GB2339791A - Detergent tablet - Google Patents

Description

2339791 Detergent Tablet

Technical Field

The present invention relates to multi-phase detergent tablets.

Background

Detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form hold several advantages over detergent compositions in particulate form, such as ease of dosing, handling, transportation and storage.

Detergent tablets are most commonly prepared by pre-mixing components of a detergent composition and forming the pre-mixed detergent components into a tablet using any suitable equipment, preferably a tablet press. Tablets are typically formed by compression of the components of the detergent composition so that the tablets produced are sufficiently robust to be able to withstand handling and transportation without sustaining damage. In addition to being robust, tablets must also dissolve sufficiently ftst so that the detergent components are released into the wash water as soon as possible at the beginning of the wash 4cle.

2 However, a dichotomy exists in that as compression force is increased, the rate of dissolution of the tablets is slower. The present invention therefore seeks to find a balance between tablet robustness and tablet dissolution.

Solutions to this problem, as seen in the prior art, have included compressing the tablets with low compression pressure. However tablets made in this way, although having a fast relative dissolution rate, tend to crumble, becoming damaged and unacceptable to the consumer. Other solutions have included preparing tablets using a high relative compression pressure, in order to achieve the required level of robustness, and comprising a dissolution aid, such as an effervescent agent.

Multi-phase detergent tablets described in the prior art are prepared by compressing a first composition in a tablet press to form a substantially planar first layer. A further detergent composition is then delivered to the tablet press on top of the first layer.

This second composition is then compressed to form another substantially planar second layer. Thus the first layer is generally subjected to more than one compression as it is also compressed during the compression of the second composition. Typically the first and second compression forces are in the same order of magnitude. The Applicant has found that where this is the case, because the compression force must be sufficient to bind the first and second compositions together, the force used in both the first and second compression steps must be in the range of from about 4,000 to about 20,000 kg (assuming a tablet cross- section of about 10 CM2). A consequence of this is a slower rate of tablet dissolution. Other multi-phase tablets exhibiting differential dissolution are prepared such that the second layer is compressed at a lower force than the first layer. However, although the dissolution rate of the second layer is improved, the second layer is soft in comparison to the first layer and is therefore vulnerable to damage caused by handling and transportation.

3 EP-B-0,055,100 describes a lavatory block formed by combining a slow dissolving shaped body with a tablet. The lavatory block is designed to be placed in the cistern of a lavatory and dissolves over a period of days, preferably weeks. As a means of slowing the rate of dissolution of the lavatory block, the document teaches admixing one or more solubility control agents. Examples of such solubility control agents are paradichlorobenzene, waxes, long chain fatty acids and alcohols and esters thereof and fatty alkylamides. Detergent tablets for use in laundry or automatic dishwashing must substantially dissolve within one cycle of the washing or dishwashing machine, i.e. within 15 to 120 minutes.

SummaU of the Invention According to a first aspect of the invention, there is provided a multi- phase detergent tablet for use in a washing machine, the tablet comprising:

a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a particulate solid compressed within said mould.

In preferred embodiments, the first phase is a compressed shaped body prepared at an applied compression pressure of at least about 40 kg/ CM2, preferably at least about 250 kg/ CM2, more preferably at least about 350 kg/cM2 (3.43 kN/cM2), even more preferably ftom about 400 to about 2000, and especially from about 600 to about 1200 kg/cm2 (compression pressure herein is the applied force divided by the cross- sectional area of the tablet in a plane transverse to the applied force - in effect, the transverse cross-sectional area of the die of the rotary press). It is also preferred that the particulate solid of the second phase (which terminology is intended to include the possibility of multiple 'second' phases, sometimes referred to herein as 'optional subsequent phases') be compressed into said mould at an applied compression pressure less than that applied to the first phase and preferably at a compression 4 pressure of less than about 350 kg/cM2, preferably in the range from about 40 kgjcM2 to about 300 kg/CM2 and more preferably from about 70 to about 270 k g/CM2, such tablets being preferred herein from the viewpoint of providing optimum tablet integrity and strength (measured for example by the Child Bite Strength [CBS] test) and product dissolution characteristics. The tablets of the invention preferably have a CBS of at least about 6kg, preferably greater than about 8kg, more preferably greater than about I Okg, especially greater than about I 2kg, and more especially greater than about 14kg, CBS being measured per the US Consumer Product Safety Commission Test Specification. Also, the compression pressures applied to the first and second phases will generally be in a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1. Thus, according to a further aspect of the invention, there is provided a multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a compressed shaped body having at least one mould therein, the shaped body being prepared at a compression pressure of at least about 350 kg/crn; and b) a second phase in the form of a particulate solid compressed within said mould, the second phase being compressed at a pressure of less than about 350 kg/crn.

In other preferred embodiments, the second phase is in the form of a compressed or shaped body adhesively contained, for example by physical or chemical adhesion, within the at least one mould of the first body. It is also preferred that the first and second phases are in a relatively high weight ratio to one another, for example at least about 6: 1, preferably at least about 10: 1; also that the tablet composition contain one or more detergent actives (for example enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents etc) which is predominantly concentrated in the second phase, for example, at least about 50%, preferably at least about 60%, especially about 80% by weight of the active (based on the total weight of the active in tablet) is in the second phase of the tablet. Again, such compositions are optimum for tablet strength, dissolution, cleaning, and pH regulation characteristics providing, for example, tablet compositions capable of dissolving in the wash liquor so as to deliver at least 50%, preferably at least 60%, and more preferably at least 80% by weight of the detergent active to the wash liquor within 10, 5, 4 or even 3 n-dnutes of the start of the wash process.

Thus, according to another aspect of the invention, there is provided a multi-phase detergent tablet for use in a washing machine, the tablet comprising:

a) a first phase in the form of a shaped body having at least one mould therein, and b) a second phase in the form of a particulate solid compressed within said mould, and wherein the tablet comprises at least one detergent active and is formulated such that at least 50%, preferably at least 60%, more preferably at least 80% by weight of the detergent active is delivered to the wash within the first 10 minutes, preferably within the first 5 n-dnutes, and more preferably within the first 3 minutes of the wash process.

An additional benefit of the invention is the ability to achieve differential dissolution of the phases, such that one phase of the tablet will dissolve significantly before another phase, and may even dissolve essentially completely before the other phase has dissolved. This is particularly valuable for the differential delivery of detergent actives.

Thus, according to another aspect of the invention, there is provided a multi-phase detergent tablet comprising:

a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, and wherein the tablet composition comprises one or more detergent actives which is predominantly concentrated in the second phase, and wherein the second phase additionally comprises a disrupting agent.

6 According to a further aspect of the invention there is provided a multi- phase detergent tablet comprising:

a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, wherein the tablet composition comprises one or more detergent actives which is predominantly concentrated in the second phase, and wherein the second phase additionally comprises a binder.

Suitably, the one or more detergent actives are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof, the enzyme actives being particularly preferred for boosting cleaning performance during the very initial cool-water stage of the washing or cleaning operation. 11ighly preferred for use herein, therefore, are enzyme detergent actives and especially enzymes and enzyme mixtures comprising one or more enzymes having enhanced or optimum activity in the temperature range from 25 "C to 55'C and at a pH value in the range of 8 to 10 (e.g. Natalase).

Thus, according to a yet another aspect of the invention, there is provided a multi phase detergent tablet comprising:

a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, and wherein the second phase additionally comprises an enzyme.

Detailed Description of the Invention

It is an object of the present invention to provide a detergent tablet that is not only sufficiently robust to withstand handling and transportation, but also at least a significant portion of which dissolves rapidly in the wash water providing rapid 7 defivery of detergent active. It is preferred that at least one phase of the tablet dissolves in the wash water within the first ten minutes, preferably five minutes, more preferably four minutes of the wash cycle of an automatic dishwashing or laundry washing machine. Preferably the washing machine is either an automatic dishwashing or laundry washing machine. The time within which the multi-phase tablet or a phase thereof or a detergent active component dissolves is detern- dned according to DIN 44990 using a dishwashing machine available from Bosch on the normal 65'C washing program with water hardness at 18'H using a minimum of six replicates or a sufficient number to ensure reproducibility.

The multi-phase detergent tablet of the present invention comprises a first phase, a second and optionally subsequent phases. The first phase is in the form of a shaped body of detergent composition comprising one or more detergent components as described below. Preferred detergent components include, builder, bleach, enzymes and surfactant. The components of the detergent composition are mixed together by, for example admixing dry components or spraying-on liquid components. The components are then formed into a first phase using any suitable equipment, but preferably by compression, for example in a tablet press. Alternatively, the first phase I 8 can be prepared by extrusion, casting, etc. The first phase can take a variety of geometric shapes such as spheres, cubes, etc but preferred embodiments have a generally axially-symmetric form with a generally round, square or rectangular crosssection. 5 The first phase is prepared such that it comprises at least one mould in the surface of the shaped body. The mould or moulds can also vary in size and shape and in their location, orientation and topology relative to the first phase. For example, the mould or moulds can be generally circular, square or oval in cross-section; they can form an internally-closed cavity or recess in the surface of the shaped body, or they can extend between unconnected regions of the body surface (for example axially-opposed facing surfaces) to form one or more topological 'holes' in the shaped body; and they can be axially or otherwise symmetrically-disposed relative to the first phase or they can be asymmetrically disposed. in a preferred embodiment the mould is created using a specially designed tablet press wherein the surface of the punch that contacts the detergent composition is shaped such that when it contacts and presses the detergent composition it presses a mould, or multiple moulds into the first phase of the multiphase detergent tablet. Preferably, the mould will have an inwardly concave or generally concave surface to provide improved adhesion to the second phase.

Alternatively, the mould can be created by compressing a preformed body of detergent composition disposed annularly around a central dye, thereby forming a shaped body having a mould in the form of a cavity extending axially between opposing surfaces of the body.

The tablets of the invention also include one or more additional phases prepared from a composition or compositions which comprise one or more detergent components as described below. At least one phase (herein referred to as a second phase) preferably takes the form of a particulate solid (which term' encompasses powders, granules, agglomerates, and other particulate solids including mixtures thereof with liquid binders, meltable solids, spray-ons, etc) compressed into/within the one or more moulds of the first phase of the detergent tablet such that the second phase itself takes 9 the form of a shaped body. Optional further phases include one or more compositions in the form a separate layer or layers. Preferred detergent components include builders, colourants, binders, surfactants, disrupting agents and enzymes, in particular amylase and protease enzymes. In another preferred aspect of the present invention the second and optionally subsequent phases comprise a disrupting agent that may be selected from either a disintegrating agent or an effervescent agent. Suitable disintegrating agents include agents that swell on contact with water or facilitate water influx and/or efflux by forn-iing channels in the detergent tablet. Any known disintegrating or effervescing agent suitable for use in laundry or dishwashing applications is envisaged for use herein. Suitable disintegrating agent include starches (such as natural, modified, and pregelatinized starches, eg those derived from corn, rice and potato starch), starch derivatives such as U-Sperse (tradename), Primojet (tradename) and Explotab (tradename), celluloses, microcrystalline celluloses and ceUulose derivatives such as Arbocel (tradename) and Vivapur (tradename) both avaUable from Rettenmaier, Nymcel (tradename) available from Metsa-serla, Avicel (tradename), Lattice NT (tradename) and Hanfloc (tradename), alginates, acetate trihydrate, burkeite, monohydrated carbonate formula Na2C03.1120, hydrated STPP with a phase I content of at least about 40%, carboxymethy1cellulose (CMC), CMCbased polymers, sodium acetate, aluminium oxide. Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervesing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with carboxylic or other acids such as citric, sulphamic, malic or maleic acid.

The components of the detergent composition are mixed together by for example admixing dry components and admixing or spraying-on liquid components. The components of the second and optionally subsequent phases are then fed into and retained within the mould provided by the first phase.

The preferred embodiment of the present invention comprises two phases; a first and a second phase. The first phase will normally comprise one mould and the second phase will normally consist of a single detergent active composition. However, it is envisaged that the first phase may comprise more than one mould and the second phase may be prepared from more than one detergent active composition.

Furthermore, it is also envisaged that the second phase may comprise more than one detergent active composition contained within one mould. It is also envisaged that several detergent active compositions are contained in separate moulds. In this way potentially chemically sensitive detergent components can be separated in order to avoid any loss in performance caused by components reacting together and potentially becon-dng inactive or exhausted.

In a preferred aspect of the present invention the first, second and/or optionally subsequent phases may comprise a binder. Where present the binder is selected from the group consisting of organic polymers, for example polyethylene and/or polypropylene glycols, especially those of molecular weight 4000, 6000 and 9000, paraffins, polyvinyl pyrolindone (PVP), especially PVP of molecular weight 90 000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, for example hydroxy propyl methyl cellulose (HPMC) and carboxy methyl cellulose (CMC); and inorganic polymers, such as hexametaphosphate. The binder is valuable both for tablet integrity and to help achieve differential dissolution of the first and second phases as described below.

In a preferred aspect of the present invention the first phase weighs greater than about 3g, preferably greater than about 4g, more preferably greater than about 5g. More preferably the first phase weighs from about fOg to about 30g, even more preferably from about 15g to about 25g and most preferably from about 18g to about 24g. The second and optionally subsequent phases weigh less than 4g. More preferably the second and/or optionally subsequent phases weigh between about 0. lg and about 3.5g, preferably between about Ig and about 3.5g, most preferably from about 1.3g to about 2.5g.

In another embodiment of the present invention, a barrier layer comprising a barrier layer composition is located between the first and second phase and/or optionally subsequent phases or indeed between the second and optionally subsequent phases.

The barrier layer composition comprises at least one binder selected from the group as described above. The advantage of the presence of a barrier layer is to prevent or reduce migration of components from one phase to another phase, for example from the first phase into the second and/or optionally subsequent phases and vice versa.

The components of the second and optionally subsequent phases are preferably compressed at a very low compression force relative to compression force normally used to prepare tablets. Thus an advantage of the present invention is that because a low compression force is used heat, force or chemically sensitive detergent components can be incorporated into the detergent tablet without sustaining the consequential loss in performance usually encountered when incorporating such components into tablets. Alternatively, the second phase or phases can be compressed at the same or higher compression force than the first phase in order to achieve differential dissolution of the phases as described below.

A further advantage of the present invention is the improved protection of the second phase against damage caused by for example handling and transportation. As described above multi-phase detergent tablets have been prepared where the second layer is compressed at a lower compression force than the first layer. However although improving dissolution rate, the second layer of these tablets becomes vulnerable to damage, tending to crumble or chip on contact. The lightly compressed phase(s) of the detergent tablets of the present invention however are protected within the mould provided by the first phase of the detergent tablet.

Yet another advantage of the present invention is the ability to prepare a multi-phase detergent tablet wherein one phase can be designed to dissolve, preferably significantly before another phase. In the present invention it is preferred that the 12 second and optionally subsequent phase(s) dissolves before the first phase. According to the preferred weight ranges described above, it preferable that the first phase dissolves in from 5 to 20 minutes, more preferably from 10 to 15 minutes and the second and/or optionally subsequent phases dissolve in less than 5 minutes, more preferably less than 4.5 minutes, most preferably less than 4 minutes. Alternatively, the second phase can dissolve after the first or other phases, for example, where it is desired to deliver cleaning or rinsing benefits towards the end of the washing operation. The time in which the first, second and/or optionally subsequent phase dissolve are independent from each other. Thus in a particularly preferred aspect of the present invention differential dissolution of the phases is achieved. A particular benefit of being able to achieve differential dissolution of the multi-phase detergent tablet is that a component that is chemically inactivated by the presence of another component can be separated into a different phase. In this case the component that is inactivated is preferably located in the second and optionally subsequent phase(s).

Yet another advantage of the present invention is the improved adherence between the phases of the multi-phase tablet. It is believed that the improved adherence is achieved by reducing exposure of the second phase in comparison to multi-phase tablets known in the art, resulting in the tablets of the present invention being less susceptible to fracture along the line of contact between the phases. Proces The multi-phase detergent tablets are prepared using any suitable tabletting equipment, e.g., a Courtoy R253. Preferably the tablets are prepared by compression in a tablet press capable of preparing a tablet comprising a mould. In a particularly preferred embodiment of the present invention the first phase is prepared using a specially designed tablet press following the procedure described below. The punch(es) of this tablet press are modified so that the surface of the punch that contacts the detergent composition has a convex surface.

A first detergent composition is delivered into the die of the tablet press and the punch is lowered to contact and then compress the detergent composition to form a 13 first phase. The first detergent composition is compressed using an applied pressure generally of at least about 250 k g/CM2, preferably between about 350 and about 2000 kg/crn, more preferably about 500 to about 1500 k g/CM2, most preferably about 600 to about 1200 kg/cM2. The punch is then elevated, exposing the first phase containing a mould. A second and optionally subsequent detergent composition(s) is then delivered into the mould. The specially designed tablet press punch is then lowered a second time to lightly compress the second and optionally subsequent detergent composition(s) to form the second and optionally subsequent phase(s). In another embodiment of the present invention where an optionally subsequent phase is present the optionally subsequent phase is prepared in an optionally subsequent compression step substantially similar to the second compression step described above. The second and optionally subsequent detergent composition(s) is compressed at a 2 pressure of preferably less than about 350 kg/cm, more preferably from about 40 to about 300 kg/cm', most preferably from about 70 to about 270 kglcm2. After compression of the second detergent composition, the punch is elevated a second time and the multi-phase detergent tablet is ejected from the tablet press. DgLegrgent Components The first and'second and or optionally subsequent phases of the multi- phase detergent tablet described herein are prepared by compression of one or more compositions comprising detergent active components. Suitably, the compositions used in any of these phases may include a variety of different detergent components including buUder compounds, surfactants, enzymes, bleaching agents, alkalinity sources, colourants, perfume, time soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers, solvents, fabric softening agents, optical brighteners and hydrotropes.

Mghly preferred detergent components of the first phase include a builder compound, a surfactant, an enzyme and a, bleaching agent. ffighly preferred detergent components of the second phase include builder, enzymes, crystal growth inhibitors and disrupting agents and/or binders Builder compound 14 The tablets of the present invention preferably contain a builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition of active detergent components.

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 oxypolycarboxylate materials such as 2-oxa- 1, 1, 3 -propane tricarboxylates described in British Patent No.

1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-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.

Aficyclic 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-forn-Ling materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that 50C, especially less than 40T.

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 6 to 2 1, and salts of phytic acid. 5 Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.

Partiallv soluble or insoluble builder comr)ound The tablets 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 _.1aundry 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 silicate of gene-al "bri-nula NaMSIXO,?+l yH?O 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 5-layered structure, as described in EP 0 1645 14 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 8Na2Si2O5, 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, watersoluble ionisable material as described in PCT Patent Application No. W092/18594.

11 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 Naz[(AI02)z(SI02)YI. xH20 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 10 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived.. Syntlietic.cry.stallirle aluminosilicate ion exchange mitterials are available under the desinations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS 15 and mixtures thereof A preferred method of synthesizing, aluminosilicate zeolites is that described by Schoeman et a] (published in Zeolite (1994) 14(2), 110-116), in which the author describes a method of preparing, colloidal aluminosilicate zeolites. The colloidal Z alurninosilicate zeolite particles should preferably be such that no more than 5% of the particles are of size greater than I Pin in diameter and not more than 5% of particles are of size less then 0.05 pm in diameter. Preferably the aluminosilicate zeolite particles have an average particle size diameter of between 0.0 1 Pm and I PM' more preferably between 0.05 pm and 0.9 pm, most preferably between 0. 1 Irn and 0.6 pm..

Zeolite A has the formula Na 12 IAL102) 12 (Si02)121. xH,?O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 I(A]02)86(SI02)1061. 276 H20. Zeollte MAP, as disclosed in EP-B-3)84,070 is a preferred zeolite builder herein. Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When 35 employed as a component of a detergent composition colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide enhanced builder performance in terms leg 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 alun-dnosilicate zeolite detergent compositions, described above, provide improved magnesium ion sequestration 10 performance versus an equal weight of commercially available zeolite A. Surfactant Surfactants are preferred detergent active components of the compositions described 15 herein. 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 20 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 composition of active detergent components. 25 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 30 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 detergent tablet. Preferred, non-limiting classes of useful nonionic surfactants are listed below.

VI Nonionic ethoalated alcohol -surfactant The alkyl ethoxylate condensation products of aliphatic alcohols with from I to 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 2 to 10 moles of ethylene oxide per mole of alcohol.

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

RIO[CH2CH(CH3)0]x[CH2CH20ly[CH2CH(OH)R2I (1) wherein RI is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I, at least 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R21- Suitable surfactants of formula I, according to the present invention, are Olin Corporation's POLY-TTERGENTO SLF- I 8B nonionic surfactants, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.

Ether-capped poly(oLcyalkylated) alcohols Preferred surfactants for use herein include ether-capped poly(oxyalkylated) alcohols having the formula:

RIO[CH2CH(R3)0]x[CH2]kCH(OM[CH2]jOR2 wherein R I and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from I to 30 carbon atoms; R3 is K or a linear aliphatic hydrocarbon radical having from I to 4 carbon atoms; x is an integer having an average value from'I to 30, wherein when x is 2 or greater R3 may be the same or different and k and j are integers having an average value of from I to 12, and more preferably I to 5.

RI and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having from I to 2 carbon atoms is most preferred for R. Preferably, x is an integer having an average value of from I to 20, more preferably from 6 to 15.

As described above, when, in the preferred embodiments, and x is greater than 2, R3 may be the same or different. That is, R3 may vary between any of the alklyeneoxy units as descrIN-d abcve., For instance, if x is 3, R3 may be be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO)-, (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO).

Of course, the inte er three is chosen for example only and the varlat on may be much larger with a higher integer value for x and include, for example, mulitple (EO) units and a much small number of (PO) units.

Particularly preferred surfactants as described above include those that have a low cloud point of less than 20'C. These low cloud point surfactants may then be employed in conjunction with a high cloud point surfactant as described in detail below for superior grease cleaninu benefits.

1.7 11.1 Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those wherein k is I and j is I so that the surfactants have the formula:

RIO[CH2CH(R3)0]xCH2CH(OH)CH2OR2 where R 1, R2 and R3 are defined as above and x is an integer with an average value of from I to 30, preferably from I to 20, and even more preferably from 6 to 18.

Most preferred are surfactants wherein R I and R2 range from 9 to 14, R3 is H forming ethyleneoxy and x ranges from 6 to 15.

2-1 The ether-capped poly(oxyalkylated) alcohol surfactants comprise three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, ou-soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water soluble portion of the molecule.

These surfactants exhibit significant improvements in spotting and filming characteristics and removal of greasy soils, when used in conjunction with high cloud point surfactants, relative to conventional surfactants.

Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants of the present invention may be produced by reacti' CY an aliphatic alcohol with an epqxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention.. Examples of methods of preparing the ether capped poly(oxyalkylated) alcohol surfactants are described below:

Preparation Of C 12/14 alkyl gjycid I ether A C 12/14 fatty al cohol ( 100. 00 g, 0. 5 15 mol.) and tin (IV) chloride (0. 5 8 g, 2.23 mmol, available from Aldrich) are combined in a 500 mL three-necked round bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 'C. Epichlorhydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise so as to keep the temperature between 60-65 'C. After stirring an additional hour at 60 'C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.77-31 mol, 50%) while being stirred mechanically. After addition is completed, the mixture is heated to 90 'C for 1.5 h, cooled, and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 mL), dried over MgS04, filtered, and concentrated. Distillation of the oil at 100- 120 C (0. 1 mm Hg) providing the glycidyl ether as an oil.

Preparation of C 12/14 alkyl-Cq/ I I ether capped alcohol surfactant Neodo]O 91-8 (20.60 g, 0.03 M) mol ethoxylated alcohol available &om the Shell chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) are combined in a 250 mL three-necked round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 0 C at which point C 12/14 alkyl glycidyl ether (11.00 g, 0. 0393 mol) is added dropwise over 15 min. After stirring for 18 h at 60 'C, the mixture is cooled to room temperature and dissolved in an equal portion of dichloromethane. The solution is passed through a I inch pad of silica gel while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then stripped in a kugelrohr oven (100 C, 0.5 mm Hg) to yield the surfactant as an oil.

Nonionic ethoxviated/propoxylated fatty alcohol surfactant The ethoxylated C6-C 18 fatty alcohols and C6-C 18 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble:

- Preferaly the ethoxylated fatty alcohols are the C 1 8 ethoxylated fatty Icohols with a degree of ethoxylation of from to 50, most preferably these are the C 12-C 18 ethoxylated fatty alcohols with a degree ofethoxylation frorn-3) to 40. Preferablythe rnixed ethoxylatedy'prcooxylated fatty alcohols have an alkyl chain!ength offrom 10 to 18 carbon atoms, a degree of ethoxylation of from 3) to 30 and a degree of propoxylation of frorn II to 10.

Nonionic EO/PO condensates with propylene -glycol The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.

The hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diarnine 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 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic"m compounds, marketed by BASF.

Mixed Nonionic Surfactant -System In a preferred embodiment of the present invention the detergent tablet comprises a 5 mixed nonionic surfactant system comprising at least one low cloud point nonionic surfactant and at least one high cloud point nonionic surfactant.

"Cloud point", as used herein, is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as rd the "cloud point" (See Kirk Othmer's Encyclopedia of Chemical Technology, 3 Ed. Vol. 22, pp. 360-379).

As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30'C, preferably less than 20'C, and most preferably less than 10'C. Typical low cloud point no.ruonir. surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyox.vpropylene (PO/EO/PO) reverse block polymers. Also, such lovv cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's PolyTergentO SLF 18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergentg SLF I 8B series of nonionics, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation)and the ethercapped poly(oxyalkylated) alcohol surfactants.

Nonionic surfactants can optionally contain propylene oxide in an amount up to 15% by weight. Other preferred nonionic surfactants can be prepared by the processes described in U.S. Patent 4,22'), 16'), issued September 16, 1980, 'Builloty, incorporated herein by reference.

Low cloud point nonionic surfactants addi tionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound. Block polyoxyethylenepolyoxypropylene polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, tri methylol propane and ethylenediamine as initiator reactive hydrogen compound. Certain of the block polymer surfactant compounds designated PLLTRONICS, REVERSED PLURONIC3, and TETRONICS by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention. Preferred examples include REVERSED PLLTRONIC@ 25R2 and TETRONIC@ 702, Such surfactants are typically useU herein as low cloud point nonionic surfactants.

As used herein, a "high cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of greater than 40'C, preferably greater than 500C, and more preferably greater than 60'C. Preferably the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an averacre basis. Such high cloud point nonionic surfactants include, for example, TeTgitol 15S9 (sppplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

It is also preferred for purposes of the present invention that the high cloud point nonionic surfactant ftirther have a hydrophile-lipophile balance ("HLB"; see Kirk Othmer hereinbefore) value within the range of from 9 to 15, preferably I I to 15.

Such materials include, for example, Ter-itol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred high cloud point nonionic surfactant is derived from a straight or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon atoms (C6-C20 alcohol), including secondary alcohols and branched chain primary C alcohols. Preferably, high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/1 I or C I 1/ 15 branched alcohol ethoxylates, condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and most preferably frorn 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.

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 anWes of methyl tauride, alkyl succinates and sulfosuccinates, monciesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18 monciesters) diesters of sulfosuccinate (especially saturated and unsaturated C6_CI4 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 scondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C 17 acyl-N-(C I -C4 alkyl) and -N-(C,,-C2 hydroxyalkyl) UILIcamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpOk"'ILICoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C I O-C 18 alkyl sulfates, more preferably the C I I -C 15 branched chain alkyl sulfates and the C 12-C 14 linear chain al kyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C I O-C 18 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 I I -C 18, most preferably C I I -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from I 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 9-')'/ 18124.

Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 Unear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-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 akl 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(CH2CFf2O)x CH2C00_M' wherein R is a C6 to C 18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such-,Ihat, on a weight basis, the amount of material where x I is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those havin- the formula RO-(CHR I -CHR2-0)-R- wherein R is a C6 to C 18 alkyl group, x is from i to 2 5, R I and R2 are selected from the roup ZZ 9 consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R- is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between I 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-methylI -undecanoic acid, 2-ethyl- I -decanoic acid, 2-propylI -nonanoic acid, 2-butyl- I -octanoic acid and 2-pentyl- I -heptanoic acid. Certain 30 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 35 (RI) CH2 COOK wherein R is a C5-C 17 linear or branched alkyl or alkenyl group, 2:1 RI is a C I -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),NO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms-, R4 is an alkylene or hydroxyalkylene group contairng. from 2 to 3 carbon atorris, or mixtures thereof, x is from 0 to.5, preferably from 0 to 3; and each-. R5 is an alkyl or hydroxyalkyl group containing from I to 3, or a polyethylene oxide 0 group containing from I to 3 ethylene oxide groups. Preferred are C I O-C 18 alkyl dimethylamine oxide, and C 10- 18 acylamic.!o alkyl - dimeihylamirie oxide.

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

Zwittefionic surfactant Zwittefionic 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+R2COowherein R is a C6-C 18 hydrocarbyl group, each R I is typically C I -C3 alkyl, and R2 is a C I CS hydrocarbyl group. Preferred betaines are C 1218 dimethyl-ammonio hexanoate and the C 10- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein, Cationic surfactant Cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (i.e. -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 C6-C 16, preferably C6-C 10 N-alkyl or alkenyl ammonium surfactants 10 wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropylgroups.

E=me Enzymes are preferred detergent components of the first phase and more particularly -s. Where present s id e. y -Is are select--, the second and/or optionally further phas a nZ r tj from the group consisting of celkilases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases. cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, 20 ligninases, pullulanases, tannases, pentosanases, malanases, 3-glucanases, arabinosidases, hyalurojildase, chondroltinase, laccase or mixtures thereof Preferred enzymes include protease, aniylase,lipase, peroxidases, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbes-oard et al, J61078384 and W096/02653 which 30 disclose fungal cellulases produced respectively from Hun-cola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated ftom novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075. 028; GB-A-2.095.2751- DE-OS-2.247.832 and W095/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other 251k suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a -43kD endoglucanase derived from Hurnicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the an-dno acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable ceflulases are the EGIII cellulases from Trichoderma longibrachiaturn described in W094/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and W091/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in W096/34092, W096/17994 and W095/24471.

Said cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, W089/09813 and in European Patent application EP No.

91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.

Preferred enhancers are substitued phenthiazine and phenoxasine 10 Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.

Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases.

include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonasfluorescenl IAM 1057.

This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-F. Other suitable commercial lipases include Arnano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter visco.s-un? var. lipolyficum NR_RLB 3673 from Toyo Jozo Co., Tagata, Japan, Chi-oniobcicler viscosum lipases from U.S. Biochemical Corp., U.S.A.

and Disoynth CO'., The. Netherlands, and [1pases ex Pseudonionas glqdioli. Especially suitable lipases are lipases such as NI I LipaseR and LipomaxR (Gist- Brocades) and LipolaseR and Lipolase UltraP-(Novo) which have found to be very effective when used in dambination with the compositions of the present invention. Also suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/0') 578, WO 95/3 53 81 and WO 96/00292 by Unilever.

Also suitable are cutinases [EC 3). 1. 1. 50] which can be considered as a special kind of lipase, namely i1pases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor)-l WO 90/09446 (Plant Genetic System) and WO 94/14963) and WO 94/14964 (Unilever).

The lipases, and/or cutinases are nornially incorporated in the detergent composition at levels from 0. 000 1% to 2% of active enzyme by weight of the detergent composition.

Suitable proteases are the subtilisins which are obtained from particular strains of B. sublifis and B. ficheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE(& by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include KANNASE0, ALCALASE8, DUR-AZYMO and SAVINASE0 from Novo and MAXATASEV, MAXACALS, PROPERASEG and MAXAPEMO (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacteria] serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is caHed herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacteria] serine protealytic enzyme which is called "Protease A" herein. Suitable is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified vatiants, particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by subs.6tutinJ a diFferent amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position + 76, preferably also in combination with one or inore amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +10"), +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, + 216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquejaciens subtilisin, as described in W095/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, filed October 13, 1994.

Also suitable for the present invention are proteases described in patent applications EP 251446 and WO 91/06637, protease BLAP19 described in W091/02792 and their variants described in WO 95/2')22 1.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Udever.

Other preferred protease enzymes include protease enzymes which are a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived by replacement of a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme correspond to position +2 10 in combination with one or more of the foHowing residues: +33, +62, +67, +76, +100, +101, +103, +104, + 107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, + 217, +218 and +222, where the numbered positions correspond to naturally- occurring subtilisin from Bacillus amvloliauefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacilltis lentus subtilisin). Preferred enzymes of this type include those having position changes +210, +76, + 103, +104, +156, and +166.

The proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to O 1% pure enzyme by weight of the composition.

I Amylases ((x and/or B) can be Included for removal of carbohy drate-based stains.

W094/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutailt amylases. See also W095/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in cleaning compositions include both (x- and 0-amylases. oc-Amylases are known in the art and I - EP 252,666- WO/91/00353, FR include those disclosed in US Pat. no. 5,003,257, 1 2,676,456-, EP 285,123 '- EP 525,6 10-1 EP 368,3)4 1, and British Patent specification no.

1,296,839 (Novo). Other suitable arnylases are stability-enhanced amylases described in W094118314, published August 18, 1994 and W096/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk).

Examples of commercial a-amylases products are Purafect Ox ArriD from Genencor and TermamylO, BanO FungamylO and DuramylO, Natalase 0 all available ftom Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases: a amylases characterised by having a specific activity at least 25% higher than the I specific activity of TermamylO at a temperature range of 25C to 55"C and at a pH value in the range of 8 to 10, measured by the PhadebasO (x-amylase activity assay.

Suitable are variants of the above enzymes, described in W096/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.

Preferred amylase enzymes include those described in W095/26397 and in copending application by Novo Nordisk PCT/DK96/00056.

The amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.000 1 % to 2%, preferably from 0.000 18% to 0. 06%, more preferably from 0,00024% to 0.048% pure.enzyme by:wFicrht of the. composition In a particularly preferred embodiment, detergent tablets of the present invention comprise amylase enzymes, pari;cularly those described in W09-,126397 and co pending application by Novo Nordisk PCT/DK96/00056 in combination 'Aith a complementary amylase.

By "complementary" it is meant the addition of one or more amylase suitable for detergency purposes. Examples of complementary amylases (a and/or B) are described below. W094/02597 and W095/10603, Novo Nordisk A/S describe cleaning compositions which incorporate mutant amylases. Other amylases known for use in cleaning cornpositions include both cc- and 0-amylases. cc- Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257,- EP 252, 666; WO/91/00353; FR 2,676,456- ' EP 285,123-, EP 525,610, EP 368,341; and Bfitish Patent specifi cation no. 1,296,839 (Novo). Other suitable amylases are stability enhanced amylases described in W094/18-3 14, and W096/05295, Genencor and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/1060'). Also suitable are amylases described in EP 277 216 (Novo Nordisk). Examples of commercial (x-amylases products are Purafect Ox AmO from Genencor and Termamyl@, BanO Fungamyle and DuramylO, all available from Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases: a-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl@ at a temperature range of 25'C to 55'C and at a pH value in the ranIge of 8 to 10, measured by the Phadebas@ (x- 34- amylase activity assay. Suitable are variants of the above enzymes, described in W096/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/3) 5') 82, Preferred complementary amylases for the present invention are the amylases sold under the tradename Purafect Ox AmR described in WO 94/18314, W096/05295 sold by Genencor; Termamyle, Fungamyl 0, BanO Natalase 0 and DuramylO, all available from Novo Nordisk A/S and MaxarnylO) by Gist-Brocades.

Said complementary amylase is generally incorporated in the detergent compositions of the present invention a level of from 0. 000 1 % to 2%, preferably from 0.000 18% to 0.06%, more preferably from 0.00024% to 0. 048% pure enzyme by weight of the -composition. Preferably a weight of pure enzyme raticr of specific -amylase to the complementary amylase is comprised between 9-1 to 1-9, more preferably between 4:1 to 1:4, and most preferably between 2A and 1:2.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, arumal, bacterial, filngal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic" acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical C) modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.

Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etccontaining one enzyme) or as mixtures of two or more enzymes ( e.g.

cogranulates).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 3) 1, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 198 1. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp.

AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Bleaching ag!tnt A highly preferred component of the composition of detergent components is a bleaching agent. Suitable bleaching agents include chlorine and oxygen- releasing bleaching agents.

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

Inorganic perhydrate ble4c'hes The compositions of detergent components preferably include a hydrogen peroxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.

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

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions 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 NaB02H202 or the tetrahydrate NaB02H202.3H20.

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 2Na2CO3.3H202, and is available commercially as a crystalline solid. Sodium 20 percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise. The percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability. 25 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 30 percarbonate lies in the range from I: 200 to I: 4, more preferably from I: 99 to I 9, and most preferably from I: 49 to I: 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S04. 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. 35 Another suitable coating material providing in product stability, comprises sodium silicate Of Si02: Na20 ratio from 1. 8: I 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 Si02 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 conipourds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as 0 1! X- %- L where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is 0 H 25 X-C-OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or 0-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 =N 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. 10 Preferred L groups are selected from the group consisting of.

Y. R3 0 0 11 A 11 -N-C-R1 -N N -N-C-CH-R4 1 5 1 1 1 R R3 Y I Y R 3 Y I I 0 0 Y 0 >-L;' 4 11 4 -N NR -C-C-R' -N' C ---,-NR C R3 0 Y 1 11 1 -U-L;=CHR4 and -N-S-CH-R4 1 3 11 R 0 and rnixtures thereof, wherein R I is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from I to 8 carbon atoms, R4 is H lap 3 or R, R5 is an alkenyl chain containing from I to 8 carbon atoms and Y is H or a 0 1 3 4 solubiMng group. Any of R, R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, an-Line, nitrosyl, arnide and ammonium or alkyl ammonium groups.

+ + + - + 3 The preferred solubilizing groups are -SO 3- M, _CO 2- M _so 4- M, N (R)4X and 0<--N(R 3)3 and most preferably _S03_M + and -CO 2- M + wherein R 3 is an alkyl chain containing from I 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 20 oxybenzene sulfonate- 0 Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for exarnple ik-(D OAc AcO 0 0 OA c OAc OBz 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 includi N-benzoyl py'frolidone, aibenzoyl taurine and benzoyl 10 pyroglutamic acid.

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

C 0 0 04 COOH Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

0 0 0 Suitable N-acylated lactam perbenzoic acid precursors have the formula:

4-1 0 11 0 C_CH2_CH2 11 1 R6-C-N--CH2_4CH21n wherein n is from 0 to 8, preferably fforn 0 to 2, and R 6 is a benzoyl group.

Perbenzoic acid derivative precur 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.; noncationic) 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 an-dde substituted compounds of the following general formulae:

R1 -C-N-R2-C-L R1 -N-C-R2-C-L 11 1 5 11 1 5 11 11 0 R 0 or R 0 0 wherein R I is an aryl or aIkaryl group with from I to 14 carbon atoms, R2 is an arylene, or alkarylene group containing from I to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing I to 10 carbon atoms and L can be essentially any leaving group. RI preferably contains from 6 to 12 carbon atoms. R2 preferably contains from. 4 to 8 carbon atoms. RI may be aryl, substituted aryl or allWlaryl containing branching, substitution, or both and may be so6red fro m; either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include allql, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R I and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

4 Cationic peroxyacid -precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on 5 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; 4,998,451; 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:

0 O-OS03 r-VI \N+ / N-" 4-22 A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

so + 0 0a 3 N Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

0 0 N N / Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:

0 0 (CH N+,_/ 2)n where n is from 0 to 12, particularly from I to 5. Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl

ammonium) ethyl sodium 4-sulphophenyl carbonate chloride. 20 Alkyl 12ercarboNylic acid.tLleach pLecurs Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis. 25 4-Lt- Preferred alkyl percarboxylic precursor compounds of the imide type include the NANINI tetra acetylated alkylene diamines wherein the alkylene group contains from I to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is 5 particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose. 10 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 Ri - N - C - R2 - C - L 11 1 5 11 1 5 11 11 0 R 0 or R 0 0 wherein RI is an alkyl.-roup with frorn I to 14 carbon atoms, R2 is an alkylene group containing from I to 14 carbon atoms, and R5 is H or an alkyl group containing I to 10 carbon atoms and L can be essentially any leaving group. RI preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. RI 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. p,5 is preferably H or methyl. RI and R5 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:

0 0 1 C(N including the substituted benzoxazins of the type 0 -2 11 R 3 0 1 4 C-Ri R5 wherein R I is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R 3 R 41 and R 5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR 6 (wherein R6 is H or an alkyl group) 10 and carbonyl functions.

An especially preferred precursor of the benzoxazin-type is:

0 11 C0 1 V U-0 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 I% 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 11 1 5 ii 0 R 0 or R1 -N-C-R2-C-OOH 1 5 11 11 R 0 0 wherein RI is an alkyl, aryl or alkaryl group with from I to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from I to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl -arOLIP containing I to 10 carbon atoms. RI preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R I may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R I and R5 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0 1703 86.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioe 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, Controlled rate of release - means A means may be provided for controlling the rate of release of bleaching agent, particularly oxygen bleach to.the wash solutioq.

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.

Another mechanism for controlling the rate of release of bleach may be by coating the bleach 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 C 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 Si02: Na20 ratio from 1.8: I 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 Si02 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 C 15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 106 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 cornbination with solvents such as water, propylene glycol and the above mentioned C I O-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the CIO- C20 mono and diglycerol ethers and also the C I O-C20 fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethy1cellulose 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 alomerator/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 compression, 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 n&rometers, 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.

Metal-containing bleach catalyst The compositions described herein which contain bleach as an detergent component may additionally contain as a preferred component, a metal containing bleach catalyst.

Preferably the metal containing bleach catalyst is a transition metal containing bleach 0 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 aluminium cations, and a sequestrant having defined stability constants for the 'Catalytic and auxiliary metal cations, particularly ethyl ened i anii netet raacet i c acid, ethylenediaminetetra(metliylejiepliosplionic 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 MnIV 2(u-O)3,(l,4,7-trimethyl- 1,4,7triazacyclononane)2-(PF6)2, MnIH2(u-0) I (u-OAc)2(l,4,7-trirnethyl1,4,7-triazacyclononane)2-(CI04)2, MnIV4(u-0)6(1,4,7-triazacyclonoilane)4-(CIO4)2, MnIlIMnIV4(u-0)1(u-OAc)2 (1,4,7-tfimethyl- 1,4,7-triazacyclononane)2-(CI04)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-trii-nethyl1,5,9- tfiazacyclododecane, 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 tile cornpositions 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 mancranese (IV) complexes such as Mn(l,4,7-trimethylI,4,7 1:1 triazacyclononane)(OCH3)3_(PF6).

Still another type of bleach catalyst, as disclose.d in U.S. Pat. 5,114, 606, is a water soluble complex of manganese (111), 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: 5 R2 R3 1, 1 4 R'-N=C-B-C=N-R wherein R 1, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R I -N=C-R2 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 0, S. COO, NR7 and C=O, wherein R5, R6, and R7 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'-bispyridylaraine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and - bispyridylamine complexes. Highly preferred catalysts include Co(2,2'- bispyridylamine)CI2, Di(isothiocyanato)bispyridylamine-cobalt (11), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)202CIO4, 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-Ndentate ligands, including N4Mnl11(u-O)2MnIVN4)+and [BiPY2Mn1II(u0)2MnlVbiPY2]-(CI04)3.

VAile the structures of the bleach-catalyzing manganese complexes of the present invention have not been eluc idated, 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), (+111), (+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 (metal loporphyrin 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 (marivanese/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[(N'H3)nM'mB'bT'tQqPp] YY 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 I or 2; most preferably 1), B' represents a bidentate ligand, b is an integer ftom 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 + R + 4q + 5p = 6; Y is one or more appropriately selected counteranions present in a number y, where y is an integer from I to 3 (preferably 2 to 3; most preferably 2 when Y is a -I 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 remairung co-ordination sites stabilise the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (111) to cobalt (H) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) versus a normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula:

[Co(NH3)n(M')m] Yy 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, brornine, hydroxide, water, and (when m is greater than 1) combinations thereof, m is an integer from I to 3 (preferably I 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 I to 3 (preferably 2 to 3; most preferably 2 when Y is a -I charged anion), to obtain a cbarge-balanced salt.

The preferred cobalt catalyst of this type useful herein are cobalt pentaarnine chloride salts having the formula [Co(NH-)5CI] Y and especially [Co(NH3)5CI]CI2. Y, More preferred are the present invention compositions which utilize cobalt (HI) bleach catalysts having the formula:

1C0(NH_3))n(M)m(B)b] Ty 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; rn is 0, 1 or 2 (preferably 1); B is a ligand co-ordinated to the cobalt by two sites; b is 0 or I (preferably 0), and when Ib=0, then m+n = 6, and when b=1, then m=O 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 I to 3; most preferably 2 when T is a -I charged anion); and wherein further said catalyst has a base hydrolysis rate constant of less than 0. 23 M- I s- 1 (2 5 0 Q.

Preferred T are selected from the group consisting of chloride, iodide, 13-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFC, BF4-, B(Ph)4-, phosphate, phosphite, silicate, tosylatp, methanesulfonate, and combinations thereof. Optionally, T can be protonated if more than one anionic group exists in T, e.g., BP04 2-, HC03-, H2PO4-, etc. Further, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g., linear 0 alkylberizene 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-, S04-2, NCS-, SCN-, S203-2, NH3, P04 3-, 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., HP042-, HC03-, H2P04-, HOC(O)CH2C(0)0-, etc.) Preferred M moieties are substituted and unsubstituted C I -C3 0 carboxylic acids having the formulas:

RC(O)O- wherein R is preferably selected from the group consisting of hydrogen and CI-C30 z (preferably CI-C 18) unsubstituted and substituted alkyl, C6-C30 (preferably C6-CI8) unsubstituted and substituted aryl, and C3-C30 (preferably C5-C18) unsubstituted and substituted heteroaryl, wherein substiftlents are selected from the group consisting of TqR13, -NR'4+, - C(O)OR', -OR', -C(O)NR'2, wherein Wis selected from the group consisting of hydrogen and CI-C6 rnoieties. Such substituted R therefore include the moieties -(CH2)nOH and -(CH2)nNR'4+, wherein n is an integer ftom I to 16, preferably from 2 to 10, and most preferably from 2 to 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 C4C12 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 an-tino 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", Ady. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table I at page 17, provides the base hydrolysis rates (designated therein as kOH) for cobalt pentaamine catalysts cornplexed with oxalate (kOH= 2.5 x 10-4 M-1 s-I (25 Q, NCS(kOH= 5.0 x 10-4 M- I s- I (25'C)), formate (kOH= 5.8 x 10-4 M- I s- I (25C)), and acetate (kOH= 9.6 x 10-4 M- I s- I (250Q. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula (Co(NH3)5OAc] TY, wherein OAc represents an acet ' ate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH-)50Ac]Cl2, as well as [Co(NH3)5OAc](OAc)2; [Co(NH3)50Ac](PF6)2, [Co(NH3)5OAc](SO4); ICO (NH3)5OAc](BF4)2, and [Co(NH3)5OAc](NO3)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), E6 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L.

Jolly (Prentice-Hall; 1970), pp. 46 1 -3, Inorg. Chem., 18, 1497-15 02 (1979);!Dar Chem. 21, 2981-2885 (1982), Inory -2025 (1979); Inorg.

- Chem., 18, 2023 Synthesis, 173-176 (1960)-, and Journal of Physical ChemLtry, L6, 22-25 (1952); as weH as the synthesis examples provided hereinafter.

Cobalt catalysts suitable for incorporation into the detergent tablets of the present invention may be produced according to the synthetic routes disclosed in U.S. Patent Nos. 5,559,261, 5,581,005, and 5,597,936, the disclosures of which are herein incorporated by reference.

These catalysts may be co-processed with adjunct materials so as to reduce the colour 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".

Organic polymerig comagu-nd Organic polymeric compounds may be added as preferred components of the detergent tablets in accord with the invention. By organic polymeric compound it is meant essentially any polymeric organic compound commonly found in detergent compositions having dispersant, anti-redeposition, soil release agents or other detergency properties.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of frorn 0. 1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.

I Examples of organic polymeric compounds include the water soluble organic homo or co-polymeric polycarboxylic acids, modified polycarboxylates 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, furnaric, nialeic, 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 traderiame Sokalan PA30, PA20, PA15, PAIO and Sokalan CP 10 by BASF GmbH, and those sold under the tradename Acusol 45N, 480N, 460N 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- CRI(CO O-R3)1- wherein at least one of the substituents R I, R2 or R3, preferably RI or R2 is a I to 4 carbon alkyl or hydroxyalkyl group, R 1 or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein RI is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer). The most prefer-red 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.

S'6 The polyamine and modified polyamine compounds are useful herein including those derived from aspartic. acid such as those disclosed in EPA-305282, EP-A-305283 and EP-A-351629.

Other optional polymers may polyvinyl alcohols and acetates both modified and nonmodified, cellulosics and modified cellulosics, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, both modified and non-modified, terephthalate esters of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.

Suitable examples are disclosed in US patent Nos. 5,591,703, 5,597,789 and 4,490,271.

Soil Release Agen 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 I to 30 oxypropylene units, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units, or (b) one or more hydrophobe components comprising W C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 allqlene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) CI-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form Of C I -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 200, although higher levels can be used, preferably from 3 to 150, more I preferably from 6 to 100. Suitable OxY C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M03S(CH2)nOCH2CH20-, 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, copolyi-neric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are cornmercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein 10 also include those selected from the group consisting Of C I - C4 alkyl and C4hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nficol, et al. Soil release agents characterized by poly(vinyl ester) hydrophobe segments include 15 graft copolymers of poly(vinyl ester), e.g., C I -C6 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. 20 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 25,000 to 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. 25 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. 30 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, 35 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 oligomefic 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 sulfbarolyl, end-capped tereplithalate esters.

Another soil release agent is an oligoiner with re eat units of terephthaloyl units, p sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. Therepeat 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 one sulfbisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy 1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-etliaiiesulfoilate.

HeM metal ion sequestrant The tablets 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, mancranese and copper.

0 Heavy metal ion sequestrants are generally present at a level of from 0. 005% to 20%, D 1 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.

I 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 couriter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof r Preferably any salts/complexes are water soluble. The molar ratio of said counter i 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 I- - ---M I hydroxy disphosphonates and nitrilo triinethylene 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 nitrilotfiacetic acid and polyarninocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediapine disuccinic acid or any salts thereof Especially preferred is ethyl ened iamine-N,N'-disuccinic acid (EDDS) or the alkafi metal, alkaline earth metal, aninioniurn, 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 tablets preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0. 1% to 2% by weight of the compositions.

By organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo amino phospho nates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.

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

Water-soluble sulfate salt The detergent tablet optionally contains a water-soluble sulfate salt. Where present the water-soluble sulfate salt is at tile level of from 0. 1% to 40%, more preferably ftom 1% to 30%, most preferably frorn 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 firorn the sulfates of the alkali and alkaline earth metals, particularly sodium Sulfate.

Alkali Metal Silicate An alkali metal silicate is a preferred component of the tablet of the present invention. A preferred alkali metal silicate is sodium silicate having an Si02: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 S'02. The alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.

Alkali metal silicate may also be present as a component of an alkalinity system.

The alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% Si02 by weight. Sodium metasilicate has a nominal Si02: Na2O ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as Si02, is preferably from 50: 1 to 5:4, more preferably from 15: 1 to 2: 1, most preferably from 10: 1 to 5:2.

Colourant The term 'colourant', as used herein, means any substance that absorbs specific wavelengths of light from the visible light spectrum. Such colourants, when added to a detergent composition have tile effect of chAnging the visible colour and thus the appearance of the detergent composition. Colourants may be for example either dyes or pigments. Preferably the colourants are stable in composition in which they are to be incorported. Thus in a composition of high pH the colourant is preferably alkali stable and in a composition of low pH the colourant is preferably acid stable.

The first and/or second and/or optionally further phases may contain a colourant, a mixture of colourants, coloured particles or mixture of coloured particles such that the various phases have different visual appearances. Preferably one of either the first or the second phases comprises a colourant. Where both the first and second and/or subsequent phases comprise a colourailt it-is preferred that the colourants have a different visual appearance.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquirione dye, quinoline dyes, monoazo, disazo and polyazo. More preferred dyes include anthraquinone, quinoline and monoazo dyes.

Preferred dyes include SANDOLAN E-HRL 180% (tradename), SANDOLAN MELLING BLUE (tradenanie), TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename) all available from Clariant M BEXACOL QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename) both available from Pointings, UK, ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFIX TURQUISE BLUE EBA (tradename) available from Bayer, USA.

The colourant may be incorporated into the phases by any suitable method. Suitable methods include mixing all or selected detergent components with a colourant in a drum or spraying all or selected detergent components with the coloufant in a rotating drum.

Colourant when present as a component of the first phase is present at a level of from 0.001% to 1.5%, preferably from 0.0 1 % to 1.0%, most preferably from 0. 1% to 0.3%. When present as a component of the second and/or optionally further phases, colourant is generally present at a level of from 0. 00 1 % to 0. 1%, more preferably from 0.005% to 0.05%, most preferably from 0.007% to 0.02%.

Corrosion inhibitor compound The tablets of the present invention suitable for use in dishwashing methods may I contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing corrosion inhibitor compounds and Mn(H) compounds, particularly Mn(II) salts of organic ligands.

E7-2- Organic silver coating agents are described in PCT Publication No. W094/16047 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 incorporated at a level of from 0.05% to 10%, preferably from 0. 1% to 5% by weight of the total composition.

The functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied. The silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are 15 being treated.

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

The fatty acid portion of the fatty ester can be obtained from mono- or polycarboxylic acids having from I to 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 0,0'- dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butylmalonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

The fatty alcohol radical in the fatty ester can be represented by monoor polyhydric alcohols having from I 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 I to 24 carbon atorns in the alkyl chain.

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

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

Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and tallowyl proprionate. Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan niono-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 com oil.

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

AJginates and gelatin are suitable organic silver coating agents herein.

Dialkyl amine oxides such as C 12-C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C 12-C20 methylammonium halides are also suitable.

Other suitable organic silver coating agents include certain polymeric materials.

Polyvinylpyrrolid ones 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 vinylin-ddazole, and cellulose derivatives such as methylcellulose, carboxymethy1cellu lose and hyd roxyet hyl cellulose 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.

A preferred organic silver coating agent is a paraffin oil, typically a predominantly D 0 branched aliphatic hydrocarbon having a number of carbon atoms in the range of &om 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 meetinlu these characteristics, having a ratio of cyclic to noncyclic hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Nitroggn-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 1, R3, R4 and R5 where RI is any of K CH20H, CONH3, or COCH-), R3 and R5 are any Of C I -C20 alkyl or hydroxyl, and R4 is any of H, NH2 or N02.

Other suitable nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, I -phenyl-5-mercapto- 1,2,3,4tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, arninotriazole, aminotetrazole and indazole.

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

Mn(ID corrosion inhibitor Compounds The detergent tablets may contain ail Mn(II) corrosion inhibitor compound. The Mn(H) compound is preferably incorporated at a level of from 0.005% to 5% by weight, more preferably from 0.01% to 1%, most preferably from 0. 02% to 0.4% by weight of the compositions. Preferably, the Mn(II) compound is incorporated at a level to provide from 0. 1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 pprn' most preferably from I ppm to 20 ppin by weight of Mn(II) ions in any bleaching solution.

The Mn (11) 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(H) compound may be a salt or complex of an organic ligand. In one preferred aspect the organic ligand is a heavymetal 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 CIO-C20 fatty acids, or their salts, especially aluminium tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa- decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable. 5 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.

Hydrocarbon oils Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from 20 to 5Q; preferred hydrocarbons are D 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 preferred hydrocarbon oil is paraffin. A paraffin oil meeting the characteristics as outlined above, having a ratio of cyclic to noncyclic hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Water-soluble bismuth compound The detergent tablets 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 0.0 1% 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.

Enz)me Stabilizing System Preferred enzyme-containing compositions herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 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 scaven(yers and mixtures thereof Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap diapersant comgaLind The tablets of the present 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 frorn 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 fime soap disperant compounds are disclosed in PCT Application No. W093/08877.

Suds suppressing system The detergent tablets of the present 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 antifoarn compound, including., for example silicone antifoam compounds, 2-alkyl and alcanol antifoarn compounds. Preferred suds suppressing systems and antifoarn compounds are disclosed in PCT Application No. W093/08876 and EP-A-705 324.

Polymeric dyeAransfer inhibiting agents The detergent tablets 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 inhibitiIII-YI agMits are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and Nvinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof 0126cal brightene The detergent tablets suitable for use in laundry washing methods as described herein, also optionally contain from 0.005% to 5% by weight of certain types of hydrophific optical brighteners. 10 Hydrophilic optical brighteners useful herein include those having the structural formula:

RI R, N H H N N 0>-N _IP_C=C--P-N-O N S03M S03M R, wherein R I is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl- N-methylan-dno, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R I is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the briahtener is 4,4',-bis[(4-anilino-6-(N2-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-LTNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R I is anilino, R2 ij N-2-hydroxyethyl-N-2methylamino and M is a cation such as sodium, the brialitener is 4,4'bis[(4-anilino-6-(N-2- 0 hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,21-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the 0 tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

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

Clgy softening system The detergent tablets suitable for use in laundry cleaning methods 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 15 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. Cationic fabric s ftening agents 20 Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention which are suitable for use in methods of laundry washing. Suitable cationic fabric softening agents include the water insoluble tertiary arnines or dilong chain amide materials as disclosed in GB-A-I 514 276 and 25 EP-B-0 0 11340.

Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from I% to 5% by weight.

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

pH of the compositigns -M-M The detergent tablets of 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 are envisaged.

0 A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, silverware, metallic items, cutlery and mixtures thereot with an aqueous liquid having dissolved or dispensed therein an effective amount of a detergent tablet in accord with the invention. By an effective amount of the detergent tablet it is meant from Sa 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.

Preferably the detergent tablets are frorn 15g to 40g in weight, more preferably from 20g to 35g in weight.

Laundj 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 tablet composition in accord with the invention. By an effective amount of the detergent tablet 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 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 thewashcycle. Its volume capacity should bLd 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 aow for release of the detergent product during the wash the device may possess a number of openings through which tile product may pass. Alternatively, the device may be made of a material which is permeable toliquid but impermeable to the soud product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at tile 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 pubUshed Patent Application No. 00 18678. 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 AppUcationNos. 0011500,0011501, 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 fbHowing meanings:

STPP Sodium tripolyphosphate Bicarbonate Sodium hydrogen carbonate Citric Acid Anhydrous Citric acid Carbonate Anhydrous sodium carbonate Silicate Amorphous Sodium Silicate (Si02:Na2O ratio 2.0) SKS-6 Crystalline layered silicate of formula 5- Na2Si2O5 PB1 Anhydrous sodium perborate monohydrate Nonionic C 13 -C 15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the tradename Plurafac by BASF TAED Tetraacetyl ethylene diamine HEDP Ethane I -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 Amylase Amylolytic enzyme. BTA Benzotriazole Sulphate Anhydrous sodium sulphate. PEG 3000 Polyethylene Glycol molecular weight approximately 3) 000 available from Hoechst PEG 6000 Polyethylene Glycol molecular weight approximately 6000 available from Hoechst pH Measured as a 1% solution in distilled water at 20'C In the following examples all levels are quoted as parts by weight:

Examples I-IV

The following illustrates examples detergent tablets of the present invention suitable for use in a dishwashing machine.

III IV V VI Phase I STPP 9.62 9.62 10.45 9.57 9.57 11.47 Silicate 0.50 0.67 1.60 1.00 1.00 2.40 SKS-6 1.5 1.50 2.30 2.25 Carbonate 2.33 2.74 3.5 3.59 4.10 5.25 BEDP 0.18 0.18 0.18 0.28 0.28 0.28 PBI 2.45 2.45 2.45 3.68 3-.68 3.68 PAAC 0.002 0.002 0.002 0.003 0.004 0.004 Amylase 0.148 0.110 0.110 0.252 0.163 0.163 Protease 0.06 0.06 0.06 0.09 0.09 0.09 Nonionic 0.40 0.80 0.80 1.20 1.20 1.20 PEG 6000 0.4 0.26 0.26 0.38 0.39 0.39 BTA 0.04 0.04 0.04 0.06 0.06 Paraffin 0.10 0.10 0.10 0.15 0.15 0.15 Perfume 0.02 0.02 0.02 0.013 0.013 0.013 Sulphate 0.502 0.05 2.843 Total 17.75g 18.55g 19.57g 23.Og 23.Og 23.Og Phase 2 Amylase 0.30 0.35 0.25 0.30 0.35 0.25 Protease 0.25 0.22 0.30 0.25 0.22 0.30 Citric acid 0.3 0.30 0.3 0.30 Sulphamic acid 0.3 0.3 Bicarbonate 1.09 0.45 0.45 1.09 0.45 0.45 Carbonate 0.55 0.55 Sificate 0.64 0. 64 CaC12 0.07 0.07 PEG 3000 0.06 0.06 0.06 0.06 0.06 0.06 Total 2.Og 2.Og 2.Og 2.Og 2.Og 2.Og The multi-phase tablet compositions are prepared as follows. The detergent active composition of phase I is prepared by admixing the granular and liquid components and is then passed into the die of a conventional rotary press. The press includes a punch suitably shaped for forming the mould.'The cross-section of the die is approximately 3008 mm. The composition is: then subjected to to a compression force of 940 kg/cM2 and the punch is then elevated exposing the first phase of the tablet containing the mould in its upper surface. The detergent active composition of phase 2 is prepared in similar manner and is passed into the die. The particulate active composition is then subjected to a compression force of 170 kg/CM2, the punch is elevated, and the multi-phase tablet ejected from the tablet press. The resulting tablets dissolve or disintegrate in a washing machine as described above within 12 minutes, phase 2 of the tablets dissolving within 5 minutes. The tablets provide excellent dissolution and cleaning characteristics together with good tablet integrity and strength. 5 V I I i 1.5

Claims (13)

Claims

1. A multi-phase detergent tablet comprising:

a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, and wherein the second phase comprises an enzyme.

2. A multi-phase detergent tablet according to claim I wherein the second phase is compressed at a pressure of less than about 350 kg/CM2.

3. A multi-phase detergent tablet comprising: a) a first phase in the form of a compressed shaped body having at least one mould therein, the shaped body being prepared at a compression pressure of at least about 350 k g/CM2; and b) a second phase in the form of a compressed body adhesively contained within said mould, the second phase being compressed at a pressure of less than about 350 kgIcm2and wherein the second phase comprises an enzyme.

4. A multi-phase detergent tablet according to any preceding claim wherein the second phase dissolves more rapidly than the first phase.

5. A multi-phase detergent tablet according to any of the preceding claims wherein the second phase dissolves in a dishwashing Machine in 5 minutes.

6. A multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a shaped body having at least one mould therein, and 6 b) a second phase'in the form of a compressed body adhesively contained within said mould, and wherein the tablet comprises an enzyme and is formulated such that at least 50%, preferably at least 60%, more preferably at least 80% by weight of the enzyme is delivered to the wash within 10 minutes, preferably within 5 minutes, and 5 more preferably within 3 minutes.

7. A multi-phase detergent tablet comprising: a) a first phase in the form of a shaped body having at least one mould therein; and b) a second phase in the form of a compressed body adhesively contained within said mould, and wherein the tablet composition comprises an enzyme predominantly concentrated in the second phase.

8. A multi-phase detergent tablet according to any of the preceding claims wherein the first and/or second phases comprise a binder.

9. A multi-phase detergent tablet according to claim 8 wherein the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers.

10. A multi-phase detergent tablet according to any of the preceding claims additionaUy comprising a barrier phase between the first and second phases.

11. A multi-phase detergent tablet according to claim 10 wherein the barrier layer comprises a binder applied in liquid form.

12. A method of washing in a washing machine comprising charging a washing machine with one or more multi-phase detergent tablet according to any of the preceding claims.

13. A method according to claim 12 wherein the multi-phase detergent tablet dissolves or disintegrates in less than 15 n-dnutes in a dishwashing washing machine according to the dissolution test method described herein.

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