer ex Vomm-Turbo Technology, Vomm Impianti E Processi SrL, Milan, Italy).
  • the process may involve preparing the slurry, spray-drying the slurry by conventional techniques using a spray tower in which the slurry is atomized and dried in a hot air stream, followed by restructuring the resulting powder, optionally after milling, in a granulation process (Lödige recycler and Lödige plow shear).
  • a granulation process Liödige recycler and Lödige plow shear.
  • the slurry is sprayed onto fine (recycled) particles and then dried to form gradually growing co-granules.
  • Another attractive possibility is to dry the slurry in a rotary drum granulator and to spray slurry onto recirculated fines, thus building up coarser particles. These particles are either simultaneously or subsequently dried to give a co-granule with a more homogeneous moisture distribution than those obtained by use of a turbine dryer.
  • the process of preparing a tablet may involve admixing the ingredients identified above, transferring the mixture to the tablet die, and compressing with a compaction pressure from about of 3x10 6 kg/m 2 to about 3x10 7 kg/m 2 . It may be preferable to pre-granulate some or all of the ingredients, optionally with surfactant to enhance dissolution, to give granulates of size 100-2000 microns and mix these together with any remaining material prior to compaction. Another possibility is to pre-coat the granulate with any liquid component of the composition via, for example, a fluid bed, pan coater or rolling drum to give encapsulates. The encapsulates are then compressed with a compaction pressure from about 1x10 6 kg/m 2 to about 3x10 7 kg/m 2 .
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous solution having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention.
  • an effective amount of the machine dishwashing composition it is meant from 8 g to 60 g of the composition dissolved or dispersed in a wash solution of volume from 3 to 10 liters, as typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • Example 1 is a granular product based on a phosphate builder while Example 2 is a liquid based on a non-phosphate builder.
  • the effect on glass patterning corrosion of a machine dishwashing composition according to Example 1 of the present invention was determined by conducting a fifteen wash-cycle procedure in which the wash articles were evaluated for fading and loss in luster of colored decorations.
  • the fifteen wash-cycle procedure consisted of the following: A set of four 8 ounce household glasses; having brightly colored, overlaid glass patterns representing garden tools, seashells, fruit, and flowers; and a pair of 8 inch dinner plates having brightly colored, overlaid glass borders in red or yellow were placed within a Miele Super-Electronic G 595 SC machine dishwasher. The glasses were placed on the upper rack and the dinner plates were placed on the lower rack.
  • the Universal 65°C washing program was selected and the wash program executed using soft water (0°FH) and 40 grams of the machine dishwashing composition comprising Example 1.
  • Each set of wash articles was put through fifteen consecutive cycles with the same formulation, after which time the articles were removed and graded for glass pattern corrosion effects. The grading was performed by two expert appraisers on each article and the results were averaged for the plates and glasses, respectively. Grading was through visual inspection according to the following six point scale:
  • water soluble copolymers which contain cationic monomer groups significantly reduce the fading of overlaid patterns on plates and glasses relative to the control.
  • water soluble copolymers which contain amphoteric monomer groups such as Acrylidone 1001
  • water soluble copolymers which do not contain such monomer groups such as 18,293-1, 41,640-1, and 41,911-7 offer no improvement relative to the control and in some cases even enhance fading.
  • water soluble copolymers containing an insufficient level of the cationic monomer groups do not deliver the optimum level of fading protection.
  • EXP 2072 and EXP 2075 each contain 9% by weight of the cationic monomer DMDAAC and do not deliver the same protection as do copolymers with higher DMDAAC levels such as FlocAid 19, FlocAid 34, Merquat 280, or Merquat 295.
  • the weight fraction of the cationic or amphoteric polymers of the invention which is composed of the above-described cationic or amphoteric monomer units can range from 1 to 100%, but is preferably in the range 10 to 100%, and is most preferably in the range from 15 to 80% of the entire polymer.
  • the cationic monomer groups themselves, such as 34,827-9 and 09657 do not offer the same degree of protection toward patterned glassware as that due to the corresponding polymers.
  • the protection observed for the cationic or amphoteric polymers is imparted by the polymers themselves and not by any unpolymerized, residual monomer.
  • Example 4 The procedure of Example 4 was repeated with the exception that 26 grams of the machine dishwashing composition comprising Example 2 was substituted for 40 grams of that of Example 1.
  • preweighed lead glass tiles of 5 cm x 5 cm dimension were added to the upper rack of the Miele Super-Electronic G 595 SC machine dishwasher.
  • the Universal 65°C washing program was selected and the glasses, plates, and lead glass tiles were put through fifteen consecutive cycles with the formulation, after which time the glasses and plates were graded as before and the weight changes of the lead glass tiles were determined as a measure of the corrosive tendency of the trial formulation towards the colored glass comprising the patterning.
  • the tile was judged for intensity and coverage of discoloration in reflected light. Scores of 0 to 5 were assigned by two expert appraisers and then averaged.

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Claims (7)

  1. Verfahren zum Verhindern von Ausbleichen oder Korrosion von Geschirr, während des Waschvorgangs in einer automatischen Geschirrspülmaschine durch Zugeben einer Zusammensetzung, die ein in Wasser lösliches kationisches oder amphoteres Polymer umfasst, zu der Geschirrspülmaschine.
  2. Verfahren zum Verhindern von Korrosion von Geschirr nach Anspruch 1 in einer automatischen Geschirrspülmaschine durch Verwendung einer Formulierung, umfassend:
    a) ein in Wasser lösliches kationisches oder amphoteres Polymer, wobei das kationische Polymer als eine Monomereinheit, eine ethylenisch ungesättigte Verbindung umfasst, wie durch Formel I
    Figure 00520001
    beschrieben, worin R1 Wasserstoff, Hydroxyl oder einen geraden oder verzweigten C1 bis C30-Alkyl-Rest darstellt; R2 Wasserstoff, einen geraden oder verzweigten C1 bis C30-Alkyl-, einen geraden oder verzweigten C1 bis C30-Alkyl-substituierten Aryl-, Aryl-substituierten geraden oder verzweigten C1 bis C30-Alkyl-Rest oder ein Polyoxyalkenkondensat eines aliphatischen Rests darstellt und R3 einen Heteroatom-enthaltenden Alkyl- oder aromatischen Rest, der entweder ein oder mehrere quaternärisierte Stickstoffatome oder eine oder mehrere Amin-Gruppen mit einem pKa-Wert von etwa 6 oder größer und einer positiven Ladung über einen Teil des pH-Wert-Intervalls von pH 6 bis 11 aufweist,
    b) 1 bis 90 Gewichtsprozent eines Builders.
  3. Verfahren zum Verhindern von Korrosion von Geschirr nach Anspruch 1, wobei das Polymer mit einem Anteil von 0,1 bis 20 Gewichtsprozent der Gesamtzusammensetzung vorliegt.
  4. Verfahren nach Anspruch 1, wobei das kationische Polymer mindestens eine Monomereinheit mit einer kationischen Ladung über einen Teil des pH-Wert-Bereichs von 6-11 aufweist.
  5. Verfahren nach einem vorangehenden Anspruch, wobei das kationische oder amphotere Polymer ausgewählt ist aus einer Gruppe, bestehend aus Co-poly-2-vinylpyridin, Co-poly-2-vinyl-N-alkyl-quaternären Pyridiniumsalz-Derivaten, Co-poly-4-vinylbenzyltrialkylammoniumsalzen, Co-poly-2-vinylpiperidin, Co-poly-2-vinylpiperidiniumsalz; Co-poly-4-vinylpiperidin, Co-poly-4-vinylpiperidiniumsalz; Co-poly-3-alkyl-1-vinylimidazoliumsalzen, Acrylamido- und Methacrylamido-Derivaten, Co-poly-methacrylamidopropyltrimethylammoniumsalz, Acrylat- und Methacrylat-Derivaten und Gemischen davon.
  6. Verfahren nach Anspruch 1, wobei das kationische Polymer ausgewählt ist aus der Gruppe, bestehend aus Copoly-vinylamin- und Copolyvinylammoniumsalz; Copolydiallyldimethylammonium, Copolyethylenimin, Copoly-ethoxyliertem Ethylenimin, Copoly-quaternisiertem ethoxyliertem Ethylenimin, Copoly[(dimethylimino)trimethylen(dimethylimino)hexamethylendisalz], Co-poly[(diethylamino)trimethylen(dimethylimino)-trimethylendisalz] und Co-poly[(dimethylimino)-2-hydroxypropylsalz].
  7. Verwendung eines in Wasser löslichen kationischen oder amphoteren Polymers in einer Zusammensetzung zur Zugabe zu einer automatischen Geschirrspülmaschine, um Ausbleichen oder Korrosion von Geschirr zu verhindern.
EP98940267A 1997-07-23 1998-07-13 Maschinengeschirrspülmittel enthaltend wasserlösliche kationische oder amphotere polymere Revoked EP0998548B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US898758 1997-07-23
US08/898,758 US5981456A (en) 1997-07-23 1997-07-23 Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
US09/075,548 US6239091B1 (en) 1997-07-23 1998-05-11 Machine dishwashing compositions with a polymer having cationic monomer units
US75548 1998-05-11
PCT/EP1998/005002 WO1999005248A1 (en) 1997-07-23 1998-07-13 Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers

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EP0998548A1 EP0998548A1 (de) 2000-05-10
EP0998548B1 true EP0998548B1 (de) 2004-09-29

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EP98940267A Revoked EP0998548B1 (de) 1997-07-23 1998-07-13 Maschinengeschirrspülmittel enthaltend wasserlösliche kationische oder amphotere polymere

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EP (1) EP0998548B1 (de)
AT (1) ATE277998T1 (de)
AU (1) AU8864298A (de)
BR (1) BR9811023A (de)
CA (1) CA2296719A1 (de)
DE (1) DE69826671T2 (de)
WO (1) WO1999005248A1 (de)

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EP2662436A1 (de) * 2012-05-11 2013-11-13 The Procter & Gamble Company Reinigungsmittelzusammensetzung
DE102014212728A1 (de) 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2023105006A1 (en) * 2021-12-09 2023-06-15 Reckitt Benckiser Finish B.V. Granular additive

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DE10342631B4 (de) * 2003-09-15 2006-04-13 Henkel Kgaa Maschinelle Geschirrspülmittel mit spezieller Polymermischung
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JP5689317B2 (ja) * 2007-11-06 2015-03-25 ロデイア・オペラシヨン 表面加工用または修飾用共重合体
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CN102300972A (zh) 2008-12-02 2011-12-28 迪瓦西公司 包含阳离子淀粉的餐具洗涤系统
DE102008060469A1 (de) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Maschinelle Geschirrspülmitteltablette
DE102009029636A1 (de) * 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschine Geschirrspülmittel
GB201107885D0 (en) * 2011-05-12 2011-06-22 Reckitt Benckiser Nv Improved composition
CA2844293A1 (en) 2011-10-19 2013-04-25 Basf Se Formulations, their use as or for producing dishwashing compositions and their preparation
EP2768936B1 (de) 2011-10-19 2017-03-01 Basf Se Formulierungen, ihre verwendung als oder zur herstellung von geschirrspülmitteln und ihre herstellung
US8846593B2 (en) 2012-04-25 2014-09-30 Basf Se Dishwashing composition comprising a covalently modified alkyleneimine polymer
BR112014026564A2 (pt) * 2012-04-25 2017-06-27 Basf Se formulação, uso de uma formulação, e, processo para a preparação de uma formulação
EP2841549B1 (de) * 2012-04-25 2016-10-26 Basf Se Formulierungen, ihre verwendung als oder zur herstellung von geschirrspülmitteln und ihre herstellung
US9732309B2 (en) 2012-04-25 2017-08-15 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
WO2014005933A1 (de) * 2012-07-06 2014-01-09 Basf Se Formulierungen und ihre verwendung zur reinigung von glasoberflächen von gebäuden
RU2656214C2 (ru) 2013-04-02 2018-06-01 Басф Се Композиции, их применение в качестве или для получения средств для мытья посуды и их получение
JP6235120B2 (ja) * 2013-04-23 2017-11-22 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 処方物、食器用洗剤としてのそれらの使用方法、又は食器用洗剤の製造のためのそれらの使用方法、及びそれらの製造
DE102014212731A1 (de) * 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Reinigungsmittel umfassend einen Glaskorrosionsinhibitor
DE102016212054A1 (de) * 2016-07-01 2018-01-04 Henkel Ag & Co. Kgaa Reinigungsmittel mit verringerter Glaskorrosion

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2662436A1 (de) * 2012-05-11 2013-11-13 The Procter & Gamble Company Reinigungsmittelzusammensetzung
US8841245B2 (en) 2012-05-11 2014-09-23 The Procter & Gamble Company Detergent composition
DE102014212728A1 (de) 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2023105006A1 (en) * 2021-12-09 2023-06-15 Reckitt Benckiser Finish B.V. Granular additive

Also Published As

Publication number Publication date
DE69826671T2 (de) 2005-02-10
AU8864298A (en) 1999-02-16
WO1999005248A1 (en) 1999-02-04
DE69826671D1 (de) 2004-11-04
ATE277998T1 (de) 2004-10-15
CA2296719A1 (en) 1999-02-04
BR9811023A (pt) 2000-09-19
EP0998548A1 (de) 2000-05-10

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