WO1998032834A1 - Process for making tabletted detergent compositions - Google Patents

Abstract

According to the present invention there is provided a process for preparing a detergent tablet suitable for use in either automatic dishwashing or fabric laundering methods wherein the process comprises the step of obtaining partially prehydrated particulate hydratable salt wherein at least 60 % of the hydratable salt has a particle size of 0.6 mm or greater and between 25 % and 70 % of the salt is present in the hydrated form.

Description

Process for making tabletted detergent compositions

Technical Field

The present invention relates to a process for making phosphate-containing detergent tablets suitable for use in either laundry or automatic dishwashing methods.

Background

Detergent compositions in tablet form are known in the art. It is understood that tabletted detergent compositions hold several advantages over granular detergent compositions. Examples of such advantages include ease of handling, transportation and storage. Tablets are therefore required to be sufficiently hard such that they do not crumble or disintegrate on handling, transportation or storage.

Detergent tablets are traditionally prepared by the compression or compaction of granular detergent compositions. The most common method used by detergent manufacturers to prepare harder tablets is to increase the tabletting compaction pressure. It has however, been found that solubility of the tablet generally decreases with increasing tablet hardness. Detergent manufacturers have directed tablet development efforts toward striking a balance between tablet hardness and solubility.

Previously the most common method used by detergent manufacturers for increasing the rate of dissolution of detergent tablets has been to decrease the compaction pressure used to make the tablets. A decrease in compaction pressure results in a tablet that has a faster dissolution rate but is also soft and prone to surface dustiness. As described above, tablets that are too soft to withstand handling, transportation or storage are prone to crumbling and disintegration and are therefore unacceptable to the consumer. In addition, tablets that exhibit a high level of surface dustiness, leaving dust on the hands of the person handling the tablet, are also unacceptable to the consumer.

Other methods of controlling tablet hardness and thus dissolution have been discussed in the prior art. Henkel EP-0170791 describes a process for making a tablet detergent composition comprising percompounds and tabletting aids, such as cross-linked polyvinyl pyrrolidone, cellulose ethers or swellable magnesium aluminium silicates. Unilever EP-0466484 and EP-0522766 describe increasing tablet disintegration by incorporating a binder/distintegrant into the detergent composition to be tabletted. Colgate-Palmolive GB-983243 and GB-989683 describe detergent tablets having improved dissolution properties, prepared by compacting spray-dried detergent powders that have been sprayed with water or with aqueous sodium silicate solution in order to reduce the proportion of fine particles (smaller than 100 mesh (US), equivalent to 149μ m) present. Colgate palmolive US 4370250 describes a tabletted detergent composition with improved solubility, wherein the detergent composition is over-sprayed with liquid synthetic detergent components prior to tabletting.

DE-2913145 describes a method for preparing a granulate for use in automatic dishwashing containing between 20% and 60% by weight anhydrous sodium tripolyphosphate (STPP) (30% to 80% of which is hexahydrate), 35% to 75% by weight sodium silicate, 0 to 25% by weight carbonate and/or sodium hydroxide, 0.2% to 2% by weight weakly foaming non-ionic surfactant. The granulate disclosed is made by hydration of anhydrous STPP in a continuous mixer and subsequent granulation of the hydrate obtained with the remaining ingredients. The average particle size of anhydrous STPP is from 0.05mm to 0.5mm. The average residence time of the STPP in the mixer is from 0.2 to 5 seconds.

Henkel EP-126 963 describes a process for the preparation of a detergent tablet composition wherein the process involves partially hydrating from 10 to 60 parts by weight anhydrous sodium tripolyphosphate (STPP)(60%-100% phase II) having average grain size of between 0.05 to 0.5 mm. This step is carried out by mixing with water for 0.2 to 5 seconds so that from 30 mole percent to less than 80 mole percent tripolyphosphate is converted to the hexahydrate. The STPP mixture is then mechanically treated until at least 85% by weight of the mixture has a grain size of above 0.2 mm. The partially hydrated STPP, after a residence time of 5 to 60 s outside the mixer, is mixed with between 20% to 70% powdered anhydrous sodium silicate and optional granulation aid, in a granulation mixer and the mixture is sprayed with water or aqueous sodium silicate. Finally, the mixture of is granulated and made into tablets

It is the object of the present invention to provide a process for preparing a detergent tablet that has an improved rate of dissolution, is sufficiently hard to withstand handling, transportation or storage and does not exhibit unacceptable surface dustiness. It has surprisingly been found that the process described herein for making detergent tablets comprising a hydratable salt wherein at least 60% of the hydratable salt has a particle size of 0.6 mm or greater and between 25% and 70% of the hydratable salt is present in the hydrated form, provides detergent tablets that exhibit a good rate of dissolution or flush-in time.

Summary of the Invention

According to the present invention there is provided a process for preparing a detergent tablet wherein the process comprises the steps of: a) obtaining partially pre-hydrated particulate hydratable salt wherein at least 60% of the hydratable salt has a particle size of 0.6 mm or greater and wherein from 25%) to 10% by weight of the salt in the hydrated state; and b) admixing the partially pre-hydrated salt with remaining detergent ingredients to form a detergent composition; and c) forming the detergent composition into tablets.

Preferably the particulate hydratable salt comprises sodium tripolyphosphate.

Description of the Invention

Hydratable Salt

The particulate hydratable salt may, for example, be a carbonate or phosphate salt or mixtures thereof, but is preferably sodium tripolyphosphate. At least 60% by weight of the hydratable salt has particle size of 0.6 mm or greater. Preferably at least 70%, or even 75%, or even 80% by weight of the hydratable salt has particle size of 0.6 mm or greater. Even larger particle size may be useful for example where at least 10%, or even at least 15%, or even at least 20%) by weight of the hydratable salt has particle size 0.7 mm or greater.

Sodium Tripolyphosphate (STPP)

The detergent tablet prepared by the process described herein comprises STPP as a preferred component. The STPP may be present at a level of from 1 % to 80% by weight, preferably from 10% to 10% by weight, most preferably from 20% to 60%> by weight of the composition. Preferably the hydratable salt of step (a) in the process comprises STPP. Preferred STPP may be either substantially anhydrous or partially hydrated such that the weight ratio of phase I STPP to phase II STPP is from 1 :4 to 1 : 1.

Process

In a preferred process according to the invention, the partially pre-hydrated particulate salt is obtained in a pre-hydration step. The pre-hydration step comprises the pre- hydration of particulate hydratable salt, prior to admixing with the remaining detergent ingredients, by contacting with water and allowing a residence time of generally at least 90 seconds, preferably at least 120 seconds or even at least 180 seconds. Longer residence times are also envisaged up to a maximum residence time of 25 minutes, preferably a maximum of 20 minutes, most preferably a maximum of 15 minutes. Preferably the hydratable salt is contacted with water by continuously spraying with water for between 90 seconds and 15 minutes. For the purposes of the present invention the particulate material includes any hydratable salt, preferably anhydrous particulate sodium tripolyphosphate (STPP). Where the hydratable salt comprises STPP, the STPP is preferably sprayed with water such that at least 15% by weight, preferably at least 20% by weight, most preferably at least 25%) by weight of the STPP is hydrated to STPP hexahydrate. Generally up to 80% by weight, preferably up to 75% by weight, but most preferably up to 70% by weight of the STPP is hydrated to STPP hexahydrate.

Any suitable low shear or high residence time continuous or batch mixer, that allows for continuous movement of particulate material may be used in the pre-hydration step. Such mixers may include for example any ribbon blender, rotary drum or vertical screw type mixer. In particular a Forberg mixer (tradename); Bepex continuator mixer (tradename) and preferably a KM Loedige (tradename) mixer may be used.

A suitable mixer comprises a drum into which particulate material can be fed and a mechanism for continuously moving the particulate material. In a preferred embodiment the mixer comprises a drum having a central shaft to which various mixing blades are attached at intervals along its length and spraying arms suspended above the area designed to contain the particulate material. The mixer is typically fitted with a form of adjustable gate which allows the residence time of the particulate material in the mixer to be varied. By continuous movement of the particulate material we mean, for example oscillatory movement, but preferably rotational movement. A mixer in which the particulate material is moved rotationally preferably has a rate of rotation of between 1 and 1000 rpm, most preferably between 1 and 500 rpm.

As the particulate material passes through the length of the mixing drum, it is sprayed with fluid from the nozzles of the spraying arms. The spraying arms and nozzles may be at a distance of from 0.1 to 8 meters from the particulate material, preferably the spraying arms and nozzles are at a distance of between 0.25 and 3 meters from the particulate material. The nozzle may be of any shape suitable for spraying fluid, it is preferred however that the nozzle be capable of spraying a fine spay (atomisation) of fluid to ensure wide spread dispersion of the fluid across the largest surface area of particulate material.

The pre-hydrated particulate hydratable salt is then admixed with any optional component to form the detergent composition prior to forming into tablets. The pre- hydration particulate salt may be admixed with optional components in any conventional way to form a substantially homogeneous mixture of a detergent compositon. Admixing may take place in any suitable mixer, for example a rotary mixer, or may take place by direct addition either of separate optional components of the detergent composition, or preferably of a pre-mix of two or more optional components. Admixing may even take place in the mixer used in the pre-hydration step, after the pre-hydration step has taken place. Preferably solid optional components are dry added to the hydrated salt after the pre-hydration step and mixed. Liquid optional components are preferably sprayed onto either the hydrated salt after the pre-hydration step or preferably after the prehydrated salt has been admixed with some or all of the solid optional components.

The resulting detergent composition is then formed into tablets using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting. Any conventional technique for forming tablets may be used. Preferably tablets are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm2, more preferably from 5 to 1 lKN/cm? so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 hardness test as supplied by I. Holland instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape. Preferably the tablets weigh between 18g and 27g, most preferably between 20g and 25g. Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution. Both industrial and small scale production of the detergent composition prepared by the process of the present invention are envisaged. Preferred equipment should be selected according to the scale of production required.

Kinetics of Dissolution

The process of the present invention enables a tablet to be prepared such that in the test method described herein the time taken to achieve 100% dissolution of the tablet is 20 minutes or less, preferably 17 minutes or less.

Tablet Dissolution Test Method

The enhanced rate of dissolution kinetics are defined with respect to a test method that measures the time taken to achieve 100% dissolution of the detergent tablet. For the purposes of the present invention dissolution of detergent tablets is achieved using a SOTAX (tradename) machine; model number AT7 available from SOTAX..

The SOTAX machine consists of a temperature controlled waterbath with lid. 7 pots are suspended in the water bath. 7 electric stirring rods are suspended from the underside of the lid, in positions corresponding to the position of the pots in the waterbath. The lid of the waterbath also serves as a lid on the pots.

The SOTAX waterbath is filled with water and the temperature gauge set to 50°C. Each pot is then filled with 1 litre of deionised water and the stirrer set to revolve at 250rpm. The lid of the waterbath is closed, allowing the temperature of the deionised water in the pots to equilibrate with the water in the waterbath for 1 hour.

One tablet is placed in each pot and the lid closed. The tablet is visually monitored until it reaches 100% dissolution. The time is noted at 100% dissolution. The time taken to achieve 100% dissolution is the dissolution rate of the tablet.

Optional Detergent Composition Components

The tablet detergent composition may optionally contain various components including bleaching agents, alkalinity sources, surfactants, additional builder compounds, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzymes and enzyme stabilisers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes.

Additional Builder compound

The tablet compositions prepared by the process of the present invention may contain an additional 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 of any of the foregoing.

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 oxypolycarbox late 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, 1,1,2,2-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 that 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.

Highly preferred builder compounds for use in the present invention are water-soluble phosphate builders. 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 polymerisation ranges from about 6 to 21 , and salts of phytic acid.

Partially soluble or insoluble builder compound

The compositions of the present invention may contain a partially soluble or insoluble builder compound. Partially soluble and insoluble builder compounds are particularly suitable for use in tablets prepared for use in laundry cleaning methods. 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. Preferred are the crystalline layered sodium silicates of general formula

NaMSi_xO₂₊i .yH₂O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so called δ-layered structure, as described in EP 0 164514 and EP 0 293640.

Methods for preparation of crystalline layered silicates of this type are disclosed in DE- A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2,3 or 4 and is preferably 2.

The most preferred crystalline layered sodium silicate compound has the formula δ- Na2Si2θ5 , known as NaSKS-6 (trade name), available from Hoechst AG.

The crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material as described in PCT Patent Application No. WO92/18594. The solid, water- soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.

Examples of largely water insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na_z[(AlO2)_z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.

A preferred method of synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14(2), 1 10-116), in which the author describes a method of preparing colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles are of size greater than lμm in diameter and not more than 5% of particles are of size less then 0.05 μm in diameter. Preferably the aluminosilicate zeolite particles have an average particle size diameter of between

0.0 lμm and lμm, more preferably between 0.05 μm and 0.9 μm, most preferably between O.lμm and 0.6 μm.

Zeolite A has the formula

Na ₁₂ [AlO₂) 12 (SiO₂)ι₂]. H₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(Alθ2)86(^siO2)l06]- ^{276 H}2°- Zeolite MAP, as disclosed in EP-B-384,070 is a preferred zeolite builder herein.

Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When employed as a component of a detergent composition colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide enhanced builder performance in terms of providing improved stain removal. Enhanced builder performance is also seen in terms of reduced fabric encrustation and improved fabric whiteness maintenance; problems believed to be associated with poorly built detergent compositions.

A surprising finding is that mixed aluminosilicate zeolite detergent compositions comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium ion sequestration performance versus an equal weight of commercially available zeolite A. Another surprising finding is that mixed aluminosilicate zeolite detergent compositions, described above, provide improved magnesium ion sequestration performance versus an equal weight of commercially available zeolite A.

Surfactant

Surfactants are preferred components of the detergent compositions prepared by the process of this invention. Suitable surfactants are selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof. Automatic dishwashing machine products should be low foaming in character and thus the foaming of the surfactant system for use in dishwashing methods must be suppressed or more preferably be low foaming, typically nonionic in character. Sudsing caused by surfactant systems used in laundry cleaning methods need not be suppressed to the same extent as is necessary for dishwashing. The surfactant 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.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December, 30, 1975. A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants typically included in automatic dishwashing detergent compositions is given for example, in EP-A-0414 549 and PCT Applications No.s WO 93/08876 and WO 93/08874.

Nonionic surfactant

Essentially any nonionic surfactants useful for detersive purposes can be included in the compositions. Preferred, non-limiting classes of useful nonionic surfactants are listed below.

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.

End-capped 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 R\ is a linear or branched, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms; R 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)R.2_J. 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 ethoxylated/propoxylated fatty alcohol surfactant

The ethoxylated C_β-C_jg fatty alcohols and C^-Cj g mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the C 1 Q-C \ g ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C^-Cj g 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.

Nonionic EO/PO condensates with propylene lvcol 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 Pluronic^M 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

Tetronic compounds, marketed by BASF.

Anionic surfactant

Essentially any anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C, ~-C, monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C_fi-C , . diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(Cι- C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary lO"Cl8 alkyl sulfates, more preferably the C1 1 -C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C\ \ - Cjg, most preferably Cj \ -C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)_x CH2C00"M⁺ wherein R is a Cg to C1 g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2-O)-R3 wherein R is a Cg to C\ g alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors. Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a Ci -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(OR4)_XNO(R )₂ wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Ci o-C^g alkyl dimethylamine oxide, and Cjo-i acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N⁺R2C00~ wherein R is a C6-C1 g hydrocarbyl group, each R^ is typically -C3 alkyl, and R² is a C1-C5 hydrocarbyl group. Preferred betaines are C\ ₂_ι dimethyl-ammonio hexanoate and the C J O- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants

Cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group. Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono Cg-Cjg, preferably C6-CJO N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Oxygen-releasing bleaching system

An optional component of the detergent composition is an oxygen-releasing bleaching system. 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 incoφorated 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 accord 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 incoφorated 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, peφhosphate, 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 utilize 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 NaBO₂H₂O₂ or the tetrahydrate NaBO₂H₂θ2.3H2θ.

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 2Na₂CO3-3H O₂, 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 incoφorated 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, granted to Interox on 9th March 1977. 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 Na SO4.n.Na₂CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Another suitable coating material providing in product stability, comprises sodium silicate of SiO₂ : Na₂O 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 SiO by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable. Other coatings which contain 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 perhydrolysis the structure of the peroxyacid produced is

O X- C - OOH

Peroxyacid bleach precursor compounds are preferably incoφorated 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, 1147871, 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:

O Λ O

-N-C-R¹ -N N — N-C-CH— R⁴ R³ Y

I Y

R I ³ Y I

O-CH=C-CH= =CH₂ -O-CH=C- -CH= =CH₂

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group contaimng from 1 to

14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or

R , R5 is an alkenyl chain containing from 1 to 8 carbon atoms 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 ammonium groups.

The preferred solubilizing groups are -SO-,^"M , -CO2~M , -SO M , -N (R ).X^" and O<~N(R )-, and most preferably -SO^^'M and -CO₂ ^"M wherein R is an 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 (i.e.; 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 R}1 — _N — _c — _R2 — _c — 1_ i| i ii i i! ^■:

O R⁵ O or R⁵ O O

wherein R* is an aryl or alkaryl group with from 1 to 14 carbon atoms, R² 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. R² preferably contains from 4 to 8 carbon atoms. R may be aryl, substituted aryl oralkylaryl contaimng 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 ammonium 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 hereinbefore. 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.

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:

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

ff 9

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.

AM percarbqxytøg flcjd bleach, preςursprs

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. Tetraacetyhetihylene 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 penta acetyl glucose.

Amide substituted alkyl peroxyacid precursors

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

_R1 — _c — _N — _R2 — _c — _{L R}1 — _N — _c — _R2 — _c — _L

O R⁵ O or R⁵ 0 O wherein R! is an alkyl group with from 1 to 14 carbon atoms, R² 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, R! preferably contains from 6 to 12 carbon atoms. R² 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 R². The substitution can include alkyl, 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.

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 R2, R3, R , and R<- may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COORg (wherein Rg 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 R¹ — N — C — R² — C — OOH

^!i !'

O R⁵ O or R⁵ O O

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 R^ 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 R^. 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 tetraacyl peroxides, 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.

Metal-containing bleach catalyst

The bleach compositions described herein may additionally contain as a preferred component, a metal containing bleach catalyst. Preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt-containing bleach catalyst.

A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn^₂(u-O)3(l ,4,7-trimethyl-l ,4,7-triazacyclononane)₂-(PF6)₂, Mεfl μ- O) i (u-O Ac)₂( 1 ,4,7-trimethy 1- 1 ,4,7-triazacyclononane)₂-(Clθ4) , Mn^{1 V}4(u-O)6( 1,4,7- triazacyclononane)4-(Clθ4)₂, Mn^πιMn^IV4(u-O) i (u-OAc)₂.( 1 ,4,7-trimethyl- 1 ,4,7- triazacyclononane)₂-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1 ,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7-- triazacyclononane, and mixtures thereof.

The bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IN) complexes such as Mn(l,4,7-trimethyl- 1,4,7- triazacyclononane)(OCH3)3_(PF6).

Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso- erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:

R² R³

R¹-N=C-B-C=N-R⁴

wherein Rl, R^, R3, and R^ can each be selected from H, substituted alkyl and aryl groups such that each Rl-N^C-R^ and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR^R", NR and C=O, wherein R^, R^, and R can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl₂, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)₂O Clθ4, Bis-(2,2'- bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N- dentate ligands, including N4MnWϊ(u-O)₂Mn^IVN4)⁺and [Bipy₂MnIH(u- O)₂MnI ^Vbipy₂]-(ClO₄)₃.

While the structures of the bleach-catalyzing manganese complexes of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+III), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi- nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn- ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stains such as tea, ketchup, coffee, wine, juice, and the like.

Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-poφhyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts having the formula:

Co[(NH₃)_nM'_mB'_bT'_tQ_qPp] Y_y

wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably 4 or 5; most preferably 5); M' represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; most preferably 1); B' represents abidentate ligand; b is an integer from 0 to 2; T' represents a tridentate ligand; t is 0 or 1 ; Q is a tetradentate ligand; q is 0 or 1 ; P is a pentadentate ligand; p is 0 or 1 ; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counteranions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and wherein further at least one of the coordination sites attached to the cobalt is labile under automatic dishwashing use conditions and the remaining co-ordination sites stabilise the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than about 0.2 volts) versus a normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula: [Co(NH₃)_n(M')_m] Y_y

wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M' is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is an appropriately selected counteranion present in a number y, which is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt.

The preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Y_y, and especially [Co(NH3)5Cl]Cl₂.

More preferred are the present invention compositions which utilize cobalt (III) bleach catalysts having the formula:

[Co(NH₃)_n(M)_m(B)_b] T_y

wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a ligand co-ordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m+n = 6, and when b=l, then m=0 and n=4; and T is one or more appropriately selected counteranions present in a number y, where y is an integer to obtain a charge-balanced salt (preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion); and wherein further said catalyst has a base hydrolysis rate constant of less than 0.23 M^~l s"l (25°C).

Preferred T are selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ", BF4", B(Ph)4", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T can be protonated if more than one anionic group exists in T, e.g., HPO42-, HCO3", H2PO4", etc. Further, T may be selected from the group consisting of non- traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.). The M moieties include, but are not limited to, for example, F", SO4^~2, NCS", SCN", S2θ3"2, NH3, PO4^", and carboxylates (which preferably are mono-carboxylates, but more than one carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety may be protonated or in its salt form). Optionally, M can be protonated if more than one anionic group exists in M (e.g., HPO42-, HCO3", H2PO4", HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted and unsubstituted C\- C30 carboxylic acids having the formulas:

RC(O)O-

wherein R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably Ci -C^g) unsubstituted and substituted alkyl, C6-C30 (preferably Cg-Ci g) unsubstituted and substituted aryl, and C3-C30 (preferably C5-C1 g) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of - NR'3, -NR' ⁺, -C(O)OR', -OR', -C(O)NR'2, wherein R' is selected from the group consisting of hydrogen and Ci -Cg moieties. Such substituted R therefore include the moieties -(CH2)nOH and -(CH2)_nNR'4⁺, wherein n is an integer from 1 to about 16, preferably from about 2 to about 10, and most preferably from about 2 to about 5.

Most preferred M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4- Cj2 alkyl, and benzyl. Most preferred R is methyl. Preferred carboxylic acid M moieties include formic, benzoic, octanoic. nonanoic. decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic. fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.

The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine).

Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. ( 1 83). 2. pages 1-94. For example. Table 1 at page 17, provides the base hydrolysis rates (designated therein as kQH) f°^r cobalt pentaamine catalysts complexed with oxalate ( oH⁼ 2- x 10^"4 M^~l s"* (25°C)), NCS^" (k₀H= ⁵-° ^{x 10~4 M_ 1 s_ 1} (25°C)), formate (k_0H= 5.8 x IO^'4 M^{" 1} s^{" 1} (25°C)), and acetate ( øH⁼ 9- x IO"⁴ M^~l s"l (25°C)). The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH3)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)2; [Co(NH₃)5OAc](PF₆)₂; [Co(NH3)₅OAc](SO₄); [Co(NH3)₅OAc](BF₄)2; and [Co(NH3)5θAc](Nθ3)2 (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article hereinbefore and the references cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem.. 18, 1497-1502 (1979); Inorg. Chem.. 21., 2881-2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952); as well as the synthesis examples provided hereinafter.

These catalysts may be coprocessed with adjunct materials so as to reduce the color impact if desired for the aesthetics of the product, or to be included in enzyme-containing particles as exemplified hereinafter, or the compositions may be manufactured to contain catalyst "speckles".

Water-soluble sulfate salt

The detergent tablet composition optionally contains a water-soluble sulfate salt. Where present the water-soluble sulfate salt is at the 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.

Alkali Metal Silicate A preferred component of the detergent composition is an alkali metal silicate. A preferred alkali metal silicate is sodium silicate having an SiO₂:Na₂O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0. Sodium silicate is preferably present at a level of less than 20%>, preferably from 1% to 15%, most preferably from 3% to 12%) by weight of SiO₂. The alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.

Hydrocarbon oils

Other preferred detergent components for use in the process of the present invenion is hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from 20 to 50; preferred hydrocarbons are saturated and/or branched; preferred hydrocarbon 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 preferrred hydrocarbon oil is paraffin. A paraffin oil meeting the characteristics as outlined above, having a ratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WTNOG 70.

Water-soluble bismuth compound

The compositions prepared by the process of the present invention suitable for use in dishwashing methods may contain a water-soluble bismuth compound, preferably present at a level of from 0.005% to 20%), more preferably from 0.01% to 5%, most preferably from 0.1% to 1% by weight of the compositions.

The water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion. Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with an organic counter anion.

Corrosion inhibitor compound

The compositions prepared by the process of the present invention and suitable for use in dishwashing methods may contain 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 copending European application No. EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are disclosed in copending European Application no. EP-A- 634,478. Mn(II) compounds for use in corrosion inhibition are described in copending European Application No. EP-A-672 749.

Organic silver coating agent may be incoφorated 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 poly-carboxylic 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, Valerie acid, lactic acid, glycolic acid and β,β'- dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butyl^nalonic 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 andsorbitan 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 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the Cι₂-C₂o 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 can also be used as an organic silver coating agent.

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 1 -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)(i) 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 MO3S(CH₂)_nOCH₂CH₂O-, 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 -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., Cj-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 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped 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- 1,2- 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 WTNOG 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 R\, R3, R4 and R5 where R\ is any of H, CH₂OH, CONH3, or COCH3, R3 and R₅ are any of Cι-C ₀ 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, moφholine, 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 incoφorated 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 incoφorated 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 C1 Q- C₂0 føtty acids, or their salts, especially aluminium tristearate. The Cι₂-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 solutionare 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 S₂O₃(ml) x Molarity (S₂O₃) 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 Cio-C₂0 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the Ci5-C₂Q 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 Ci ()-C₂o alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the Ci Q-C₂O mono- and diglycerol ethers and also the CIQ-C₂O 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.

Alkalinity system

The compositions preferably contain an alkalinity system containing sodium silicate having an SiO₂ : Na₂O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0, present preferably at a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12%o by weight of SiO₂. The alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.

The alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4%) SiO₂ by weight. Sodium metasilicate has a nominal SiO₂ : Na₂O ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO₂, is preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.

Heavy metal ion sequestrant

The detergent compositions of the invention preferably 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, incoφorated 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 -C4 diphosphonic acid, more preferably a C₂ diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1 - hydroxy- 1,1 -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 incoφorated 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 incoφorated 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 by Novo Industries A/S. Amylase enzyme may be incoφorated 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 incoφorated 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, PA 15, PA 10 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 R\ , 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 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.

Clay softening system

The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents. 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.

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 EP-A-705 324.

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 from polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

Optical brightener

The detergent compositions herein also optionally contain from about 0.005%> to 5% by weight of certain types of hydrophilic optical brighteners. Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R\ is selected from anilino, N-2-bis-hydroxy ethyl and NH-2 -hydroxy ethyl; R? is selected from N-2-bis-hydroxy ethyl, N-2-hydroxyethyl-N-methylamino,moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R\ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, R\ is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

Cationic fabric softening agents

Cationic fabric softening agents can also be incoφorated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A- 1 514 276 and EP-B-0 011 340. Cationic fabric softening agents are typically incoφorated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.

Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions

The detergent compositions used in the present invention 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 12.5, more preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.

Machine dishwashing method

Any suitable methods for machine washing or cleaning soiled tableware, particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product 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. Laundry washing method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 001 1501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Examples

Abbreviations used in Examples

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

STPP Sodium tripolyphosphate (STPP) wherein 63.2% by weight of the STPP has particle size greater than

0.6 mm and wherein 50% by weight of the STPP is in the hydrated hexahydrate form.

Carbonate Anhydrous sodium carbonate Silicate Amoφhous Sodium Silicate (SiO₂:Na₂O ratio = 2.0) PB1 Anhydrous sodium perborate monohydrate PB4 Sodium.perborate tetrahydrate of nominal formula

NaBO₂.3H₂O.H₂O₂

Percarbonate Anhydrous sodium percarbonate of nominal formula

2.Na CO3.3H₂O

Nonionic Epoxy-capped poly(oxyalkylated) alcohol nonionic surfactant of of example III of WO 94/22800 wherein

1,2 epoxydodecane is substituted for 1,2 epoxydecane sold under the tradename SLF18B by Olin (low foaming)

TAED Tetraacetyl ethylene diamine HEDP Ethane 1 -hydroxy- 1,1 -diphosphonic acid PAAC Pentaamine acetate cobalt (III) salt Paraffin Paraffin oil sold under the tradename Winog 70 by

Wintershall.

Protease Proteolytic enzyme of activity 4KNPU/g sold under the tradename Savinase by Novo Industries A/S

Amylase Amylolytic enzyme of activity 60KNU/g sold under tradename Termamyl 60T by Novo Industries A/S

MA/AA Random copolymer of acrylate/maleate, average molecular weight approx. 70,000.

BTA Benzotriazole

Sulphate Anhydrous sodium sulphate. 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:

The following detergent tablets, examples A to D, were prepared in accord with the process of the present invention by admixing pre-hydrated STPP with other detergent components, as listed below. The resulting detergent composition is then compressed at a pressure of 13KN/cm2 using a standard 12 head rotary press to produce a tablet of 20g weight:

Claims

What is claimed is:

1. A process for preparing a detergent tablet wherein the process comprises the steps of; a) obtaining partially pre-hydrated particulate hydratable salt wherein at least 60% of the hydratable salt has a particle size of 0.6 mm or greater and wherein from 25% to 70% by weight of the salt is in the hydrated state; b) admixing the partially pre-hydrated salt with the remaining detergent ingredients to form a detergent composition; and c) forming the detergent composition into tablets.

2. A process for preparing a detergent tablet wherein the process comprises the steps of; a) partially pre-hydrating particulate anhydrous hydratable salt wherein at least 60% of the hydratable salt has a particle size of 0.6 mm or greater in a pre-hydration step comprising contacting with water for a residence time sufficient to produce between 25% and 70%) of the salt in the hydrated state; b) admixing the partially pre-hydrated salt with remaining detergent ingredients to form a detergent composition; and c) forming the detergent composition into tablets.

3. A process according to either of Claims 1 or 2 wherein the hydratable salt comprises particulate anhydrous sodium tripolyphosphate (STPP).

4. A process according to Claim 2 where in the pre-hydration step the hydratable salt is contacted with water by spraying for between 90 seconds and 25 minutes in a continuously moving mixer to produce between 25% and 70%) of the salt in the hydrated state.

5. A process for preparing a detergent tablet according to any of Claims 1 to 4 additionally comprising at least 0.1% of a bleaching agent.

6. A process for preparing a detergent tablet according to any of Claims 1 to 5 additionally comprising a non-ionic surfactant.

7. A process for preparing a detergent tablet according to any of Claims 1 to 6 wherein the tablet produced has a dissolution rate such that in the test method, described herein, the time taken to achieve 100%> dissolution of the tablet is less than 20 minutes.

8. A process for preparing a detergent tablet according to any of Claims 1 to 7 wherein the tablet produced has a dissolution rate such that in the test method, described herein, the time taken to achieve 100% dissolution of the tablet is less than 17 minutes.

9. A detergent tablet produced according to any of claims 1 to 8 for use in dishwashing.

10. A detergent tablet produced according to any of claims 1 to 9 for use in laundry washing.

11. Use of a detergent tablet according to Claim 9 or 10 in a dishwashing or laundry washing method.