WO1998051769A1 - Process for removing tarnish from tarnished silverware - Google Patents

Abstract

A process for removing tarnish from tarnished silverware comprising contacting the tarnish silverware with an anti-tarnish composition in an automatic dishwasher. The anti-tarnish composition comprises an alkaline electrolyte and a metal additive.

Description

Process for Removing Tarnish from Tarnished Silverware

Technical Field

The present invention relates to a process for removing tarnish from tarnished silverware in automatic dishwashing methods.

Background

Detergent compositions designed for use in automatic dishwasher machines are well known, and a consistent effort has been made by detergent manufacturers to improve the cleaning and/or rinsing efficiency of said composition on dishes and glassware, as reflected by numerous patent publications.

The present invention is concerned with silverware washed in automatic dishwashers, and in particular with the silver-tarnishing problem encountered with current automatic dishwashing detergent compositions containing bleaching agents.

Previously, techniques used for removing silver-tarnish have involved manual exertion or total submersion of the silverware in the tarnish solvent for a period of time. It has surprisingly been found that the process for removing tarnish from silverware described herein can be used in an automatic dishwasher.

EP-B-0 257 037 describes a method of removing tarnish from silverware using a container of electrolyte to which a sheet of metal foil is attached. The tarnished silverware and metal foil are arranged in the container such that the silverware and the metal foil are in constant direct contact with one another. The tarnished silverware and the metal foil and electrolyte are then submerged in water. It has been found that such methods do not always provide 100% silver tarnish removal. In particular it has been found that silver tarnish tends to remain at points of contact between the silverware or between the silverware and the metal foil. Summary of the Invention

According to the present invention there is provided a process for removing tarnish from tarnished silver, comprising contacting the tarnished silver with an anti-tarnish composition in an automatic dishwasher, said composition comprising

a) an alkaline electrolyte; and b) a metal additive wherein the metal has a more negative redox potential than silver.

Detailed Description of the Invention

The anti-tarnish composition described herein comprises as essential components an alkaline electrolyte and a metal additive.

Alkaline Electrolyte

Any alkaline electrolyte that enhances conductivity of electrons, ultimately increasing redox reaction kinetics, may be suitable for use in the process of the present invention. Preferably the alkaline electrolyte is water soluble such that when dissolved in the wash water it has the effect of increasing alkalinity such that a 1% solution of the anti-tarnish composition dissolved in wash water has pH greater than 9.0, preferably greater than 9.5, more preferably greater than 10.0 or even 10.5. Preferred alkaline electrolytes include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, silicates and metasilicates or mixtures thereof.

In a preferred embodiment of the present invention, the anti -tarnish composition may also be a detergent composition. In this case the alkaline electrolyte is preferably compatible with other components of the detergent composition. According to this aspect of the present invention the preferred alkaline electrolyte is sodium silicate, sodium metasilicate or mixtures thereof. Preferred sodium silicate is that having a SiO2:Na2O ratio of from 1.8 to 3.0, more preferably from 1.8 to 2.4, most preferably 2.0. The alkali metal silicate may be in the form of either the anhydrous salt or hydrated salt.

The alkaline electrolyte may also comprise sodium metasilicate, present at a level of at least 0.4% Siθ2 by weight. Sodium metasilicate has a nominal Siθ2 : Na2θ ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as Siθ2, is preferably from 50: 1 to 5:4, more preferably from 15: 1 to 2:1, most preferably from 10:1 to 5:2.

Metal Additive

Any metal additive that has a standard redox potential more negative than silver may be suitable for use in the present invention. The standard redox potential is measured relative to the standard hydrogen electrode at 25°C. The standard hydrogen electrode consists of a platinum wire and a piece of platinum foil covered with finely divided platinum. Thus electrode is encased in a glass tube so that hydrogen ions can bubble over the platinum. The electrode is operated under standard-state conditions wherein the concentration of hydrogen ions is 1 molar and the atmospheric pressure of hydrogen gas is 1 atmosphere. The reduction of H⁺ to form H2 is the universal reference and is assigned a standard reduction potential of zero volts. Standard redox potentials for other compounds are measured relative to this universal standard.

The metal additive is employed in its atomic rather than ionic state. Typically metal additives are selected from the group consisting of aluminium, zinc, manganese, magnesium and iron. The metal additive may be in any form but is preferably particulate or sheet metal. The particulate/sheet metal is preferably of sufficiently large size such that the metal may be removed from the dishwasher either by hand or trapped in the filter of the dishwasher and removed after completion of the rinse cycle. Preferably the particulate sheet metal is not so large that it causes damage to the silverware during the dishwasher cycle. The most preferred metal additive is aluminium. The most preferred form of aluminium is finely divided pieces of sheet foil having a thickness of from lOOμm to 1500μm, preferably from 200μm to lOOOμm, most preferably from 300μm to 750μm and cut into pieces of dimensions between OJmm and 3mm, preferably between 0.5mm and 2mm.

The weight ratio of alkaline electrolyte to metal additive is from 30:1 to 10:1, preferably from 27:1 to 20:1. Machine Dishwashing Method

In the process of the present invention tarnished silverware is contacted with an anti- tarnish composition in an automatic dishwasher. The silverware and anti-tarnish composition are loaded into the dishwasher and subjected to a treatment step during which the silverware is contacted with the anti-tarnish composition. The treatment step may comprise a pre-wash step, a washing step, a rinsing step or mixtures thereof. Preferably the treatment step is followed by a further rinsing step to remove excess anti-tarnish composition. The silverware may be loaded into any known automatic dishwashing machine and in any position within the dishwashing machine. The anti-tarnish composition may be loaded into the dishwasher by any suitable means, but is preferably loaded by way of the dispenser or the cutlery basket.

When the dishwasher is turned on, water enters the dishwasher, generally it is sprayed into the dishwasher from spraying arms located at the top and bottom of the dishwasher. The alkaline electrolyte of the anti-tarnish composition dissolves in the water (known as the wash water) increasing the alkalinity. The pH of the wash water measured in a 1% solution of the anti-tarnish composition dissolved in wash water is generally elevated to at least 8, preferably at least 9.5, most preferably at least 10. The wash water containing dissolved alkaline electrolyte and metal additive, is dispersed and circulated throughout the dishwasher contacting the tarnished silverware at intervals throughout the treatment step.

The amount of anti-tarnish composition used is an effective amount that can effectively remove silver tarnish. Whilst this may be dependant upon the amount of silverware loaded into the dishwasher and the degree to which such silverware is tarnished, generally be an effective amount of the anti-tarnish or machine dishwashing composition it is meant from 8g to 60g of the composition dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.

On completion of the treatment step, the de-tarnished silverware is removed from the dishwasher. For best results the de-tarnished silverware is preferably subjected to a post-treatment step wherein the de-tarnished silver is contacted with an absorbent material for, example fabric or paper, in a wiping or buffing action. Other soiled articles may be present in the dishwashing machine such as articles selected from crockery, glassware, and cutlery and mixes thereof.

Preferably when they are present, the anti-tarnish process is also a cleaning process and the anti-tarnish composition may comprise any conventional detergent composition ingredient.

Detergent Composition Ingredients

Thus according to a preferred aspect of the invention there is provided an anti- tarnish and cleaning composition comprising an alkaline electrolyte, a metal additive, wherein the metal has a more negative redox potential than silver, a builder and a nonionic surfactant.

Builder Compound

The detergent compositions used in the process of the present invention may contain as a highly preferred component a builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.

Water-Soluble Builder Compound

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures thereof.

The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1,1,3 -propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1 J ,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3 -propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1,2,3, 4,5, 6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less than about 50°C, especially less than about 40°C. Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra- fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and 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.

Partially Soluble or Insoluble Builder Compound

The compositions of the present invention may less preferably contain a partially soluble or insoluble builder compound. Examples of partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Examples of largely water insoluble builders include the sodium aluminosilicates, including Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.

Nonionic Surfactant

Any nonionic surfactants useful for detersive purposes can be included in the detergent compositions. Preferred, non-limiting classes of useful nonionic surfactants are listed below. The surfactant system is typically present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of the compositions.

Nonionic Ethoxylated Alcohol Surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.

Nonionic Ethoxylated/Propoxylated Fatty Alcohol Surfactant

The ethoxylated C6-Cιg fatty alcohols and C6-C^g mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the CjQ-Ci ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the l2" l 8 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Endcapped Alkyl Alkoxylate Surfactant

A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula:

R₁O[CH₂CH(CH3)O]_x[CH2CH2O]_y[CH₂CH(OH)R2] (I)

wherein Rj is a linear or branched, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms; x is an integer having an average value of from 0.5 to about 1.5, more preferably about 1 ; and y is an integer having a value of at least about 15, more preferably at least about 20.

Preferably, the surfactant of formula I, at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present invention, are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation. Nonionic EO/PO Condensates with Propylene Glycol

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Nonionic EO Condensation Products with Propylene Oxide/Ethylene Diamine Adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.

Optional Detergent Ingredients

In addition to the essential ingredients described herein above, the detergent compositions used in the process of the present invention may be formulated to additionally comprise detergent ingredients, preferably selected from bleach, heavy metal ion sequestrants, crystal growth inhibitors, enzymes, organic polymeric compounds, additional corrosion inhibitors and suds suppressors.

Oxygen-Releasing Bleaching System

An oxygen-releasing bleaching system is a preferred component of the detergent compositions used in the process of the present invention. In one preferred aspect the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred aspect a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic Perhydrate Bleaches

The compositions in accordance with the invention preferably include a hydrogen peroxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.

The inorganic perhydrate salts are normally incorporated in the form of the sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilise a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

Sodium perborate can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate N Bθ2H2θ2-3H2θ.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3-3H2θ2, and is available commercially as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise. The percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability.

A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0J to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

O X- C - L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is

O X- C - OOH

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1 147871, 2143231 and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilise for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

V A 0

II

-N-C-R¹ -N N

I , I I — N- -C-CH-

X ' 1 R³ ' 1 F^³

I Y

I

Y

R³ Y

0-CH=C-CH=CH₂ -0-CH=C-CH= =CH₂

R³ 0 Y

¹ " ' -0-C=CHR⁴ , and — N-S-CH-R⁴ II

R³ 0

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from

1 to 14 carbon atoms, R 3 is an alkyl chai •n containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups

alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:

Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

Ac = COCH3; Bz = Benzoyl

Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:

Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

Suitable N-acylated lactam perbenzoic acid precursors have the formula:

wherein n is from 0 to 8, preferably from 0 to 2, and R is a benzoyl group. Perbenzoic Acid Derivative Precursors

Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged le; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.

A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:

R¹ - — C N R² — C - L R¹ — N — C R² — C L

O R⁵ O or R⁵ O O

wherein R! is an aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R* preferably contains from 6 to 12 carbon atoms. R^ preferably contains from 4 to 8 carbon atoms. Rl may be aryl, substituted aryl oralkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R^. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. Rl and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Cationic Peroxyacid Precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described herein before. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451 ; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 (attorney's docket no. CM642F) and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906 (attorney's docket no.s 5413 to 5416).

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

O o

Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:

O O

where n is from 0 to 12, particularly from 1 to 5.

Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis. Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide Substituted Alkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:

R — c- - N R² -c- - L R - N — -c R² — C L

O R⁵ 0 or R⁵ O O

wherein R! is an alkyl group with from 1 to 14 carbon atoms, R^ is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group, Rl preferably contains from 6 to 12 carbon atoms. R^ preferably contains from 4 to 8 carbon atoms, R! may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R^. The substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R-> is preferably H or methyl, R! and R^ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Benzoxazin Organic Peroxyacid Precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

including the substituted benzoxazins of the type

wherein R, is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R~, R-,, R., and R_<- may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR^ (wherein R^ is H or an alkyl group) and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is:

Preformed Organic Peroxyacid

The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

R¹ - c N R² C OOH

0 R⁵ 0 or

R - N - - c R² C OOH

R⁵ 0 0

wherein R! is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms, R! preferably contains from 6 to 12 carbon atoms. R^ preferably contains from 4 to 8 carbon atoms. R! may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R-> is preferably H or methyl. R* and R^ should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N- phthaloylaminoperoxicaproic acid are also suitable herein.

Water-Soluble Sulfate Salt

In a preferred aspect the detergent composition may contain a water-soluble sulfate salt, preferably present at a level of from 0.1% to 40%, more preferably from 1% to 30%, most preferably from 5% to 25% by weight of the compositions. The water-soluble sulfate salt may be essentially any salt of sulfate with any counter cation. Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.

Additional Corrosion Inhibitor Compound

The compositions may contain additional corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.

Organic silver coating agents are described in PCT Publication No. WO94/16047 and EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are disclosed in European Application no. EP-A-634478. Mn(II) compounds for use in corrosion inhibition are described in EP-A-672749.

Organic silver coating agent may be incorporated at a level of from 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition.

The functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied. The silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.

Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained from mono- or polycarboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and β,β'- dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n- butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

The fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

Preferably, the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.

Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.

The glycerol esters are also highly preferred. These are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above.

Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl proprionate. Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.

Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.

Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.

Waxes, including microcrystalline waxes are suitable organic silver coating agents herein. Preferred waxes have a melting point in the range from about 35°C to about 110°C and comprise generally from 12 to 70 carbon atoms. Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.

Alginates and gelatin are suitable organic silver coating agents herein.

Dialkyl amine oxides such as C12-C20 rnethylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C12- 2O methylammonium halides are also suitable.

Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such polymeric materials.

Certain perfume materials, particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.

Polymeric soil release agents known to those skilled in the art of formulating laundry detergent compositions can be used as the organic silver coating agent herein.

Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate :C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4- C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C \ -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(j) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as Mθ3S(CH2)_nOCH2CH2θ-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1 -C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci -Cg vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.

Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.

Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,71 1,730, issued December 8, 1987 to Gosselink et al, the anionic endcapped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.

Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.

A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predominantly branched C25-45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 :10 to 2:1, preferably from 1 :5 to 1 :1. A paraffin oil meeting these characteristics, having a ratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Nitrogen-Containing Corrosion Inhibitor Compounds

Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139, 279 and British Patent GB-A- 1,137,741, which also discloses a method for making imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Ri , R₃, R4 and R₅ where R is any of H, CH₂OH, CONH3, or COCH3, R₃ and R5 are any of C1-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2.

Other suitable nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, l-phenyl-5-mercapto-l ,2,3,4- tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.

Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulphate or diammonium hydrogen citrate are also suitable.

Mn(II) Corrosion Inhibitor Compounds

The compositions may contain an Mn(II) corrosion inhibitor compound. The Mn(II) compound is preferably incorporated at a level of from 0.005% to 5% by weight, more preferably from 0.01% to 1%, most preferably from 0.02% to 0.4% by weight of the compositions. Preferably, the Mn(II) compound is incorporated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution. The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The Mn(II) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.

The Mn(II) compound may be a salt or complex of an organic ligand. In one preferred aspect the organic ligand is a heavy metal ion sequestrant. In another preferred aspect the organic ligand is a crystal growth inhibitor.

Other Corrosion Inhibitor Compounds

Other suitable additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated C\ 0-C20 fatty acids, or their salts, especially aluminium tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa- decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.

Copolymers of butadiene and maleic acid, particularly those supplied under the trade reference no. 07787 by Polysciences Inc have been found to be of particular utility as corrosion inhibitor compounds.

Total Available Oxygen (AvO Level

It has been found that, for optimal anti-silver tarnishing performance, the level of available oxygen in the present compositions, measured in units of % available oxygen by weight of the composition, is preferably controlled; the level of available oxygen should hence preferably be in the range from 0.3% to 2.5%, preferably from 0.5% to 1.7%, more preferably from 0.6% to 1.5%, most preferably from 0.7% to 1.2%, measured according to the method described hereunder. Rate of Release of AvO

The rate of release of available oxygen is preferably also controlled; the rate of release of available oxygen from the compositions herein preferably should be such that, when using the method described hereinafter, the available oxygen is not completely released from the composition until after 3.5 minutes, preferably the available oxygen is released in a time interval of from 3.5 minutes to 10.0 minutes, more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0 minutes to 8.5 minutes.

Method for Measuring Level of Total Available Oxygen (AvO) and Rate of Release of AvO in a Detergent Composition

Method

1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrer speed is selected to ensure that the product is evenly dispersed through the solution.

2. The detergent composition (typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler), is added and simultaneously a stop clock is started.

3. The temperature control should be adjusted so as to maintain a constant temperature of 20°C throughout the experiment.

4. Samples are taken from the detergent solution at 2 minute time intervals for 20 minutes, starting after 1 minute, and are titrated by the "titration procedure" described below to determine the level of available oxygen at each point.

Titration Procedure

1. An aliquot from the detergent solution (above) and 2ml sulphuric acid are added into a stirred beaker 2. Approximately 0.2g ammonium molybdate catalyst (tetra hydrate form) are added

3. 3mls of 10% sodium iodide solution are added

4. Titration with sodium thiosulphate is conducted until the end point. The end point can be seen using either of two procedures. First procedure consists simply in seeing the yellow iodine colour fading to clear. The second and preferred procedure consists of adding soluble starch when the yellow colour is becoming faint, turning the solution blue. More thiosulphate is added until the end point is reached (blue starch complex is decolourised).

The level of AvO, measured in units of % available oxygen by weight, for the sample at each time interval corresponds to the amount of titre according to the following equation

Vol S₂0₃(ml) x Molarity (S₂0₃) x 8 Sample mass (g)

AvO level is plotted versus time to determine the maximum level of AvO, and the rate of release of AvO

Controlled Rate of Release - Means

A means may be provided for controlling the rate of release of oxygen bleach to the wash solution.

Means for controlling the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution. Such means could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.

Suitable controlled release means can include coating any suitable component with a coating designed to provide the controlled release. The coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.

The coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1 :99 to 1 :2, preferably from 1 :49 to 1 :9.

Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.

Other suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.

A preferred coating material, particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of Siθ2 : Na2θ ratio from 1.8 : 1 to 3.0 : 1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of Siθ2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

Any inorganic salt coating materials may be combined with organic binder materials to provide composite inorganic salt/organic binder coatings. Suitable binders include the C10- 2O alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10^ preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C\ 0-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the C10-C20 mono- and diglycerol ethers and also the C10-C20 fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.

One method for applying the coating material involves agglomeration. Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.

Other means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compaction, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.

Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.

Additional protocols for providing the means of controlled release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved.

Heavy Metal Ion Sequestrant

The detergent compositions used herein may contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.

Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 :1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.

Crystal Growth Inhibitor Component

The detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions. By organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.

The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-lJ -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.

Enzyme

Another optional ingredient useful in the compositions is one or more enzymes. Preferred enzymatic materials include the commercially available Upases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN byNovo Industries A S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions. The lipase may be fungal or bacterial in origin. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is described in Granted European Patent, EP-B-0218272.

An especially preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Enzyme Stabilizing System

Preferred enzyme-containing compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof. Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Organic Polymeric Compound

Organic polymeric compounds may be added as preferred components of the compositions in accord with the invention. By organic polymeric compound it is meant essentially any polymeric organic compound commonly used asdispersants, and anti-redeposition and soil suspension agents in detergent compositions.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof. Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.

Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.

Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CRι(CO- O-R3)]- wherein at least one of the substituents Rj, R2 or R3, preferably R\ or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R\ or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R j is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Lime Soap Dispersant Compound

The compositions of the invention may contain a lime soap dispersant compound, preferably present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. Preferred lime soap disperant compounds are disclosed in PCT Application No. WO93/08877 (attorney's docket no. CM466M). Suds Suppressing System

The compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2- alkyl and alcanol antifoam compounds. Preferred suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 and European Application No. EP-A-705324.

Polymeric Dye Transfer Inhibiting Agents

The compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected frompolyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

pH of the Compositions

The present compositions are preferably not formulated to have an unduly high pH, in preference having a pH measured as a 1% solution in distilled water of from 8.0 to 12.0, more preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.

Form of the Compositions

The compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels and tablets, granular forms being preferred.

The bulk density of the granular detergent compositions in accordance with the present invention is typically of at least 650 g/litre, more usually at least 700 g/litre and more preferably from 800 g/litre to 1200 g/litre. The particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4mm in diameter and not more than 5% of particles are less than 0J5mm in diameter.

Generally, if the compositions are in liquid form the liquid should be thixotropic (ie; exhibit high viscosity when subjected to low stress and lower viscosity when subjected to high stress), or at least have very high viscosity, for example, of from 1,000 to 10,000,000 centipoise.

Examples

Anti-Silver Tarnish Composition

One example of an anti-tarnish composition of the present invention comprises 2g of finely divided aluminium foil and 50g of sodium hydroxide pellets.

The following represents further examples of the present invention wherein the anti- tarnish composition also comprises an automatic dishwashing detergent composition. In this embodiment the anti-tarnish composition comprises 2g of finely divided aluminium foil and 50g of automatic dishwashing detergent composition.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

STPP Sodium tripolyphosphate

Citrate Tri-sodium citrate dihydrate Bicarbonate Sodium hydrogen carbonate Carbonate Anhydrous sodium carbonate Silicate Amorphous Sodium Silicate (SiO2:Na2O ratio = 1.6-

3.2)

Metasilicate Sodium metasilicate (SiO2:Na2O ratio = 1.0)

PB1 Anhydrous sodium perborate monohydrate

PB4 Sodium perborate tetrahydrate of nominal formula

NaBθ2.3H₂O.H₂θ2

Percarbonate Anhydrous sodium percarbonate of nominal formula

2.Na CO3 3H₂O₂

Plurafac C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5

Polytergent SLF18B Epoxy-capped poly(oxyalkylated) alcohol of Example

III of WO 94/22800 wherein 1 ,2-epoxydodecane is substituted for 1 ,2-epoxydecane.

Tergitol Secondary alcohol ethoxylate TAED Tetraacetyl ethylene diamine HEDP Ethane 1-hydroxy-lJ -diphosphonic acid DETPMP Diethyltriamine penta (methylene) phosphonate, marketed by monsanto under the tradename Dequest

2060

MnTACN Manganese 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane. PAAC Pentaamine acetate cobalt (III) salt BzP Benzoyl Peroxide Paraffin Paraffin oil sold under the tradename Winog 70 by

Wintershall.

Protease Proteolytic enzyme Amylase Amylolytic enzyme. BTA Benzotriazole PA30 Polyacrylic acid of average molecular weight approximately 4,500

MA AA Randon copolymer of 7:3 acrylate/maleate, average molecular weight about 70,000

480N Random copolymer of 7:3 acrylate/methacrylate, average molecular weight about 3,500

Polygel/Carbopol High molecular weight crosslinked polyacrylates.

Sulphate Anhydrous sodium sulphate.

NaOCl Sodium hypochlorite

NaDCC Sodium dichloroisocyanurate

NaOH Sodium Hydroxide solution

KOH Potassium Hydroxide solution

NaBz Sodium Benzoate

SCS Sodium Cumene Sulphonate pH Measured as a 1% solution in distilled water at 20°C

In the following examples all levels are quoted as % by weight of the composition: Example 1

The following compact high density (0.96Kg/l) dishwashing detergent compositions A to H were prepared in accord with the invention:

Example 2

The following granular dishwashing detergent compositions examples I to Q of bulk density 1.02Kg/L were prepared in accord with the invention:

Example 3

The following liquid detergent compositions in accord with the present invention X to AA of density l JOKg/L were prepared:

Example 4

The following tablet detergent composition examples V to Zl in accord with the present invention were prepared by compression of a granular dishwashing detergent composition at a pressure of 13KN/CM2 using a standard 12 head rotary press:

Test for Silver Tarnish Removal

Test 1

2g of finely divided aluminium foil was mixed with 50g of sodium hydroxide pellets and placed in the dispenser of the automatic dishwasher. Twenty tarnished silver spoons were visually graded and placed in the cutlery basket of the dishwasher. The dishwasher was set to run on a wash cycle at 65°C with water of 1.28mmol/L hardness. On completion of the dishwasher cycle the spoons are removed, wiped dry and visually graded immediately. The average visual grades for silver tarnish are given in table 1 below.

Test 2

The protocol used in the second test is identical to that from test 1 except that the 50g of sodium hydroxide is replaced with 50g of composition D, described in Example 1 above.

The degree of silver tarnish is graded visually on a scale of 0 to 4, wherein 0 indicates untarnished and 4 indicates heavily tarnished. Tests 1 and 2 were executed with heavily tarnished silverware (tests la and 2a) and moderately tarnished silverware (tests lb and 2b). The results are given in Table 1 below.

Claims

What is claimed is:

1. A process for removing tarnish from tarnished silverware, comprising contacting the tarnished silverware with an anti-tarnish composition in an automatic dishwasher, said composition comprising

a) an alkaline electrolyte; and b) a metal additive wherein the metal has a more negative standard redox potential than silver, measured relative to a standard hydrogen electrode at 25┬░C.

2. A process according to Claim 1 wherein the alkaline electrolyte is an alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate salt.

3. A process according to Claim 2 wherein the alkaline electrolyte is sodium hydroxide.

4. A process according to any of Claims 1 to 3 wherein the metal additive is selected from the group consisting of aluminium, manganese, magnesium, iron, zinc.

5. A process according to any of Claims 1 to 4 wherein the metal additive is aluminium.

6. A process according to any of Claims 1 to 5 wherein the weight ratio of alkaline electrolyte to metal additive is between 27:1 and 20:1.

7. An anti-tarnish detergent composition comprising:

a) an alkaline electrolyte; b) a metal additive wherein the metal has a more negative standard redox potential than silver, measured relative to a standard hydrogen electrode at 25┬░C. c) at least 1% builder compound; and d) at least 1% nonionic surfactant

8. A detergent composition according to Claim 7 wherein a 1% solution of the detergent composition dissolved in water has pH greater than 9.0.

9. A detergent composition according to either of Claims 7 or 8 wherein the alkaline electrolyte comprises sodium silicate or sodium metasilicate or mixtures thereof.

10. A detergent composition according to any of Claims 7 to 9 wherein the metal additive is selected from the group consisting of aluminium, manganese, magnesium, iron and zinc.

11. A detergent composition according to any of Claims 7 to 10 wherein the metal additive is aluminium.

12 A detergent composition according to any of Claims 7 to 11 wherein the weight ratio of alkaline electrolyte to metal additive is between 27: 1 and 20: 1.

13. An anti-silver tarnish and cleaning process comprising the steps of contacting the silverware and optionally other soiled articles with an anti-tarnish and cleaning composition, said composition comprising

a) an alkaline electrolyte; b) a metal additive wherein the metal has a more negative standard redox potential than silver, measured relative to a standard hydrogen electrode at 25┬░C. c) at least 1% builder compound; and d) at least 1 % nonionic surfactant.