DE69826671T2 - MACHINE DISHWASHER CONTAINING WATER-SOLUBLE CATIONIC OR AMPHOTERE POLYMERS - Google Patents

Abstract

An automatic dishwashing machine detergent composition is described which contains an effective amount of a defined water soluble cationic or amphoteric polymer and a phosphate or nonphosphate builder. The polymers are soluble or dispersible to at least 0.01 % by weight in distilled water at 25 DEG C. A method of using the polymers to prevent fading or corrosion of dishware is also described.

Description

Field of the invention

The The present invention relates to the field of machine dishwashing. In particular, the invention comprises automatic dishwashing detergents in granular, liquid, Gel, solid and tablet form containing a cationic or amphoteric, soluble in water Polymer for reducing fading or corrosion of Dishes, such as decorative glassware contains.

Background of the invention

Automatic dishwasher detergents provide a generally recognized proprietary class of detergent compositions In general, machine dishwashing detergents are mixtures of ingredients, whose purpose in combination is to mine and reduce leftovers remove; Foam, which is caused by certain dietary solids to inhibit; the wetting of the laundry items to promote, to minimize visually observable staining and filming or to eliminate; Stains caused by drinks, such as coffee and tea, or caused by plant contamination, such as carotene contamination could become, to remove; a collection of dirt films on to be washed dishes surfaces to prevent; and reduce the tarnish tarnish or to remove. An additional and critical property of a machine dishwashing detergent owns, is the ability all the above objects without substantial etching or Corroding or other damage the surface of glasses or to carry dishes. It is especially critical that fading or loss of Shine of brightly colored Decor on glasses and dishes are prevented.

In usual dish washing for facilities and Household creates a strong alkaline solution and is used for washing of dishes, glasses and other cooking and eating utensils. ordinary Tap water can be used in making these highly alkaline cleaning solutions and for rinsing of the laundry items be used after the cleaning step. However in European applications This tap water is common treated (softened) to hardness ions, like calcium and magnesium, to remove, with the result that Residues of hard water on dishes are reduced. Nonetheless can Staining and filming of debris and fancy fabrics remain as a problem, especially if the ion exchange unit, the dishwasher serves, works ineffective. This problem can be solved with a machine dishwashing composition contains a relatively high proportion of polyphosphate which is used to mask hardness ions acts and supports soil removal and stabilization, minimized become. additionally usually contain these detergents a chlorine bleach system for stain removal and additional Cleaning enhancement via oxidation of proteinaceous soils, causing the removal of staining supported on glassware becomes.

Even though the cleaning performance of these conventional detergent compositions satisfactory, have high levels of phosphate, chlorine bleach and high alkalinity strong disadvantages for Environment and consumers. As a result, became an alternative technology developed for the release of less alkaline products. In similar This way, non-phosphated builders are replaced to reduce the environmental profile to improve the composition. As a consequence, reduced cleaning efficiency with modified composition are different washing enzymes, including amylolytic and proteolytic enzymes, in the detergent composition included in the removal of starch or proteinaceous soils to reinforce. Because these enzymes are not compatible with chlorine bleach systems, An oxygen bleaching system can serve as a substitute, resulting in a Reduction of bleaching performance leads. Frequently, enzyme compositions, based on oxygen bleach, with a phosphate builder markets formulated where it is the local Legislation allowed to ensure good overall performance. An unfavorable weakness in the Properties of this alternative technology, both in formulations, which are phosphated (i.e., containing inorganic phosphate builder salts), as well as those that are not phosphated, is that They especially tend to attack decorative glasses and dishes. The striking color of this decor is often a key reason for the Order the item and its fast fading to relative few dishwashers can be particularly conspicuous and give rise to an unfavorable Assessment of an otherwise good performing machine dishwashing product through the consumer.

It is an object of the present invention to provide compositions suitable for use in machine dishwashing processes having a reduced tendency to bleach or otherwise corrode bright decorative dishes and glasses while maintaining good cleaning performance against soiled items.

UK Patent Application GB 2 295 625 A and WO 96/17051 disclose compositions for Use for washing machineware, comprising a mixture of Disilicate and metasilicate, wherein the weight ratio of Disilicate to metasilicate is 50: 1 to 3: 2. It is described that the low content of metasilicate reduces glass decore corrosion.

WHERE 96/20268 describes a copolymer of an organomercury silicate, obtained by condensation polymerization of an alkali metal disilicate and an alkali metal silicoate as an additive for a machine dishwashing formulation for the Purpose of reducing weight loss and visible corrosion on glass.

WHERE 96/20129 discloses an alkali metal silicate, partially substituted with calcium, magnesium, strontium or cerium as counterion. It will described that this modified silicate when used in a machine dishwashing composition incorporated, the weight loss and visible corrosion of washed glass reduced.

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 gloss of decorative glass during machine dishwashing.

Of the The prior art thus describes the use of special Silicates and modified silicates to fade or corrosion while washing dishes to avoid. This basis limits the type of formulation, on which these solutions are applicable. In particular, corrosion of decorative glassware can be quite be strong with formulations of low alkalinity, where silicates due their low stability of limited application.

Recently became the use of transition metal salts, in particular of aluminum, in US Patent 5,698,506 for use in reducing the fading of colors of decorative glassware. The use of aluminum complexes with such a citrate has been in U.S. Patent 5,624,892.

EP-A-0 560,519, DE-A-195 32 542 and EP-A-0 177 588 disclose compositions for use in automatic dishwashing machines, the water-soluble cationic or amphoteric polymers. However, they are in these documents applied to prevent staining or filming when rinse aids, or foaming to diminish. Your application for preventing fading or Corrosion is not revealed.

Brief description of the invention

It has now been found to be water-soluble, cationic or amphoteric Polymers have an unexpected and excellent degree of protection for decorative glassware, when incorporated into a machine dishwashing detergent. Such protection is by preventing fading and loss on gloss of color decor and the reduction of weight loss washed glass objects, but not limited thereto.

The The invention relates to a method for preventing bleaching or the corrosion of dishes during the washing process in an automatic dishwasher by adding a composition which is a water-soluble cationic or amphoteric polymer to the dishwasher.

• 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
  
  beschrieben, worin R¹ Wasserstoff, Hydroxyl oder einen geraden oder verzweigten C₁ bis C₃₀-Alkyl-Rest darstellt; R² Wasserstoff oder 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 pK_a-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.

The present invention further provides a method of preventing fading or corrosion of dishes during the washing process in an automatic dishwashing machine by adding to the dishwasher a composition comprising:

• a) a water-soluble cationic or amphoteric polymer, wherein the cationic polymer comprises as a monomer unit an ethylenically unsaturated compound as represented by formula I.
  
  wherein R ^{1 is} hydrogen, hydroxyl or a straight or branched C ₁ to C ₃₀ alkyl radical; R ^{2 is} hydrogen or a straight or branched C ₁ to C ₃₀ alkyl, a straight or branched C ₁ to C ₃₀ alkyl substituted aryl, aryl substituted straight or branched C ₁ to C ₃₀ alkyl radical or Polyoxyalkene condensate of an aliphatic radical; and R ^{3 represents} a heteroatom-containing alkyl or aromatic radical containing either one or more quaternary nitrogen atoms or one or more amine groups having a pK _a of about 6 or greater and a positive charge over one part having the pH interval of pH 6 to 11,
• b) 1 to 90 percent by weight of a builder.

Farther is the use of water-soluble cationic or amphoteric Polymer in a composition for addition to an automatic dishwasher for preventing fading or corrosion of dishes.

"In water soluble polymers are, provided not otherwise defined herein to include polymers which due to their molecular weight or their monomer composition soluble or at least to the extent of 0.01 wt% dispersible in distilled water at 25 ° C are. "Cationic" polymers include Polymers in which at least one of the monomer units, the make up the polymer, a cationic charge over part of the wash pH range of pH 6 to pH 11, the monomer units of which contain no cationic charges, which are non-ionic in nature. Become "amphoteric" polymers herein defined as polymers wherein at least one of the contained Monomer units have a cationic charge over part of the pH range of Contains 6-11 and at least one the monomer units contained an anionic charge over the same portion of the pH range of 6-11. The overall composition On the other hand, an amphoteric polymer may be free from other monomers, contain the cationic charge (s), monomers that are anionic Charge (s) contain monomer units that are both cationic and also contain anionic charge (s), and monomer units, the are non-ionic in nature, as long as the above the specified definition is sufficient becomes.

It It is expected that the washing pH at which this invention is applied would be either, of course in the aforementioned Proportion of the pH range of 6-11 would fall or possibly in the area would be buffered.

In Water soluble cationic or amphoteric polymers can be added to a rinse aid in which case the pH at which the polymers are their Charge should be as low as 2 would be.

Description of the invention in detail

The present composition as essential components a water-soluble cationic or amphoteric Polymer and optionally a builder containing a phosphate or May be non-phosphate builders.

phosphate builder

The compositions according to the invention, the one soluble in water Using phosphate builders typically contains this builder in a proportion of 1 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 70% by weight the composition. Specific examples of water-soluble Phosphate builders are the alkali metal tripolyphosphates, sodium, Potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, Natriumpolymeta / phosphate, wherein the degree of polymerization in the range from 6 to 21 and salts of phytic acid. Sodium or potassium tripolyphosphate is particularly preferred.

Non-phosphate builder

The compositions according to the invention, the one soluble in water Non-phosphate builders typically contain this Builder in a proportion of 1 to 90 weight percent, preferably 10 to 80 weight percent, more preferably 20 to 70 weight percent the composition. Suitable examples of no phosphorus-containing infer inorganic builder soluble in water Alkali metal carbonates, bicarbonates, sesquicarbonates, borates, -silicate, including Phyllosilicates, such as SKS-6 from 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 Phyllosilicates and zeolites, a.

organic Detergent builders can also used as a non-phosphate builder in the present invention become. examples for close organic builders Alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, Nitrilotriacetates, oxydisuccinates, alkyl and alkenyl disuccinates, Oxydiacetate, Carboxymethyloxysuccinate, Ethylenediaminetetraacetate, Tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starch, oxidized heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates, such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, Polyacrylate / polymaleate and polyacrylate / polymethacrylate copolymers, Acrylate / maleate / vinyl alcohol terpolymers, aminopolycarboxylates and Polyacetate carboxylates and polyaspartates and mixtures thereof. Such carboxylates are disclosed in US Pat. Nos. 4,144,226; 4,146,495 and US Pat 4,686,062. Alkali metal citrates, nitrilotriacetates, oxydisuccinates, acrylate / maleate copolymers and acrylate / maleate / vinyl alcohol terpolymers are particularly preferred non-phosphate builders.

Soluble in water cationic or amphoteric polymer

One soluble in water Cationic or amphoteric polymer is defined herein as polymers include, due to their molecular weight and their monomer composition soluble or at least to the extent of 0.01 wt% dispersible in distilled water at 25 ° C are. Soluble in water cationic or amphoteric polymers include polymers in which or more of the constituent monomers from the list of copolymerisable ones cationic monomers selected are. These monomer units contain a positive charge over one Part of the pH range from 6-11. A partial list of such monomers is described in "Water-Soluble Synthetic Polymers: Properties and Behavior, Volume II ", by P. Molyneux, CRC Press, Boca Raton, 1983, ISBN 0-8493-6136, herein by reference included. Other monomers can be found in the "International Cosmetic Ingredient Dictionary, 5th Edition ", edited by J. A. Wenninger and G.N. McEwen, The Cosmetic, Toiletry and Fragrance Association, Washington DC, 1993, ISBN 1-882621-06-9, incorporated herein by reference, being found. A third source of such monomers can be found in "Encyclopedia of Polymers and Thickeners for Cosmetics ", by R. Y. Lochhead and W.R. Fron, Cosmetics & Toiletries, Volume 108, May 1993, pages 95-135, incorporated herein.

beschrieben werden, worin R¹ Wasserstoff, Hydroxyl oder einen geraden oder verzweigten C₁ bis C₃₀-Alkyl-Rest darstellt; R² Wasserstoff oder 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 pK_a-Wert von etwa 6 oder größer und einer positiven Ladung über einen Teil des pH-Wert-Intervalls von pH 6 bis 11 aufweist. Solche Amin-Gruppen kön nen weiterhin als einen pK_a-Wert von etwa 6 oder größer, wie definiert von R. Laughlin in „Cationic Surfactants, Physical Chemistry", herausgegeben von D. N. Rubingh und P. M. Holland, Marcel Dekker, New York, 1991, ISBN 0-8247-8357-3, aufweisend angegeben werden.Specific monomers useful in this invention may be structurally represented as ethylenically unsaturated compounds represented by Formula I.

wherein R ^{1 is} hydrogen, hydroxyl or a straight or branched C ₁ to C ₃₀ alkyl radical; R ^{2 is} hydrogen or a straight or branched C ₁ to C ₃₀ alkyl, a straight or branched C ₁ to C ₃₀ alkyl substituted aryl, aryl substituted straight or branched C ₁ to C ₃₀ alkyl radical or Polyoxyalkene condensate of an aliphatic radical; and R ^{3 represents} a heteroatom-containing alkyl or aromatic radical containing either one or more quaternary nitrogen atoms or one or more amine groups having a pK _a of about 6 or greater and a positive charge over one part the pH interval of pH 6 to 11 has. Such amine groups can be further characterized as having a pK _a of about 6 or greater, as defined by R. Laughlin in "Cationic Surfactants, Physical Chemistry", edited by DN Rubingh and PM Holland, Marcel Dekker, New York, 1991, ISBN 0-8247-8357-3, indicating.

Examples of cationic polymers include co-poly-2-vinylpyridine and its co-poly-2-vinyl-N-alkyl quaternary pyridinium salt derivatives; Co-poly-4-vinylpyridine 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-vinylpiperidine and co-poly-2-vinylpiperidinium salt; Co-poly-4-vinylpiperidine and co-poly-4-vinylpiperidinium salt; Co-poly-3-alkyl-1-vinylimidazolium salts, such as co-poly-3-methyl-1-vinylimidazolium salts; Acrylamido and methacrylamido derivatives such as co-polydimethylaminopropylmethacrylamide, co-polyacrylamidopropyltrimethylammonium salt and co-polymethacrylamidopropyltrimethylammonium salt; Acrylate and methacrylate derivatives, such as copolydimethylaminoethyl (meth) acrylate, co-polyethanamine-N, N, N-trimethyl-2 - [(1-oxo-2-propenyl) oxy] -salt, co-polyethanaminium N, N, N-trimethyl-2 - [(2-methyl-1-oxo-2-propenyl) oxy] -salt and co-polyethanamine-N, N, N-ethyldimethyl-2 - [(2-methyl-1 oxo-2-propenyl) oxy] salt, but are not limited thereto.

Also included in the cationic polymers used for this Are suitable co-polyvinylamine and co-polyvinylammonium salt; Co-polydiallylamine, co-polymethyldiallylamine and co-polydiallyldimethylammonium salt; the ion class of internal cationic monomers as described 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 by reference, defined. This class includes co-polyethylenimine, co-poly-ethoxylated Ethyleneimine and co-poly-quaternized ethoxylated ethyleneimine; Co-poly [(dimethylimino) trimethylene (dimethylimino) hexamethylendisalz]; Co-poly [(diethylimino) trimethylene (dimethyl imino) trimethylene di-salt]; Co-poly [(dimethylimino) -2-hydroxypropylsalz]; as defined in the "International Cosmetic Ingredient Dictionary, 5th Edition ", edited by J. A. Wenninger and G.N. McEwen, a.

worin n eine Zahl von 1 bis 10000 ist und X^– jedes geeignete Gegenion, vorzugsweise Cl^–, und das quaternärisierte Polyimidazolin mit der chemischen Struktur der Formel III

worin X^– jedes geeignete Gegenion, vorzugsweise CH₃OSO₂ ^–, darstellt.Preferred cationic polymers are the cationic copolyamidoamine having the chemical structure of the formula II.

wherein n is a number from 1 to 10,000 and X ^- any suitable counterion, preferably Cl ^- , and the quaternized polyimidazoline having the chemical structure of formula III

wherein X ^{- represents} any suitable counterion, preferably CH ₃ OSO ₂ ^- .

A another class of cationic polymers suitable for this invention is, are those made of natural Sources, and cocodimethylammonium hydroxypropyloxyethylcellulose, Laurydimethylammoniumhydroxypropyloxyethylcellulose, stearyldimethylammoniumhydroxypropyloxyethylcellulose and stearyldimethylammonium hydroxyethylcellulose; Guar 2-hydroxy-3- (trimethylammonium) propylethersalz; Cellulose 2-hydroxyethyl 2-hydroxy-3- (trimethylammonio) propylethersalz lock in, but not limited thereto.

It it is also conceivable that polymers containing cationic sulfonium salts, such as co-poly-1- [3-methyl-4- (vinylbenzyloxy) phenyl] tetrahydrothiophenium chloride would also be applicable in the present invention.

The Counterion of the cationic comonomer is freely selected the halides: chloride, bromide and iodide; or of hydroxide, phosphate, Sulfate, hydrosulfate, ethylsulfate, methylsulfate, formate and acetate.

In Water soluble amphoteric polymers suitable for incorporation in the present invention are suitable also include polymers, wherein one or more of the constituent monomers are from the list of copolymerizable, internally amphoteric monomers are selected. These monomer units contain both one or more positive, as well as one or more negative charges over part of the pH range from 6-11. Such internal amphoteric monomers include those types which are formal have anionic and cationic charges, such as N, N-dimethyl-N-acetylaminoethyl (meth) acrylate. Also included are monomers, although no formal charges possess one or more resonance forms, which are in Occurrence of broken cationic and anionic charges, which are distributed within the monomer result. Monomers in of this class are by vinylpyrrolidone 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, typified. Other examples include vinyloxazolidone; Vinylmethyoxazolidon; and vinylcaprolactam.

worin R⁴, R⁵ und R⁶ unabhängig Wasserstoff, eine C₁ bis C₃-Alkyl-, eine Carboxylat-Gruppe oder eine Carboxylat-Gruppe, substituiert mit einem linearen oder verzweigten Heteroatom-enthaltenden C₁ bis C₃₀-Alkyl- oder aromatischen Rest, einen Heteroatom-enthaltenden Rest oder ein Polyoxyalken-Kondensat eines aliphatischen Rests darstellen.The weight fraction of the cationic or amphoteric polymer composed of the cationic or amphoteric monomer units described above may be in the range of 1 to 100%, preferably 10 to 100%, and more preferably 15 to 80% of the entire polymer. The remaining monomer units comprising the cationic or amphoteric polymer are selected from the class of anionic monomers and the class of nonionic monomers or just from the class of nonionic monomers. In the preceding class, the polymer is an amphoteric polymer, while in the latter case it may be a cationic polymer provided that there are no amphoteric co-monomers. The anionic monomers comprise a class of monounsaturated compounds having a negative charge over the portion of the pH range of pH 6 to 11 wherein the cationic monomers have a positive charge. The nonionic monomers comprise a class of monounsaturated compounds that are uncharged over the pH range of pH 6 to 11 wherein the cationic monomers have a positive charge. It is expected that the wash pH to which this invention would be applied would either naturally fall within the aforementioned part of the pH range of 6 to 11 or be optionally buffered in the range. A preferred class of both anionic and nonionic monomers are the vinyl (ethylenically unsaturated) substituted compounds corresponding to formula IV.

wherein 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 linear or branched heteroatom-containing C ₁ to C ₃₀ alkyl or represent an aromatic radical, a heteroatom-containing radical or a polyoxyalkene condensate of an aliphatic radical.

The class of anionic monomers is represented by the compound described by Formula IV wherein at least one of R ⁴ , R ⁵ or R ^{6 is} a carboxylate, substituted carboxylate, phosphonate, substituted phosphonate, sulfate, substituted sulfate, Sulfonate or substituted sulfonate group. Preferred monomers in this class include α-ethacrylic acid, α-cyanoacrylic acid, β, β-dimethacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, acrylic acid, ethylidynetic acid, propylidynetic acid, crotonic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, β- Styrylacrylic acid (1-carboxy-4-phenylbutadiene-1,3), citraconic acid, glutaconic acid, aconitic acid, α-phenylacrylic acid, β-acryloxypropionic acid, citraconic acid, vinylbenzoic acid, N-vinylbernsteinamidic acid and mesaconic acid are, but are not limited thereto. Also included in the list of preferred monomers are co-polystyrenesulfonic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryloyloxypropane-1-sulfonic acid, 3- (vinyloxy) propane-1-sulfonic acid, ethylene sulfonic acid, vinylsulfuric acid, 4-vinylphenylsulfuric acid, ethylenephosphonic acid and vinyl phosphoric acid. Particularly preferred Mo monomers include acrylic acid, methacrylic acid and maleic acid. The polymers usable in this invention may contain the above monomers and the alkali metal, alkaline earth metal and ammonium salts thereof.

The class of nonionic monomers is represented by the compounds of formula IV wherein none of R ⁴ , R ⁵ or R ⁶ contains any of the radicals mentioned above containing the negative charge. Preferred monomers in this class include vinyl alcohol; vinyl acetate; vinyl methyl ether; vinyl ethyl ether; acrylamide; Methacrylamide and other modified acrylamides; propionate; Alkyl acrylates (esters of acrylic or methacrylic acid); and hydroxyalkyl acrylate esters, but are not limited thereto. A second class of nonionic monomers includes co-polyethylene oxide, co-polypropylene oxide, and co-polyoxymethylene. A third class of nonionic monomers includes naturally derived materials such as hydroxyethyl cellulose.

The average molecular weight of the polymers of this invention is in the range of about 1000 to about 10 ⁷ , with the preferred range of molecular weight depending on the polymer composition. An effective amount of the polymer is 0.1 to 20%, preferably 0.5 to 10%, most preferably 1 to 5%, all by weight of the total detergent formulation.

Optional components

In addition to The essential components described hereinbefore may be Compositions of the invention also be formulated as detergent compositions conventional Ingredients, preferably selected from enzymes, buffering systems, Oxygen bleaching systems, surfactants, heavy metal ion sequestering agents, Anti-scaling agents, corrosion inhibitors and anti-foaming agents, include.

enzymes

enzymes which facilitate the removal of contaminants from a substrate can, can also in a combined amount of up to about 10% by weight of the active enzyme present. Such enzymes include proteases, amylases, lipases, Esterases, cellulases, pectinases, lactases and peroxidases, such as conventionally incorporated in detergent compositions.

preferred commercially available Close Protease Enzymes those marketed under the trade names Alcalase, Savinase and Esperase from Novo Industries A / S (Denmark); and those sold by Genencor International under the trade name Purafect OxP, a. Preferred commercially available amylases include those alpha-amylases, sold under the trade names Termamyl and Duramyl from Novo Industries and those distributed by Genencor International the trade name Purafect OxAm, a. A preferred lipase is commercially from Novo Industries under the trade name Lipolase available.

Buffering systems

The buffering systems can present to a pH from about 6 to about 11 in the wash leach. Materials, the for the buffering system is selected could be, shut down soluble in water Alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, phyllosilicates, such as SKS-6 from Hoechst, Metasilicate, phytic acid, Citric acid, Borate and crystalline and amorphous aluminosilicates and mixtures thereof one. Preferred examples include sodium and potassium carbonate, Sodium and potassium bicarbonates, borates and silicates, including phyllosilicates, one.

Oxygen bleaching systems

The optionally, the present invention may be an oxygen bleaching source included, selected from the following:

Peroxy bleach

• i) Peroxybenzoesäure und Ring-substituierte Peroxybenzoesäuren, beispielsweise Peroxy-α-naphthoesäure, und Magnesiummonoperoxyphthalat.
• ii) aliphatische und substituierte aliphatische Monoperoxysäuren, beispielsweise Peroxylaurinsäure, Peroxystearinsäure, ε-Phthalimido-peroxyhexansäure und o-Carboxybenzamidoperoxyhexansäure, N-Nonylamidoperadipinsäure und N-Nonylamidoperbernsteinsäure.
• iii) kationische Peroxysäure, wie jene, beschrieben in US 5 422 028 , 5 294 362 und 5 292 447 , Oakes et al., US S/N 08/738 504 (WO-A-97/16515) und US S/N 08/210 973 (WO-A-94/21605), Oakes et al..
• iv) Sulfonylperoxysäuren, wie Verbindungen, beschrieben in US 5 039 447 (Monsanto Co.) Typische hierin verwendbare Diperoxysäuren schließen Alkyldiperoxysäuren und Aryldiperoxysäuren ein, wie:
• v) 1,12-Diperoxydodecandisäure
• vi) 1,9-Diperoxyazelainsäure
• vii) Diperoxybrassylsäure; Diperoxysebacinsäure und Diperoxy-isophthalsäure
• viii) 2-Decyldiperoxybutan-1,4-disäure
• ix) N,N¹-Terephthaloyl-di(6-aminopercapronsäure).

The oxygen bleaches of the compositions include organic peroxyacids and diacyl peroxides. Typical monoperoxy acids useful herein include alkyl peroxyacids and aryl peroxyacids such as:

• i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example peroxy-α-naphthoic acid re, and magnesium monoperoxyphthalate.
• ii) aliphatic and substituted aliphatic monoperoxy acids, for example peroxylauric acid, peroxystearic acid, ε-phthalimido-peroxyhexanoic acid and o-carboxybenzamidoperoxyhexanoic acid, N-nonylamidoperadipic acid and N-nonylamido-succinic acid.
• iii) cationic peroxyacid, such as those described in U.S. Pat US 5,422,028 . 5,294,362 and 5,292,447 Oakes et al., US Ser. Nos. 08 / 738,504 (WO-A-97/16515) and US Ser. No. 08 / 210,973 (WO-A-94/21605), Oakes et al.
• iv) sulfonyl peroxyacids, such as compounds described in US 5 039 447 (Monsanto Co.) Typical diperoxyacids useful herein include alkyl diperoxyacids and aryl diperoxyacids, such as:
• v) 1,12-diperoxydodecanedioic acid
• vi) 1,9-Diperoxyazelaic acid
• vii) diperoxybrassic acid; Diperoxysebacic acid and diperoxy-isophthalic acid
• viii) 2-decyldiperoxybutane-1,4-diacid
• ix) N, N ¹ -terephthaloyl-di (6-aminopercaproic acid).

One Typical diacyl peroxide useful herein includes dibenzoyl peroxide one.

inorganic Peroxygen compounds are also for the present invention suitable. Examples of materials usable in this invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate and percarbonate.

preferred Peroxy bleaches include ε-phthalimido-peroxyhexanoic acid, o-carboxybenzamidoperoxyhexanoic acid and Mixtures of one.

The organic peroxyacid is present in the composition in such an amount that the Proportion of organic peroxyacid in the washing solution about 1 ppm to about 300 ppm AvOx, preferably about 2 ppm to about 200 ppm AvOx, is.

The Oxygen bleaching agent can be incorporated directly into the formulation be or can be in any number of encapsulation techniques be encapsulated.

One The preferred encapsulation process is disclosed in U.S. Patent 5,200,236, filed by Lang et al., incorporated herein by reference. In the patented Process, the bleach is used as the core in a paraffin wax material encapsulated with a melting point of about 40 ° C to 50 ° C. The wax coating has a thickness of 100 to 1500 microns.

Bleach precursors

suitable peracid precursors for peroxy bleach compounds were detailed described in the literature, including GB 836 988, 855 735, 907,356, 907,358, 907,950, 1,003,310 and 1,246,339, U.S. Patent 3 332 882 and 4 128 494.

typical examples for Precursors are polyacylated alkylenediamines, such as N, N, N ', N'-tetraacetylethylenediamine (TAED) and N, N, N ', N'-tetraacetylmethylenediamine (TAMD); acylated glycolurils such as tetraacetylglycoluril (TAGU); Triacetyl cyanurate, sodium sulfophenyl ethyl carbonic acid ester, Sodium acetyloxybenzenesulfonate (SABS), sodium nonanoyloxybenzenesulfonate (SNOBS) and choline sulfophenyl carbonate. Peroxybenzoic precursors are known in the art, for example as described in GB-A-836988. Examples of suitable Precursors are phenyl benzoate; p-nitrobenzoate; Benzoic acid o-nitrophenyl ester; Benzoic acid o-carboxy-phenyl ester; Benzoic acid p-bromophenyl; Sodium or potassium benzoyloxybenzenesulfonate; and benzoic anhydride.

preferred Peroxygen bleach precursors are sodium p-benzoyloxybenzenesulfonate, N, N, N ', N'-tetraacetylethylenediamine, Sodium nonanoyloxybenzenesulfonate and choline sulfophenyl carbonate.

The peroxygen bleach precursors are present in the composition in an amount of from about 1 to about 20 weight percent, preferably from about 1 to about 15 weight percent, more preferably from about 2 to about 15 weight percent. In order to release a functional peroxygen bleach as a precursor, a source of hydrogen peroxide is required. The hydrogen peroxide source is preferably a compound which releases hydrogen peroxide upon dissolution. Preferred sources of hydrogen peroxide are sodium perborate, either as the mono- or tetrahydrate and sodium percarbonate. The hydrogen peroxide source, when included in these compositions, is present at a level of from about 1% to about 40%, preferably from about 2% to about 30%, more preferably from about 4% to about 25% by weight.

Bleach Catalyst

A effective amount of a bleach catalyst may be used in the invention also present. A number of organic catalysts are also available, such as the sulfonimines, as described in U.S. Patent Nos. 5,041,232, 5,047,163 and U.S. Patent Nos. 5,416,163; 5,463,115.

Transition metal bleach catalysts are also usable, especially those based on manganese, iron, Cobalt, titanium, molybdenum, Nickel, chromium, copper, ruthenium, tungsten and mixtures thereof. These shut down simply soluble in water Salts, such as those of iron, manganese and cobalt, as well as catalysts, containing the complex ligands.

Suitable examples of manganese catalysts containing organic ligands are described in US Pat. Nos. 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 Patent Application Publication Nos. 544,440, 544,490, 549,271 and 549,272. Preferred examples of these catalysts include Mn ^IV ₂ (μ-o) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (μ-o) ₁ (μ -OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (CIO ₄ ) ₂ , Mn ^IV ₄ (μ-O) ₆ (1,4,7-triazacyclononane) ₄ (CIO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (μ-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 described in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.

Iron- and manganese salts of aminocarboxylic acids are generally useful herein, including iron and manganese aminocarboxylate salts, bleaching in the photographic color-processing areas are disclosed. A particularly useful transition metal salt is from Ethylenediaminedi succinate and a complex of this ligand with Derived iron or manganese.

One another type of bleach catalyst as described in US Pat. 5,114,606 discloses is a more soluble in water Complex of manganese (II), (III) and / or (IV) with a ligand, which is a non-carboxylate polyhydroxy compound having at least three successive groups represents C-OH. Preferred ligands include sorbitol, Iditol, dulcitol, mannitol, xylitol, arabitol, adonite, mesoerythritol, meso-inositol, Lactose and mixtures thereof. Particularly preferred is sorbitol.

US Pat. 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. Other examples include Mn-gluconate, Mn (CF ₃ SO ₃ ) ₂ , and binuclear Mn complexed with 4-N-dentate and 2-N-dentate ligands, including [bipy ₂ Mn ^III (μ-O) ₂ Mn ^IV bipy ₂ ] - (ClO ₄ ) ₃ , a.

Other Bleach catalysts are described, for example, in the European patent application, Pub. 408,131 (cobalt complexes), 384,503 and 306,089 (metallo-porphyrins), US Pat. 4 728 455 (manganese / polydentate Ligand), U.S. Pat. 4,711,748 (absorbed manganese on aluminosilicate), US Pat. 4,601,845 (aluminosilicate support of manganese, zinc or magnesium salt), US Pat. 4,626,373 (Manganese / Ligand), U.S. Pat. 4,119,557 (ferric complex), US Pat. 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations) and U.S. Pat. 4,728,455 (manganese gluconate) described.

Useful cobalt-based catalysts are described in WO 96/23859, WO 96/23860 and WO 96/23861 and US Pat. 5 559 261. WO 96/23860 describes cobalt catalysts of the type [Co _n L _m X _p ] ^z Y _z , wherein L represents an organic ligand molecule containing more than one heteroatom selected from N, P, O and S; X represents a coordinating species; n is preferably 1 or 2; m is preferably 1 to 5; p is preferably 0 to 4 and Y is a counterion. An example of such a catalyst is N, N'-bis (salicylidene) ethylenediamine cobalt (II). Other cobalt catalysts described in these applications are based on Co (III) complexes with ammonia and 1-, 2-, 3- and 4-dentate ligands such as [Co (NH ₃ ) ₅ OAc] ²⁺ with Cl ^- , OAc ^- , PF ₆ ^- , SO ₄ ⁼ , and BF ₄ ^- anions.

Certain transition metal-containing bleach catalysts can be prepared in situ by reaction of a transition metal salt with a suitable chelating agent, for example, a mixture of manganese sulfate and ethylenediamine disuccinate. Highly colored transition metal-containing Bleach catalysts can be processed along with zeolites to reduce color degradation.

If in the present case, the bleach catalyst is typically used with a content of about 0, 0001 to about 10 weight percent, preferably about 0.001 to about 5 weight percent incorporated.

surfactants

Optional a surfactant can be selected from the list, including anionic, nonionic, cationic, amphoteric and zwitterionic Surfactants and mixtures of these surfactants in the machine dishwashing formulation be included. Such surfactants are in the detergent field well known and become detailed in "Surface Active Agents and Detergents ", Volume 2 of Schwartz, Perry and Birch, Interscience Publishers, Inc. Described in 1959.

preferred Surfactants are one or a mixture of:

Anionic surfactant (s)

anionic synthetic detergents can are broadly described as surface-active compounds with one or more negatively charged functional groups. A important class of anionic compounds are those in water soluble Salts, in particular the Alkalime tallsalze, of organic sulfur reaction products with in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms, and a rest, selected from the group consisting of sulfonic and sulfuric acid ester residues.

Primary alkyl sulfates

R ⁷ OSO ₃ M wherein R ^{7 represents} a primary alkyl group of 8 to 18 carbon atoms and M represents 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 alkyl groups R ^{7 have} a chain length of 8 to 18 carbon atoms. This will be the case when R ^{7 represents,} for example, coconut alkyl. The solubilizing cation can be a range of cations that are generally monovalent and exhibit water solubility. In particular, an alkali metal, in particular sodium, is conceivable. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.

alkyl ether

R ⁷ O (CH ₂ CH ₂ O) _n SO ₃ M wherein R ^{7 represents} a primary alkyl group of 8 to 18 carbon atoms, n has an average value in the range of 1 to 6, and M represents 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 alkyl groups R ^{7 have} a chain length of 8 to 14 carbon atoms. This will be the case when R ^{7 represents,} for example, coconut alkyl. Preferably, n has an average of 2 to 5.

fatty acid ester

R ⁸ CH (SO ₃ M) CO ₂ R ⁹ wherein R ^{8 represents} an alkyl group having 6 to 16 carbon atoms, R ^{9 represents} an alkyl group having 1 to 4 carbon atoms and M represents a solubilizing cation.

The group R ⁸ may have a mixture of chain lengths. Preferably, at least two-thirds of these groups have from 6 to 12 carbon atoms. This will be the case when the unit R ⁸ CH (-) CO ₂ (-) is derived from, for example, a coconut source. It is preferred that R ^{9 is} a straight chain alkyl, especially methyl or ethyl.

alkylbenzenesulfonates

R ¹⁰ ArSO ₃ M wherein R ^{10 represents} an alkyl group of 8 to 18 carbon atoms, Ar represents a benzene ring (C ₆ H ₄ ), and M represents 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 having from 8 to 22 carbon atoms, preferably from 12 to 16 carbon atoms, in the alkyl chain. These surfactants are commercially available as Hostapur SAS available from Hoechst Celanese.

olefin having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. U.S. Patent 3,332,880 a description for suitable olefin sulfonates.

anionic Surfactants based on organic phosphate 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 alkylene carboxylate moiety attached with a terminal hydroxyl group of the nonionic surfactant to an ether linkage. Counterions too these salts for all of the preceding ones those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types be.

Particularly preferred anionic surfactants are the fatty acid ester sulfonates of the formula: R ⁸ CH (SO ₃ M) CO ₂ R ⁹ wherein the moiety R ⁸ CH (-) CO ₂ (-) is derived from a coconut source and R ^{9 is} either methyl or ethyl; primary alkyl sulfates having the formula: R ⁷ OSO ₃ M wherein R ^{7 represents} a primary alkyl group having 10 to 18 carbon atoms and M represents a sodium cation; and paraffin sulfonates, preferably having from 12 to 16 carbon atoms for the alkyl moiety.

Nonionic surfactants

nonionic Surfactants can largely as surface-active Compounds with one or more uncharged hydrophilic substituents To be defined. A major class of nonionic surfactants are those compounds formed by the condensation of alkylene oxide groups with an organic hydrophobic material, aliphatic or May be alkyl-aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical, which is hydrophobic with each individual Group is condensed, can easily be adjusted to one soluble in water Connection with a desired degree of balance between hydrophilic and hydrophobic elements. illustrative, however, non-limiting examples of various suitable ones nonionic surfactant types are:

Polyoxyalkylene condensates of aliphatic carboxylic acids, whether linear or branched chain and unsaturated or saturated, in particular ethoxylated and / or propoxylated aliphatic acids which contain from about 8 to about 18 carbon atoms in the aliphatic chain and about 2 to about 50 ethylene oxide and / or propylene oxide units include. Suitable carboxylic acids include "coconut" fatty acids (derived from Coconut oil) containing on average about 12 carbon atoms, "tallow" fatty acids (derived of tallow class fats), which average about 18 carbon atoms contain, palmitic acid, Myristic acid, stearic acid and lauric acid one.

Polyoxyalkylene condensates of aliphatic alcohols, whether linear or branched and unsaturated or saturated, in particular ethoxylated and / or propoxylated aliphatic alcohols, which contain from about 6 to about 24 carbon atoms and about 2 to about include about 50 ethylene oxide and / or propylene oxide units. Suitable alcohols include "coconut" fatty alcohol, "tallow" fatty alcohol, lauryl alcohol, Myristyl alcohol and oleyl alcohol.

Ethoxylated fatty alcohols can be used singly 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 are 6 to 20 carbon atoms. Notably, the group R ^{11 may have} chain lengths in a range of 9 to 18 carbon atoms.

The mean of n should be at least 2. The number of ethylene oxide residues can be a statistical distribution around the mean. However, as is known, the distribution can be influenced by the production process or altered by fractionation after ethoxylation. Particularly preferred ethoxylated fatty alcohols have a group R ¹¹ having 9 to 18 carbon atoms while n is 2 to 8.

worin R¹² einen linearen Alkylkohlenwasserstoff-Rest mit im Durchschnitt 6 bis 18 Kohlenstoffatomen darstellt, R¹³ und R¹⁴ jeweils lineare Alkylkohlenwasserstoffe mit etwa 1 bis etwa 4 Kohlenstoffatomen darstellen, x eine ganze Zahl von 1 bis 6 ist, y eine ganze Zahl von 4 bis 20 ist und z eine ganze Zahl von 4 bis 25 ist.Also included in this category are nonionic surfactants having the formula:

wherein R ^{12 is} a linear alkyl hydrocarbon radical having on average 6 to 18 carbon atoms, R ¹³ and R ^{14 are} each linear alkyl hydrocarbons having from about 1 to about 4 carbon atoms, x is an integer from 1 to 6, y is an integer of 4 is up to 20 and z is an integer from 4 to 25.

worin R¹⁵ einen linearen, aliphatischen Kohlenwasserstoff-Rest mit etwa 4 bis etwa 18 Kohlenstoffatomen, einschließlich Gemische davon, darstellt; und R¹⁶ einen linearen, aliphatischen Kohlenwasserstoff-Rest mit etwa 2 bis etwa 26 Kohlenstoffatomen, einschließlich Gemische davon, darstellt; j eine ganze Zahl mit einem Wert von 1 bis etwa 3 ist; k eine ganze Zahl mit einem Wert von 5 bis etwa 30 ist; und l eine ganze Zahl mit einem Wert von 1 bis etwa 3 ist. Besonders bevorzugt sind Zusammensetzungen, worin j 1 ist, k etwa 10 bis etwa 20 ist und l 1 ist. Diese Tenside werden in WO 94/22800 beschrieben. Andere bevorzugte nichtionische Tenside sind lineare Fettalkoholalkoxylate mit einer verkappten endständigen Gruppe, wie in U.S. 4 340 766 BASF beschrieben. Besonders bevorzugt ist Plurafac LF403 von BASF.A preferred nonionic surfactant of the above formula is Poly-Tergent SLF-18, a registered trademark of Olin Corporation, New Haven, Connecticut, having a composition of the above formula wherein R ^{12 is} a linear C ₆ -C ₁₀ alkyl mixture, R ¹³ and R ^{14 is} methyl, x is on average 3, y is on average 12 and z is on average 16. Another preferred nonionic surfactant is:

wherein R ^{15 represents} a linear aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms, including mixtures thereof; and R ^{16 represents} 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 1 to about 3; k is an integer having a value of 5 to about 30; and l is an integer having a value of 1 to about 3. Particularly preferred are compositions wherein j is 1, k is from about 10 to about 20, and l is 1. These surfactants are described in WO 94/22800. Other preferred nonionic surfactants are linear fatty alcohol alkoxylates having a capped terminal group as described in US Pat. No. 4,340,766 to BASF. Particularly preferred is Plurafac LF403 from BASF.

Another nonionic surfactant included in this category are compounds of the formula: R ¹⁷ - (CH ₂ CH ₂ O) _q H wherein R ^{17 is} a linear or branched C ₆ -C ₂₄ alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably, R ^{17 is} a linear C ₈ -C ₁₈ alkyl mixture and q is a number from 2 to 15.

polyoxyethylene or polyoxypropylene condensates of alkylphenols, whether linear or labeledchain and unsaturated or saturated, containing about 6 to 12 carbon atoms and about 2 to about Incorporate 25 moles of ethylene oxide and / or propylene oxide.

Polyoxyethylene derivatives sorbitan mono-, di- and tri-fatty acid esters, wherein the fatty acid component has between 12 and 24 carbon atoms. The preferred polyoxyethylene derivatives are sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, Sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, Sorbitan tristearate, sorbitan monooleate and sorbitan trioleate. The Polyoxyethylene chains can between about 4 and 30 ethylene oxide units, preferably about 10 to 20, included. The sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains, depending on whether they are mono-, Di- or tri-acid esters represent.

Polyoxyethylene polyoxypropylene block copolymers with the 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 represent the corresponding polyethylene oxide and polypropylene oxide blocks of the polymer. The polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer. The material preferably has a molecular weight between about 1000 and 15000, more preferably about 1500 to about 6000. These materials are well known in the art. They are available under the trademarks "Pluronic" and "Pluronic R", a product of BASF Corporation.

Amine oxides of the formula

R ¹⁸ R ¹⁹ R ²⁰ N = O wherein R ¹⁸ , R ¹⁹ and R ^{20 represent} saturated aliphatic radicals or substituted saturated aliphatic radicals. Preferably, amine oxides are those wherein R ^{18 is} an alkyl chain having from 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 containing from about 6 to about 14 Represent carbon atoms and R ^{20 represents} a methyl or ethyl group.

amphoteric synthetic detergents - can be largely are described as derivatives of aliphatic tertiary amines, wherein the aliphatic radical may be straight-chain or branched and wherein one of the aliphatic substituents is about 8 to about Contains 18 carbon atoms and an anionic water-solubilizing group, d. H. Carboxy, sulfo, sulfato, phosphato or phosphono contains. Examples for connections, which fall into this definition are sodium 3-dodecylaminopropionate and Natium 2-dodecylaminopropansulfonat.

zwitterionic synthetic detergents - can be largely as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds wherein the aliphatic radical may be straight or branched and wherein one of the aliphatic Substituent contains from about 8 to about 18 carbon atoms and one an anionic water-solubilizing group, for example Carboxy, sulfo, sulfato, phosphato or phosphono contains. These Connections become common referred to as betaine. In addition Alkylbetainen alkylamino and Alkylamidobetaines within this invention.

Alkyl glycosides

R ²¹ O (R ²² O) _n (Z ¹ ) _p wherein R ^{21 is} a monovalent organic radical (for example, a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) of about 6 to about Contains 30 (preferably about 8 to 18 and more preferably about 9 to about 13) carbon atoms; R ^{22 is} a divalent Koh hydrogen radical containing from 2 to about 4 carbon atoms, such as ethylene, propylene or butylene (most preferably the moiety (R ²² O) _{n represents} repeating units of ethylene oxide, propylene oxide and / or random or block combinations thereof); n is a number with an average of 0 to about 12; Z ^{1 represents} a unit derived from a reducing saccharide containing 5 or 6 carbon atoms (more preferably a glucose unit); and p is a number having an average of from 0.5 to about 10, preferably from about 0.5 to about 5.

Examples of commercially available materials from Henkel Kommanditgesellschaft Aktien Dusseldorf, Germany, include APG 300, 325 and 350, where R ^{21 is} C ₉ -C ₁₁ , n is 0 and p is 1.3, 1.6 and 1.8-2, respectively , 2 is; APG 500 and 550, wherein R ^{21 is} C ₁₂ -C ₁₃ , n is 0 and p is 1.3 or 1.8-2.2, respectively; and APG 600, wherein R ^{21 is} C ₁₂ -C ₁₄ , n is 0 and p is 1.3.

While esters are particularly considered by glucose, it is envisaged that corresponding Materials based on other reducing sugars, such as galactose and mannose, are also suitable.

Especially preferred nonionic surfactants are polyoxyethylene and polyoxypropylene condensates of linear aliphatic alcohols.

Of the preferred range of surfactant is about 0.5 to about 30 weight percent, more preferably about 0.5 to 15 percent by weight of the composition.

masking agents

The Detergent compositions herein may also optionally be used or more transition metal chelating agents contain. These components can also have calcium and magnesium chelating capacity, however, they preferably show selectivity for binding heavy metal ions. Such Chelating agents can from the group consisting of aminocarboxylates, aminophosphates, polyfunctional substituted aromatic chelating agents and mixtures in it, selected become. Without wishing to be bound by any theory, will assumed that the advantage of these materials due to Part of pronounced ability Iron and manganese ions from washing solutions through the formation of soluble Removing chelates is.

When optional aminocarboxylates useful in chelating agents include ethylenediamine tetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, Triethylenetetramine hexaacetates, diethylenetriamine pentaacetate, ethylenediamine disuccinate and ethane diglycinates, alkali metal, ammonium and substituted Ammonium salts in it and mixtures in it.

Amino phosphonates are also for use as chelating agents in the compositions of the invention suitable if at least low levels of total phosphorus in Detergent compositions are allowed and include ethylenediaminetetrakis (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably these aminophosphonates contain no alkyl or alkenyl groups with more than about 6 carbon atoms.

polyfunctionally substituted aromatic chelating agents are also known in the Compositions useful herein. See U.S. Patent 3,812,044, filed May 21, 1974, Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

If In general, these chelating agents are about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if used, the chelating agents from about 0.1% to about 5.0% by weight of such compositions include.

Antiscalants

Scale formation on dishes and machine parts can be a major problem. It can grow from a variety of sources, but it arises primarily from the precipitation of either alkaline earth metal carbonates, phosphates or silicates. Calcium carbonate and phosphates are the most significant problem. To alleviate this problem, ingredients to minimize scaling may be incorporated into the composition. These include polyacrylates of molecular weight from 1000 to 400000, examples of which are given by Rohm & Haas, BASF and Alco Corp. and polymers based on acrylic acid combined with other units. These include acrylic acid, combi with maleic acid, such as Sokalan CPS and CP7, supplied by BASF or Acusol 479N, obtained from Rohm &Haas; with methacrylic acid, such as colloid 226/35, obtained from Rhone-Poulenc; with phosphonate, such as Casi 773, purchased from Buckman Laboratories; with maleic acid and vinyl acetate, such as polymers, obtained from Hüls; with acrylamide; with sulfophenol methallyl ether, such as Aquatreat AR 540, supplied by Alco; with 2-acrylamido-2-methylpropanesulfonic acid, such as Acumer 3100, obtained from Rohm & Haas or as K-775, obtained from Goodrich; with 2-acrylamido-2-methylpropanesulfonic acid and sodium styrenesulfonate, such as K-798, obtained from Goodrich; with methyl methacrylate, sodium methallyl sulfonate and sulfophenol methallyl ethers, such as Alcoperse 240, supplied by Alco; Polymaleates, such as Belclene 200, purchased from FMC; Polymethacrylates, such as Tamol 850, purchased from Rohm &Haas;polyaspartates;ethylenediamine; Organopolyphosphonic acids and their salts, such as the sodium salts of aminotri (methylenephosphonic acid) and ethane-1-hydroxy-1,1-diphosphonic acid. The anti-scaling agent, if present, is included in the composition from about 0.05 to about 10 weight percent, preferably 0.1 to about 5 weight percent, more preferably about 0.2 to about 5 weight percent.

corrosion inhibitors

The composition may optionally contain corrosion inhibitors to reduce the tarnishing of silverware. Such inhibitors include benzotriazole and other members of the azole family. Particularly preferred are azoles, including imidazoles. Additional anti-tarnish 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-paraffinic oil organic agents, such as fatty esters of monohydric or polyhydric alcohols, as described in U.S. Pat EP 0 690 122 A2 claimed, a.

Anti-foaming agents

The compositions according to the invention, when to use for machine dishwashing formulated, preferably comprise an antifoam system. suitable Antifoam systems for use herein may be essentially any known antifoam compounds include, for example Silicone antifoam, silicone oil, Mono- and distearyl acid phosphates, mineral oil and 2-alkyl and alkanolic antifoam compounds. Even if the machine dishwashing composition only defoaming Contains surfactants, supports the antifoaming agent while minimizing foam, the food soil can generate. The compositions may be from 0.02 to 2% by weight 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) described.

Form of the composition

The Machine dishwashing compositions according to the invention can in any desired form formulated as powders, granules, pastes, liquids, Gels, solids or tablets. As an example, the method for preparing a granule, preparing a slurry of above-identified ingredients and drying of the mixture with the help of suitable equipment, like a turbine dryer (turbo granulation dryer from Vomm-Turbo Technology, Vomm Impianti E Processi SrL, Milan, Italy). Also, the method may include preparing the slurry, spray-drying the slurry conventional Techniques using a spray tower wherein the slurry is sprayed and sprayed in a hot air stream is dried, followed by restructuring of the obtained powder, optionally after milling, in a granulation process (Lödige Recycler and Lödige Ploughshare). In a particularly preferred method gets the slurry sprayed on fine (recycled) particles and then dried under Formation of stepwise growth of co-granules. Another attractive possibility is it, the slurry in a rotating drum granulator and dry the slurry to spray recirculating, fine materials to build up coarser Particles. These particles will be either simultaneously or sequentially dried to a co-granules with a more homogeneous distribution of moisture to surrender than those by the application of a turbine dryer is obtained.

The method of making a tablet may include mixing the above-identified ingredients, transferring the mixture to the tablet nozzle, and compacting at a compaction pressure of from about 3 x 10 ⁶ kg / m ² to about 3 x 10 ⁷ kg / m ² . It may preferably be pre-granulated of any or all of the ingredients, optionally with surfactant to increase the dissolution to yield granules of size 100-2000 microns and mixing them together with any remaining material rial before compaction. Another possibility is to precoat the granules with any liquid component of the composition via, for example, a fluidized bed, pan coating or roller drum to produce encapsulations. The encapsulants are then compressed at a compaction pressure of about 1 x 10 ⁶ kg / m ² to about 3 x 10 ⁷ kg / m ² .

machine dishwashing

One preferred machine dishwashing method includes treating solid objects selected from Tableware, glassware, hollowware, silverware and cutlery and blends of it, with an aqueous one solution solved with it or dispersing an effective amount of a machine dishwashing composition according to the invention. An effective amount of the machine dishwashing composition means 8 g to 60 g of the composition, dissolved or dispersed in one wash solution with the volume 3 to 10 liters, as typical product dosing and wash solution volume, the usual in conventional machine dishwashing be applied.

The The following examples serve for a better understanding of Distinguishing this invention from the prior art and explaining its Embodiments. Unless otherwise indicated, all parts, percentages and Parts referred to herein by weight.

Examples 1-2

Maschinengeschirrspülwaschmittelformulierungen are prepared as detailed below. All Numbers refer to parts by weight. Example 1 is a granular product which is based on a phosphate builder, while Example 2 is a liquid which is based on a non-phosphate builder.

Example 3

The The following cationic or amphoteric polymers have been used in the Formulations of Examples 1-2 above.

key

AA

acrylic acid

AT THE

acrylamide

APTAC

acrylamidopropyltrimethyl

DMDAAC

dimethyldiallylammonium

DMIHPC

Dimethylimino 2 hydroxypropylchlorid

DQPDMS

diquaternary polydimethylsiloxane

EEDMOPO (ES or C)

Ethanaminium N, N, N-ethyldimethyl-2 - [(2-methyl-1-oxo-2-propenyl) oxy] ethyl or chloride salt

ETMOPO (ES or C)

Ethanaminium-N, N, N-trimethyl-2 - [(2-methyl-1-1-oxo-2-propenyl) oxyl] ethyl sulfate or salt

HEC

hydroxyethyl

HPA

hydroxypropyl acrylate

IAE

Itaconic acid, alkyl ethoxylate ester

MAPTAC

Methylacrylamidopropyltrimethylammoniumchlorid

MVI

methylvinylimidazolium

VP

vinylpyrrolidone

Example 4

The Effect of a machine dishwashing composition according to example 1 of the present invention on glass decore corrosion was by means of To run a fifteen-wash procedure determines in which the objects to be washed on fading and loss were rated on gloss of color decor.

The fifteen wash procedure consisted of the following: a row of four 8 ounce household jars with brightly colored overlaid glass patterns representing garden tools, clam shells, fruit and flowers, and a pair of 8 inch dinner plates that are lightly colored, overlaid glass shutters in red and yellow, were placed in a Miele Super-Electronic G 595 SC dishwashing machine. The glasses were placed on the top shelf and the dinner plates were placed on the bottom shelf. The Universal 65 ° C wash program was selected and the wash program performed using soft water (0 ° FH) and 40 grams of the machine dishwashing composition comprising Example 1. Each row of items to be washed was passed through fifteen successive courses of the same formulation, after which the items were removed and evaluated for glass decoctional corrosion. The classification was carried out by two expert groups on each item and the results were averaged for the plates, respectively glasses. The rating was by visual examination according to the following six-point scale:
0 = no fading, identical to unwashed article
1 = very faint, noticeable only when referring to the unwashed article
2 = bleaching is noticeable, but colors are still bright and shiny
3 = medium fading, reduced color intensity content
4 = severe fading, pale, washed out colors
5 = very fade, color substantially completely removed

As shown by the above example, water-soluble copolymers containing cationic monomer groups significantly reduce the fading of overlay patterns on plates and glasses in terms of control. Similarly, water-soluble copolymers containing amphoteric monomer groups, such as Acrylidone 1001, also significantly reduce the fading of overlay patterns. However, water-soluble copolymers that do not contain such monomer groups as 18,293-1, 41,640-1 and 41,911-7 do not provide any improvement in control and, in some instances, bleach enhancement. Likewise, water-soluble copolymers containing insufficient cationic monomer groups do not provide the optimum level of fade protection. As an example, EXP 2072 and EXP 2075 each contain 9 weight percent of the cationic monomer DMDAAC and do not release the same protection as copolymers with higher DMDAAC levels, such as FlocAid 19, FlocAid 34, Merquant 280 or Merquant 295.

This Example shows that the weight fraction of the cationic or amphoteric polymers selected from those described above is composed of cationic or amphoteric monomer units, may range from 1 to 100%, but preferably in the range from 10 to 100%, and more preferably in the range of fifteen to 80% of the total polymer. In addition, the cationic monomer groups open up itself, like 34,827-9 and 09657, do not have the same degree of protection against patterned glassware as due to the corresponding polymers. Consequently will the for the cationic or amphoteric polymers observed protection the polymers themselves are impaired and not by any unpolymerized residual monomer.

Example 5

The The procedure of Example 4 was repeated except that 26 grams of Example 2 machine dishwashing composition 40 grams were replaced by that of Example 1. Additionally were pre-weighed lead glass tiles of dimension 5 cm × 5 cm in the upper shelf of the Miele Super-Electronic G 595 SC dishwasher given. The universal 65 ° C Washing program was selected and the glasses, Panels and leaded glass tiles were joined by fifteen successive aisles the formulation, after which the glasses and plates as above were classified and the weight changes of the lead glass tiles were as a measure of Corrosion tendency of the experimental formulation against the colored glass, which includes the decor, determined. Also, the tile was on intensity and coverage of discoloration estimated in reflected light. Ratings from 0 to 5 were marked by two groups of experts and then averaged. On this six-point scale, 0 indicates that the full tile surface free from discoloration was and 5 indicates that the entire tile surface is reflected in Light discolored very strongly blue was. The results in the presence and absence of a cationic Polymers of the present invention were as follows:

This Example shows that a water-soluble copolymer, the cationic Contains monomer groups, the fading of overlay patterns on plates and glasses in a dishwashing detergent without phosphate essential reduced. additionally is the weight loss and discoloration of lead glass tiles, dimensions the tendency of the detergent to corrosive to colored glass, which comprises the decor, also significantly reduced.

Claims (7)

Method for preventing fading or Corrosion of dishes while washing in an automatic dishwashing machine by adding a composition which is a water-soluble cationic or amphoteric polymer to the dishwasher. A method of preventing crockery corrosion according to claim 1 in an automatic Ge dishwasher by use of a formulation comprising: a) a water-soluble cationic or amphoteric polymer, wherein the cationic polymer comprises as a monomer unit, an ethylenically unsaturated compound as represented by formula I

wherein R ^{1 is} hydrogen, hydroxyl or a straight or branched C ₁ to C ₃₀ alkyl radical; R ^{2 is} hydrogen, a straight or branched C ₁ to C ₃₀ alkyl, a straight or branched C ₁ to C ₃₀ alkyl substituted aryl, aryl substituted straight or branched C ₁ to C ₃₀ alkyl radical or Polyoxyalkene condensate of an aliphatic radical; and R ^{3 represents} a heteroatom-containing alkyl or aromatic radical containing either one or more quaternary nitrogen atoms or one or more amine groups having a pK _a of about 6 or greater and a positive charge over one part the pH interval of pH 6 to 11, b) 1 to 90 weight percent of a builder. Method for preventing corrosion of dishes according to claim 1, wherein the polymer is in a proportion of 0.1 to 20 weight percent of the total composition is present. The method of claim 1, wherein the cationic Polymer at least one monomer unit with a cationic charge over a Part of the pH range of 6-11 having. A method according to any preceding claim, wherein the cationic or amphoteric polymer is selected from a group consisting from co-poly-2-vinylpyridine, co-poly-2-vinyl-N-alkyl quaternary pyridinium salt derivatives, Co-poly-4-vinylbenzyltrialkylammoniumsalzen, Co-poly-2-vinylpiperidine, co-poly-2-vinylpiperidinium salt; Co-poly-4-vinyl piperidine, Co-poly-4-vinylpiperidiniumsalz; Co-poly-3-alkyl-1-vinylimidazolium salts, Acrylamido and methacrylamido derivatives, co-poly-methacrylamidopropyltrimethylammonium salt, Acrylate and methacrylate derivatives and mixtures thereof. The method of claim 1, wherein the cationic Polymer selected is selected from the group consisting of copoly-vinylamine and copolyvinylammonium salt; Copolydiallyldimethylammonium, copolyethyleneimine, copoly-ethoxylated Ethyleneimine, copoly-quaternized ethoxylated ethyleneimine, co-poly [(dimethylimino) trimethylene (dimethylimino) hexamethylene di-salt], Co-poly [(diethylamino) trimethylene (dimethylimino) trimethylene d] and co-poly [(dimethylimino) -2-hydroxypropyl salt]. Use of a water-soluble cationic or amphoteric Polymer in a composition for addition to an automatic Dishwasher, to prevent fading or corrosion of dishes.