MXPA00001179A - Detergent tablet - Google Patents

Abstract

The present invention provides a detergent tablet comprising:a) a compressed portion comprising active detergent components;b) a non compressed, non-encapsulating portion comprising active detergent components. Detergent components which are sensitive to compression can be incorporated into tablets and greater control of washing processes can be achieved.

Description

DETERGENT TABLET FIELD OF THE INVENTION The present invention provides a detergent tablet comprising a compressed portion and a non-compressed, non-encapsulating portion.

BACKGROUND Detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form contain several advantages over detergent compositions in the form of particles, such as ease of handling, transportation and storage. Detergent tablets are most commonly prepared by pre-mixing components of a detergent composition in a tablet using a tablet press. Tablets are typically formed by compressing the components of the detergent composition in a tablet. However, the Applicants have discovered that some components of a detergent composition are adversely affected by the compression pressure used to form the tablets. Those components could not be previously included in a detergent tablet composition without sustaining a loss in performance. In some cases the components may still become unstable or inactive as a result of compression. In addition, as the components of the detergent composition are compressed, the components are put in close proximity to one another. A result of the close proximity of the components may be that certain components will react with one another, becoming unstable, inactive or worn. One solution to this problem, as seen in the prior art, has been to separate the components of the detergent composition that can potentially react with one another when the detergent composition is compressed into a tablet. The separation of the components has been achieved by, for example, the preparation of multilayer tablets in which the components that can potentially react with one another are contained in different layers of the tablet. Multilayer tablets are traditionally prepared using multiple compression steps. The layers of the tablet that are subjected to more than one compression step are subjected to a total and potentially larger cumulative compression pressure. An increase in the compression pressure of the tabletting press is known to decrease the dissolution rate of the tablet with the effect that said multiple layer may not dissolve satisfactorily during use. Other methods to achieve separation of the detergent components have been described. For example, EP-A 0,224,135 discloses a dishwashing detergent in a form comprising a melt soluble in warm water, in which a tablet soluble in cold water is pressed. The document teaches a detergent composition consisting of two parts, the first part dissolving in the pre-rinse and the second part dissolving in the main washing of the dish washer. EP-B-0,055,100 discloses a toilet block formed by the combination of a formed body that dissolves slowly with a tablet. The toilet block is designed to be placed in a toilet cistern and dissolves for a period of days, preferably weeks. As a means of controlling the dissolution of the toilet block, the document teaches mixing one or more solubility control agents. Examples of said solubility control agents are paradichlorobenzene, waxes, long chain fatty acids and alcohols and esters thereof and fatty alkylamides. Detergent tablets for use in a laundry or automatic dishwashing machine must be substantially dissolved within a washing cycle or the dishwashing machine, ie within 30 to 120 minutes. The Applicant has discovered that by providing a detergent tablet comprising a compressed portion and a non-compressed, non-encapsulating portion, detergent components that were previously considered to be unacceptable for detergent tablets, can be incorporated into a detergent tablet. In addition, potentially reactive components of the detergent composition can be effectively separated.

An additional advantage of using a detergent tablet as described herein is the performance benefits that can be achieved by being able to prepare the detergent tablet so that, if required, the compressed portion and the uncompressed portion have speeds different from dissolution. Said performance benefits are achieved by selectively supplying active detergent components in the wash solution at different times.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention there is provided a detergent tablet comprising: (a) a compressed portion consisting of an active detergent component; and (b) a non-compressed, non-encapsulating portion comprising an active detergent component, characterized in that the detergent tablet consists of an enzyme. In an alternate embodiment, a detergent tablet is also provided comprising: (a) a compressed portion consisting of an active detergent component; and (b) a non-compressed, non-encapsulating portion comprising an active detergent component, characterized in that the weight ratio of the compressed portion to the uncompressed portion is greater than 0.5: 1 and the detergent tablet consists of silicate. In another alternate embodiment, a detergent tablet is provided comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion comprising an active detergent component, characterized in that the weight ratio of the compressed to the uncompressed portion is greater than 0.5: 1 and the detergent tablet has a larger dissolution rate of 0.33 g / min. as determined using the SOTAX dissolution test method described herein. In yet another alternate embodiment, a detergent tablet is provided comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion comprising an active detergent component, characterized in that the detergent tablet is less than 40 g and the detergent tablet has a dissolution rate greater than 0.33 g / min. as determined using the SOTAX dissolution test method described herein. In yet another alternate embodiment, a detergent tablet is provided comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion comprising an active detergent component, characterized in that the compressed portion provides a mold for accommodating the non-compressed portion. In addition, a method for preparing the detergent tablets described herein is also provided.

DETAILED DESCRIPTION OF THE INVENTION In this way, according to the present invention it has been discovered that active detergent components of a detergent tablet previously adversely affected by the compression pressure used to form the tablets, can now be included in a detergent tablet. Examples of these components include bleaching agents and enzymes. Further, in accordance with the present invention it has been discovered that active detergent components of a detergent tablet can be separated from one another by having one or more compatible components contained in a compressed portion and one or more compatible components contained in an uncompressed portion of the Tablet. Examples of components that may interact and therefore may require separation include bleaching agents, bleach activators or catalysts and enzymes; bleaching agents and catalysts or bleach activators; bleaching agents and surfactants; alkalinity sources and enzymes. Additionally, it may be advantageous to provide the compressed and non-compressed portions so that they dissolve in the wash water with different dissolution rates. Controlling the dissolution speed of each portion in relation to each other, and by selecting the active detergent components in the respective portions, the order of release in the wash water can be controlled and the cleaning performance of the detergent tablet can be improved. For example it is often preferred that the enzymes are supplied to the wash before the bleaching agent and / or bleach activator. It may also be preferred that a source of alkalinity be released into the wash water more quickly than other components of the detergent tablet. It is also contemplated that it may be advantageous to prepare a detergent tablet according to the present invention in which the release of certain components of the tablet is retarded relative to other components. It is also contemplated that the tablet may consist of a plurality of compressed and non-compressed portions. For example, a plurality of compressed portions may be arranged in layers and / or a plurality of uncompressed portions may be present as discrete sections of the tablet separated by a compressed portion. In this manner, there may be a first and a second and optional subsequent compressed and non-compressed portions, each consisting of an active detergent component and in which at least the first and second portions may consist of different active detergent components or mixtures thereof. components. Said plurality of compressed and uncompressed portions may be advantageous, allowing a tablet to be produced which has, for example, a first and a second optional subsequent portions so as to have different dissolution rates. Said performance benefits are achieved by selectively supplying active detergent components in the wash water at different times.

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The detergent tablets described herein are preferably between 15 g and 100 g by weight, more preferably between 18 g and 80 g by weight, even more preferably between 20 g and 60 g by weight. The detergent tablet described herein that is suitable for use in automatic dishwashing methods are more preferably between 20 g and 40 g in weight. Detergent tablets suitable for use in laundry methods are more preferably between 40g and 100g by weight, more preferably between 40g and 80g, more preferably between 40g and 65g by weight. The weight ratio of compressed portion to non-compressed portion is generally greater than 0.5: 1, preferably larger than 1: 1, more preferably larger than 2: 1, even more preferably larger than 3: 1, or even 4: 1, more preferably at least 5: 1. The detergent tablets described herein have Child Bite Resistance (CBS) which is generally larger than 10Kg, preferably larger than 12Kg, more preferably larger than 14Kg. The CBS is measured by the Test Specification of the Consumer Product Safety Commission of E.U.A. (U.S. Consumer Product Safety Commission Test Specification). Child Bite Resistance Test Method: According to this method the tablet is placed horizontally between two bands / metal plates. The upper and lower plates are joined by hinges on one side, so that the plates look like a human jaw. A force is applied that increases down to the top plate, simulating the closing action of the jaw, until the tablet breaks. The CBS tablet is a measure of the force in kilograms required to break the tablet. The detergent tablets described herein generally have a dissolution rate of faster than 0.33 g / min, preferably faster than 0.5 g / min, more preferably faster than 1.00 g / min, even more preferably faster than 2.00 g / min. min, more preferably faster than 2.73 g / min. The rate of dissolution is measured using the SOTAX dissolution test method. For the purposes of the present invention the dissolution of the detergent tablets is achieved using a SOTAX machine (trademark); AT7 model number available from SOTAX. SOTAX Dissolution Test Method: The SOTAX machine consists of a water bath with a temperature controlled lid. 7 kettles are suspended in the water bath. 7 electric stirring rods are suspended from the bottom side of the lid, in the position corresponding to the position of the kettles in the water bath. The lid of the water bath also serves as a lid over the kettles. The SOTAX water bath is filled with water and the temperature meter is set at 50 ° C. Each kettle is then filled with 1 liter of deionized water and the agitator is set to rotate at 250 rpm. The lid of the water bath closes, allowing the temperature of the deionized water in the kettles to equilibrate with the water in the water bath for 1 hour.

The tablets are heavy and one tablet is placed in each pot, then the lid is closed. The tablet is monitored visually until it dissolves completely. The time is recorded when the tablet has completely dissolved. The dissolution rate of the tablet is calculated as the average weight (g) of the tablet dissolved in deionized water per minute.

Compressed portion The compressed portion of the detergent tablet comprises at least one active detergent component but may consist of a mixture of more than one active detergent components, which are compressed. Any detergent tablet component used conventionally in known detergent tablets is suitable for incorporation into the compressed portion of the detergent tablets of this invention. The suitable active detergent components are described below. Preferred active detergent components include detergency builder compound, surfactants, bleaching agent, bleach activator, bleach catalyst, enzyme and a source of alkalinity. The active detergent components present in the compressed layer can optionally be prepared with a carrier and / or binder eg water, polymer (eg PEG), liquid silicate. The active detergent components are preferably prepared in the form of particles (for example in the form of granules or powders) and can be prepared by any known method, for example conventional spray drying, granulation or agglomeration. The active detergent components are then compressed using any suitable equipment for the formation of tablets, blocks, bricks or compressed briquettes; described in more detail right away.

Portion not compressed, not encapsulating The non-compressed, non-encapsulating portion (hereinafter "non-compressed portion") comprises at least one active detergent component, but may consist of a mixture of more than one active detergent component. Active detergent components suitable for incorporation into the non-compressed portion include components that interact with one or more detergent components present in the compressed portion. In particular, the preferred components of the non-compressed portion are those that are adversely affected by compression pressure of for example a tablet compression press. Examples of such active detergent components include, but are not limited to, surfactants, bleaching agents, bleach activator, bleach catalyst, enzyme, corrosion inhibitor, perfume and a source of alkalinity. These components are described in more detail below. The active detergent components can be in any form, for example particles (ie powder or granular), gel or liquid form. The non-compressed portion in addition to comprising an active detergent component, may also consist of a carrier component. The active detergent component can be present in solid, gel or liquid form, before the combination with a carrier component. The non-compressed portion of the detergent tablet may be in solid, liquid or gel form. The detergent tablet of the present invention requires that the non-compressed portion be supplied to the compressed portion in such a manner that the compressed portion and the uncompressed portion contact one another. The non-compressed portion can be supplied to the compressed portion in solid or flowable form. Where the non-compressed portion is in solid form, it is pre-prepared, optionally formed and then supplied to the compressed portion. The non-compressed portion is then fixed to the pre-formed compressed portion, for example by adhesion or by insertion of the non-compressed portion to a cooperating surface of the compressed portion. Preferably the compressed portion comprises a pre-prepared mold or depression in which the non-compressed portion is supplied. The non-compressed portion is preferably delivered to the compressed portion in a flowable manner. The non-compressed portion is then fixed to the compressed portion for example by adhesion, by forming a coating on the non-compressed layer to secure it to the compressed portion, or by hardening, for example (i) by cooling below the melting point in where the flowable composition becomes a solidified cast iron; (ii) by evaporation of a solvent; (iii) by crystallization; (iv) by polymerization of a polymeric component of the flowable non-compressed portion; (v) through pseudo-plastic properties wherein the non-compressible flowable portion consists of a polymer and shear forces are applied to the non-compressed portion; (vi) combining a binder with the non-compressible flowable portion. In an alternate embodiment, the non-compressible flowable portion may be an extruded material that is fixed to the compressed portion by, for example, any of the mechanisms described above or by expanding the extrudate to the parameters of a mold provided by the compressed portion. Preferably the compressed portion comprises a pre-prepared mold or depression (hereinafter referred to as "mold") in which the non-compressed portion is supplied. In an alternate embodiment the surface of the compressed portion comprises more than one mold in which the non-compressed portion can be delivered. The mold (s) preferably at least partially accommodates one or more uncompressed portions. The uncompressed portions are then supplied to the mold and fixed in the compressed portion as described above. The non-compressed portion may consist of particles. The particles can be prepared by any known method, for example conventional spray drying, granulation, encapsulation or agglomeration. The particles may be attached to the compressed portion by incorporating a binder or by forming a coating layer on the non-compressed portion. Where the detergent tablet comprises more than one non-compressed portion, the first and second and optionally subsequent non-compressed portions may consist of particles having substantially different average particle sizes. By substantially different average particle sizes it means that the difference between average particle sizes of the first and second and / or subsequent compositions is larger than 5%, preferably larger than 10%, more preferably larger than 15% or even larger. 20% of the smallest average particle size. The average particle size of the active detergent components in particles used herein is calculated using a series of Tyler sieves. The series consist of a number of sieves each having different opening sizes. The samples of a composition of active detergent components are screened through the series of sieves (typically 5 sieves). The weight of a sample of composition retained on the screen is plotted against the size of the screen opening. The average particle size of the composition is defined as the aperture size through which 50% by weight of the sample of the composition would pass. In another embodiment, the first and second and optional subsequent compositions of active detergent components have substantially different density so that the difference between the density of the The first and second and / or optional subsequent compositions are larger than 5%, preferably larger than 10%, more preferably larger than 15% or even 20% of the smallest density. The density of the particulate composition of active detergent components can be measured by any known method suitable for measuring density of particulate material. Preferably the density of the composition of active detergent components is measured using a simple funnel and cup device consisting of a conical funnel rigidly molded on a base and provided with a fin valve at its lower end to allow the contents The funnel is emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower ends. It is mounted so that the lower end is 140 mm above the upper surface of the base. The cup has a total height of 90mm, an internal height of 87mm and an internal diameter of 84mm. Its nominal volume is 500 ml. A measure of density is taken by pouring the composition into the funnel by hand. Once the funnel is full, the flap valve is open and the powder is allowed to run through the funnel. Overfilled the cup. The full cup is removed after the structure and the excess powder is removed from the cup by passing a straight edge implement, for example a knife through its upper edge. The full cup is weighed later and the The value obtained for the powder weight is doubled to provide a volumetric density in grams / liter. Repeated measurements are made as required. Tablets in which one or more of the non-compressed portions comprise particles and the average particle size and / or density of the first and second and optional subsequent uncompressed portions are substantially different are preferred where the first and second portions do not. Subsequent optional compresses are required to have different dissolution rates. Where the non-compressed portion consists of a solidified melt, the melt is prepared by heating a composition comprising an active detergent component and optional carrier component (s) above its melting point to form a flowable melt. The flowable melt is then poured into a mold and allowed to cool. As the cast cools it becomes solid, taking the form of the mold at room temperature. Where the composition comprises one or more carrier components, the carrier component (s) can be heated above its melting point, and then the active detergent component can be added. Suitable carrier components for preparing a solidified cast are typically non-active components that can be heated above their melting point to form a liquid and cooled to form an intermolecular matrix that can effectively trap active detergent components. A preferred non-active carrier component is an organic polymer that is solid at room temperature. Preferably, the active detergent component is polyethylene glycol (PEG). The compressed portion of the detergent tablet preferably provides a mold to accommodate the casting. The non-compressible flowable portion may be in a form comprising a dissolved or suspended active detergent component. The non-compressible flowable portion can be cured over time to form a solid, semi-solid or highly viscous non-compressed portion by any of the methods described above. In particular, the non-compressible flowable portion can be cured by evaporation of a solvent. Suitable solvents for use herein may include any known solvent in which a binder is soluble. Preferred solvents may be polar or non-polar and may include water, alcohol, (for example ethanol, acetone) and alcohol derivatives. In an alternate mode, more than one solvent may be used. The non-compressible flowable portion may consist of one or more binder agents. Any binder that has the effect of causing the composition to become solid, semi-solid or highly viscous over time is contemplated for use herein. While not wishing to be bound by theory, it is believed that the mechanism by which the binder causes a non-solid composition to become solid, semi-solid or highly viscous include: chemical reaction (as with chemical entanglement), or interaction of effect between two or more components of the flowable composition either. The binding agents include a combination of sugar / gelatin, starch, glycerol and organic polymers. The sugar can be any monosaccharide (for example glucose), disaccharide (for example sucrose or maltose) or polysaccharide. The most preferred sugar is commonly available sucrose. For the purposes of the present invention, type A or B gelatin, available for example from Sigma, may be used. Type A gelatin is preferred because it has greater stability under alkaline conditions compared to type B. The preferred gelatin also has an efflorescence resistance of between 65 and 300, more preferably between 75 and 100. Preferred organic polymers include polyethylene glycol (PEG) of molecular weight from 500 to 10,000, preferably from 750 to 8000, more preferably from 1000 to 6000 available from Hoechst. Where the non-compressed portion is an extruded material, the extruded material is prepared by pre-mixing the active detergent components with optional carrier components to form a viscous paste. The viscous paste is then extruded using any commonly available suitable extrusion equipment such as for example a single or twin screw extruder available for example from APV Baker, Peterborough, U.K. The extruded material is then cut to size either after delivery to the compressed portion, or prior to delivery to the compressed portion of the detergent tablet. The compressed portion of the tablet preferably comprises a mold in which the extruded uncompressed portion can be delivered. In a preferred embodiment the non-compressed portion is coated with a coating layer. The coating can be used to fix a non-compressed portion to the compressed portion. This can be particularly advantageous where the non-compressed portion comprises flowable particles, gels or liquids. The coating layer preferably consists of a material that becomes solid upon contacting the compressed and / or non-compressed portions within preferably less than 15 minutes, more preferably less than 10 minutes, still more preferably less than 5 minutes, more preferably less than 60 seconds. Preferably the coating layer is water-soluble. Preferred coating layers comprise materials selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA), polyethylene glycol (PEG) and mixtures thereof. Preferred carboxylic or dicarboxylic acids preferably comprise an even number of carbon atoms. The carboxylic or dicarboxylic acids preferably comprise at least 4, more preferably at least 6, even more preferably at least 8 carbon atoms, more preferably between 8 and 13 carbon atoms. Preferred carboxylic or dicarboxylic acids include adipic acid, suberic acid, azelaic acid, subic acid, undecanedoic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof. Preferred fatty acids are those that have a carbon chain length of C12 to C22, more preferably from C18 to C22. The coating layer may also preferably consist of a breakdown agent. When present, the coating layer is generally present at a level of at least 0.05%, preferably at least 0.1%, more preferably at least 1%, more preferably at least 2% or even at least 5% of the detergent tablet. As an alternative embodiment, the coating layer can encapsulate the detergent tablet. In this embodiment the coating layer is present at a level of at least 4%, more preferably at least 5%, more preferably at least 10%, of the detergent tablet. In a preferred embodiment the compressed and non-compressed portions and / or the coating layer additionally comprise a disrupting agent. The disrupting agent can be a disintegrating or effervescent agent. Suitable disintegrating agents include agents that swell upon contact with water or facilitate the influx and / or efflux of water to form channels in the compressed and / or uncompressed portions. Any known disintegrating or effervescing agent suitable for use in laundry or dishwashing machine applications is contemplated for use herein. Suitable disintegrating agents include starch, starch derivatives, alginates, carboxymethyl cellulose (CMC), polymers based on CMC, sodium acetate, aluminum oxide. Suitable effervescent agents are those that produce a gas upon contact with water. Suitable effervescent agents can be oxygen, nitrogen dioxide or species that evolve from carbon dioxide. Examples of preferred effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic acids such as citric or maleic acid. | g ^ u gg Mfe ^^ A | g ^ í | j | An advantage of including a disrupting agent in the detergent tablet of the present invention are the transport, storage and handling benefits that can be achieved by increasing the hardness of the detergent tablet without adversely affecting the cleaning performance.

Process According to the present invention there is also provided a process for preparing a detergent tablet comprising the steps of: a) compressing an active detergent component to form a compressed portion; and b) supplying a non-compressed, non-encapsulating portion comprising an active detergent component to the compressed portion. As described above, the detergent tablets described herein are prepared by separately preparing the composition of active detergent components that form the respective compressed portion and the uncompressed portion, then delivering or adhering the composition of the non-compressed portion to the compressed portion. . The compressed portion is prepared by obtaining at least one active detergent component and pre-mixing optionally with carrier components. Any pre-mixing will be carried out in a suitable mixer, for example a tray mixer, a rotating drum, vertical mixer or high shear mixer. Preferably the dry particulate components are mixed in a mixer, as described above, and the liquid components are applied to the dry particulate components, for example by spraying the liquid components directly onto the dry particulate components. The resulting composition is then formed into a compressed portion in a compression step using any suitable equipment. Preferably the composition is formed into a compressed portion using a tablet press, in which the tablet is prepared by compressing the composition between an upper and a lower punch. In a preferred embodiment of the present invention the composition is supplied in a punch cavity of a tablet press and compressed to form a compressed portion using a pressure of preferably larger than 6.3 KN / cm2, more preferably larger than 9 KN / cm2, more preferably larger than 14.4 KN / cm2. In order to form a preferred tablet of the invention, in which the compressed portion provides a mold for receiving the non-compressed portion, the compressed portion is prepared using a modified tablet press comprising modified upper and / or lower punches. The upper and lower punches of the modified tablet press are modified so that the compressed portion provides one or more indentations which form a mold (s) into which the non-compressed portion is delivered. The non-compressed portion comprises at least one active detergent component. Where the non-compressed portion comprises more than one active detergent component the components are pre-mixed using any suitable mixer equipment known. In addition, the non-compressed portion may optionally consist of a carrier with which the active detergent components are combined. The non-compressed portion can be prepared in solid or flowable form. Once prepared the composition is supplied to the compressed portion. The non-compressed portion can be supplied to the compressed portion by manual delivery or by using a nozzle feeder or extruder. Where the compressed portion comprises a mold, the non-compressed portion is preferably supplied to the mold using exact delivery equipment, for example a nozzle feeder, as a loss-in-weight screw feeder available from Optimum, Germany, or an extruder. Where the non-compressed portion is in the form of particles the process comprises supplying a non-compressible flowable portion to the compressed portion in a delivery passage and then coating at least one The portion of the non-compressed portion with a coating layer such that the coating layer has the effect of substantially adhering the non-compressed portion to the compressed portion. Where the non-compressible flowable portion is fixed to the compressed portion by hardening, the method comprises a step of A supply in which the non-compressible flowable portion is supplied to the compressed portion and a subsequent conditioning passage, in which the non-compressed portion hardens. Said conditioning step may consist of drying, cooling, agglutination, polymerization, etc. of the non-compressed portion, during which the non-compressed portion becomes solid, semi-solid or highly viscous. The heat can be used in a drying step. Heat, or exposure to radiation can be used to effect polymerization in a polymerization step. It is also contemplated that the compressed portion can be prepared having a plurality of molds. The plurality of molds is then filled with a non-compressed portion. It is also contemplated that each mold may be filled with a different non-compressed portion or alternatively, each mold may be filled with a plurality of different non-compressed portions.

Active Detergent Components The compressed portion of the detergent tablets described herein is prepared by compressing the composition of active detergent components. A suitable composition can include a variety of different active detergent components including builder compound, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfume, lime soap dispersants, organic polymeric compounds including transfer inhibition polymeric agents of ink, crystal growth inhibitors, heavy metal ion sequestrants, metal salts, enzyme stabilizers, corrosion inhibitors, foam suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes. The highly preferred active detergent components include a builder, a surfactant, an enzyme and a bleaching agent.

Compound Meiorador de deterqencia The detergent 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, more preferably from 20% to 60% by weight of the composition of active detergent components.

Compound meiorador of water soluble deterqencia Suitable water-soluble builder compounds include the water-soluble monomeric polycarboxylates, or their acid forms, homo- or co-polymeric polycarboxylic acids, or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more of two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder may be of monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water-soluble salts of lactic acid, glycolic acid, and the 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 ether carboxylates and sulfinyl caboxylates. 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, the lactoxysuccinates described in British Patent No. 1, 389,732, the aminosuccinates described in the Netherlands application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in the patent British No. 1, 387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described 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 described in British Patents Nos. 1, 398,421 and 1, 398,422, and in the US patent. No. 3,936,448, and the pyrolyzed sulfonated citrates described in British Patent No. 1, 439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis.cis.cis-tetracarboxylates, cyclopentadienidepentacarboxylates, 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 described in British Patent No. 1, 425, 433. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The original acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example citric acid or citrate / citric acid mixtures are also contemplated as useful builders components. Borate builders, as well as detergency builders containing borate-forming materials that can produce borate under detergent storage or washing conditions can also be used but are not preferred under wash conditions of less than 50 ° C , especially less than 40 ° C. Examples of carbonate builders are earth-alkali metal and alkali metal carbonates, including sodium carbonate and sesqui-carbonate, and mixtures thereof with ultrafine calcium carbonate as described in German Patent Application No. 2,321,001 of 15 November 1973. The highly preferred builders compounds for use in the present invention are the water-soluble phosphate builders. Specific examples of water-soluble phosphate builders are alkali metal tri-phosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphates, potassium and sodium orthophosphate, sodium polymetate / phosphate in which the degree of polymerization is in the range of 6 to 21, and salts of acid picítico.

Compound meiorador de deterqencia partially soluble or insoluble The detergent tablets of the present invention may contain a partially soluble or insoluble builder compound. The partially soluble or insoluble builder compounds are particularly suitable for use in tablets prepared for use in laundry cleaning methods. Examples of partially water-soluble builders include the layered crystalline silicates as described in, for example, EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline layered sodium silicates of the general formula: NaMSixO2 + 1 «yH2O In which M is sodium or hydrogen, x is a n. { 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 d-layered structure, as described in EP 0 164514 and EP 0 293640. Methods for the preparation of crystalline layered silicates of this type are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4 and preferably is 2. The most preferred crystalline layered sodium silicate compound has the formula d-Na2Si2O5, 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 particle intimately mixed with a solid, water soluble, ionizable material, as described in PCT patent application No. WO92 / 18594. The solid, water soluble, ionizable material is selected from organic acids, salts of organic or inorganic acid and mixtures thereof, with citric acid being preferred. Examples of widely water-soluble detergency builders include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having the unit cell formula Naz [(AIO2) z (SiO2) and] "xH2O in which z and" y "are at least 6; the molar ratio of zay 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 is in hydrated form and is preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. A preferred method for synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14 (2), 10-1 16), in which the author describes a method for preparing colloidal aluminosilicate zeolites. The particles of colloidal aluminosilicate zeolites must be such that no more than 5% of the particles are of a size larger than 1 μm in diameter and no more than 5% of the particles are of size less than 0.05 μm in size. diameter. Preferably the particles of aluminosilicate zeolites have an average particle diameter size between 0.01 μm and 1 μm, more preferably between 0.05 μm and 0.9 μm, more preferably between 0.1 μm and 0.6 μm. Zeolite A has the formula: Na12 [(Al? 2) i2 (Si? 2) i2] xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(1? 2) 86 (S? 2) i06.'276H2 ?. Zeolite MAP, as described in EP-B-384,070 is a preferred builder here. The preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When used as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloid zeolite A, provide improved builder performance in terms of providing improved spot removal. The improved builder performance is also seen in terms of reduced fabric embedding and improved fabric whiteness maintenance; problems that are believed to be associated with poorly constructed detergent compositions. A surprising finding is that the mixed detergent compositions of aluminosilicate zeolite comprising zeolite A colloid and zeolite Y colloid provide equal calcium sequestrant performance against an equal amount of commercially available zeolite A. Another surprising discovery is that the mixed detergent compositions of aluminosilicate zeolite, described above, provide improved yield of magnesium ion sequestrant against an equal amount of commercially available zeolite A.

Surfactant Surfactants are preferred active detergent components of the compositions described herein. Suitable surfactants are selected from anionic, nonionic, cationic, ampholytic, and zwitterionic surfactants, and mixtures thereof. The products for automatic dishwashing machines should be of low foaming character and therefore the foaming of the surfactant system for use in dishwashing methods should be suppressed or preferably be low foaming, typically of non-ionic character. The foaming caused by the surfactant systems used in laundry cleaning methods need not be suppressed to the same extent as that required for dishwashing. The surfactant is typically present at a level of 0.2% to 30% by weight, m. { preferably from 0.5% to 10% by weight, m. { preferably from 1% to 5% by weight of the composition of active detergent components. A typical listing of anionic, non-ionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the US patent. No. 3,929,678, issued to Laughiin and Heuring on December 30, 1975. A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. A list of surfactants typically included in detergent compositions for automatic dishwashing machine is given, for example, in EP-A-0414 549 and PCT applications Nos. WO. 93/08876 and WO 93/08874.

Nonionic surfactant Essentially any nonionic surfactants useful for detersive purposes can be included in the detergent tablet. Non-limiting, preferred classes of useful nonionic surfactants are listed below.

Nonionic surfactant of ethoxylated alcohol The alkylethoxylated condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either 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.

Locked-end alkyl alkoxylate surfactant A suitable blocked end alkyl alkoxylate surfactant is the poly (oxyalkylated) alcohols represented by the formula: R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] and [CH 2 CH (OH) R 2] (1) In which 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 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 epoxy unit [CH2CH (OH) R2]. Suitable surfactants of formula I, according to the present invention, are the nonionic surfactants POLY-TERGENT® SLF-18B from Olin Corporation, as described in, for example, WO 94/22800, published on October 13 of 1994, by Olin Corporation. j $ t **? HiSSt. A ^ & S ^ fc * Poly (oxyalkylated) alcohols of blocked ether Preferred surfactants for use herein include blocked ether poly (oxyalkylated) alcohols having the formula: R 1 O [CH 2 CH (R 3) O] x [CH 2] kCH (OH) [CH 2], OR 2 Wherein R1 and R2 are an aliphatic or aromatic hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30, in which when x is 2 or larger R3 may be the same or different ykyj are integers having an average value of 1 to 12, and more preferably 1 to 5 R1 and R2 are preferably aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 6 to 22 carbon atoms, with from 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms is more preferred for R3. Preferably x is an integer having an average value of 1 to 20, more preferably 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 can vary between any of the alkyleneoxy units as described ^^^^^^ íf ftiffilrl previously. For example, if x is 3, R3 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and can 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 integer three is selected for example only and the variation can be much longer with a higher integer value for x and includes, for example, multiple units (EO) and a much smaller number of units (PO). Particularly preferred surfactants as described above include those that have a low cloud point of less than 20 ° C. These low cloud point surfactants can be used in conjunction with a high-point cloud surfactant as described in detail below for superior grease cleaning benefits. The most preferred blocked ether poly (oxyalkyl) surfactants are those in which k is 1 and j is 1 such that the surfactants have the formula: R1O [CH2CH (R3) O] xCH2CH (OH) CH2OR2 Where R1, R2 and R3 are as defined above and x is an integer with an average value of 1 to 30, preferably 1 to 20, and even more preferably 6 to 18. Surfactants in which R1 and R2 are in the range of 9 to 14 are more preferred, R3 is H forming ethyleneoxy and x is in the range of 6 to 15.

The ether-blocked poly (oxyalkylated) alcohol surfactants comprise three general components, ie a linear or branched alcohol, an alkylene oxide and a blocked end of alkyl ether. The alkyl ether and alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the water-soluble, hydrophilic portion of the molecule. These surfactants exhibit significant improvements in film formation characteristics and stain removal and removal of greasy stains, when used in conjunction with high-cloud point surfactants, in relation to conventional surfactants. Generally speaking, the blocked ether poly (oxyalkylene) surfactants of the present invention can be produced by reacting an aliphatic alcohol with an epoxide 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 for preparing the blocked ether poly (oxyalkylated alcohol) surfactants are described below: Preparation of C12 / 14 Crycidyl alkyl ether A C12 / 14 fatty alcohol (100.00 g, 0.515 mol), and tin (IV) chloride (0.58 g, 2.23 mmol, available from Aldrich) are combined in a 500-ml flask ml, round bottom, three-necked, equipped with a ^ - ^^^^ a ^ ^? ^^ = B ^ «« »s ^? A» ^. ^ > ? ifa, ^^ «afefeAtel -H capacitor, argon outlet, additional funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise to maintain 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% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) while being mechanically stirred. After the addition is complete, the mixture is heated at 90 ° C for 1.5 hours, cooled, and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO 4, filtered and concentrated. Distillation of the oil at 100-120 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

C12 / 14 alcohol surfactant preparation of C9 / 11 alkyl of blocked ether Neodol® 91-8 (20.60 g, 0.0393 moles ethoxylated alcohol available from Shell Chemical Co. and tin (IV) chloride (0.58 g, 2.23 mmoles) are combined in a 250 ml round bottom, three-necked flask equipped with a condenser, argon tap, addition funnel, magnetic stirrer and internal temperature probe.The mixture is heated to 60 ° C at which point C12 / 14 glycidyl alkyl ether (11.0 g, 0.0393 mol) is added dropwise over 15 minutes.After stirring for 18 h at 60 ° C the mixture is cooled to room temperature and dissolved in an equal portion of dichloromethane. Solution is passed through a 2.54 cm pad of silica gel Ü &SNMkJiia &? - A. while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then released in a kugeirohr oven (100 ° C, 0.5 mm Hg) to yield the surfactant as an oil.

Ethoxylated / Propoxylated Fatty Alcohol Nonionic Surfactant Ethoxylated C6-C-? 8 Fatty Alcohols and Mixed C6-Ci8 ethoxylated / propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water-soluble. preferably the ethoxylated fatty alcohols are the ethoxylated fatty alcohols of C-io-C-is with an ethoxylation degree of 3 to 50, more preferably those are the ethoxylated fatty alcohols of C? 2-C-? 8 with a degree of ethoxylation from 3 to 40. Preferably the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

EO / PO nonionic 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 1500 to 1800 and exhibits insolubility in water. Examples of compounds of this type include certain commercially available Pluronic® surfactants, marketed by BASF.

EO nonionic condensation products with propylene oxide / ethylenediamine 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 portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactants include certain commercially available Tetronic® compounds, marketed by BASF.

Mixed Non-ionic Surfactant System In a preferred embodiment of the present invention the detergent tablet comprises a mixed non-ionic surfactant system comprising at least one low-point non-ionic surfactant and a high-point nonionic surfactant of turbidity. "Turbidity point", as used herein, is a well-known property of nonionic surfactants which is the result of the surfactant becoming less soluble with an increase in temperature, the temperature at which the appearance of a second phase referred to as "cloud point" (See Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed. Vol. 22, pp. 360-379). As used herein, a "low cloud point" nonionic surfactant is defined as an ingredient of a surfactant system having a cloud point of less than 30 ° C, preferably less than 20 ° C, and more preferably less than 10 ° C. Typical low cloud point nonionic surfactants include alkoxylated nonionic surfactants, especially ethoxylates derived from primary alcohol, and poly (oxypropylene) / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. In addition, said low-cloud point nonionic surfactants include, for example, ethoxylated / propoxylated alcohol (for example Poly-Tergent® SLF 18 from Olin Corporation), poly (oxyalkylated blocked epoxy alcohols (for example the Poly non-ion series). -Tergent® SLF 18B from Olin Corporation, as described for example in WO 94/22800, dated Octo13, 1994 by Olín Corporation), and the surfactants of poly (oxyalkylated alcohols of blocked epoxy.) Nonionic surfactants can optionally containing propylene oxide in an amount of up to 15% by weight Other preferred nonionic surfactants can be prepared by the process described in U.S. Patent No. 4,223,163, Septem16, 1980, Builloty, incorporated herein By reference, the low-cloud point nonionic surfactants additionally comprise a polymeric polyoxyethylene block compound, polyox Polypropylene polyoxyethylene-polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylpropane and ethylenediamine as a starting reactive hydrogen compound. Some of the surfactant block polymer compounds designated as PLURONIC®, REVERSED PLURONIC®, TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactants are typically useful herein as low-cloud point nonionic surfactants. As used herein, a "high cloud point" nonionic surfactant is defined as an ingredient of a nonionic surfactant system having a cloud point greater than 40 ° C, preferably more than 50 ° C. ° C, and more preferably more than 60 ° C. Preferably the system of nonionic surfactants 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 alkylphenol on an average base. Such high-cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied 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 also has a hydrophilic-lipophilic balance value ("HLB").; see Kirk Othmer here above) within the range of 9 to 15, pref 11 to 15. Such materials include, for example, Tergitol 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-chain or preferably branched secondary fatty alcohol containing from 6 to 20 carbon atoms (C6-C2o alcohol), including secondary alcohols and branched-chain primary alcohols. . Preferably the high-cloud point nonionic surfactants are ethoxylated or branched secondary alcohols, more preferably branched ethoxylated alcohol of C9 / 11 or C11 / 15 mixed, condensed with an average of 6 to 15 moles, preferably 6 to 12 moles, and more preferably from 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant derived in this way has a narrow ethoxylate distribution in relation to the average. In a preferred embodiment, the detergent tablet comprising said mixed surfactant system also comprises an amount of water-soluble salt to provide conductivity in deionized water measured at 25 ° C greater than 3 milli Siemens / cm, preferably larger than 4 milli Siemens / cm, more preferably larger than 4.5 milli Siemens / cm, as described in GB co-pending patent application (attorney's file number CM 1573F).

In another preferred embodiment, the blended surfactant system is dissolved in water having a hardness of 1,246 mmole / L in any suitable cold-filled automatic dishwashing machine to provide a solution with a surface tension of less than 4 Dynes / cm2 at less than 45 ° C, preferably less than 40 ° C, more preferably less than 35 ° C as described in the co-pending US patent application (lawyer's file number 6252). In another preferred embodiment, the high cloud point and low cloud point surfactants of the mixed surfactant system are separated so that one of any of the high cloud point or low cloud point surfactants is present in a first matrix and the other is present in a second matrix as described in the co-pending US patent application (lawyer's file number 6252). For purposes of the present invention, the first matrix can be a first particle and the second matrix can be a second particle. A surfactant can be applied to a particle by any known suitable method, preferably the surfactant is sprayed on the particle. In a preferred aspect the first matrix is the compressed portion and the second matrix is the non-compressed portion of the detergent tablet of the present invention. Preferably the low cloud point surfactant is present in the compressed portion and the high cloud point surfactant is present in the uncompressed portion of the detergent tablet of the present invention.

Anionic surfactant Essentially any anionic surfactant useful for detersive purposes is suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the ammonium sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) sulfosuccinate diesters (especially saturated and unsaturated Cβ-C-1,4 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.

Sulfate anionic surfactant Sulfate-based anionic surfactants suitable for used herein include the linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, the acyl glucaminesulfates of C5-C-17-N- (C1-C4 alkyl) and -N- (C1-C2 hydroxyalkyl), and sulphates of ! & *; - < / RTI > alkylcarbosaccharides such as alkylpolyglucoside sulphates (non-sulfated nonionic compounds are described herein). The alkylsulfate surfactants are preferably selected from linear and branched primary C 1 or C 18 alkyl sulfates, more preferably the branched chain C 9 -C 15 alkyl sulfates and the C 2 alkanol sulphates. of linear chain. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C- | o-C- | 8 alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C 11 -C 8 alkylsulfate > more preferably of Cn-C-15, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been described in PCT application No. WO 93/18124.

Anionic Sulfonate Surfactant The sulfonic anionic surfactants suitable for use herein include the linear alkylbenzene sulphonate salts of C5-C20. alkyl esters sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH2?) XCH2COO-M + in which R is an alkyl group of CQ to C- | 8. x is on the scale from 0 to 10, and the ethoxylate distribution is such that, based on weight, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR-? -CHR2-O) -R3 in which R is an alkyl group of CQ to C- | 8. x is from 1 to 25, R- | and R are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. The preferred secondary soap surfactants for use herein are the water-soluble members - ^ ^ ^ ^ ^ U ^^^^^ i ^ selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1- acid nonanoic, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R 1) CH 2 COOM, in which R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is an alkyl group of C-1-C4 and M is an alkali metal group. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) XN0 (R5) 2 > wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R ^ is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of C- | Q-Ci8 and the acrylamidodimethylamine oxide of C-? O-C-18- A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. 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. The surfactants of sultaine and betaine are illustrative zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- in which R is a hydrocarbyl group of C6-C- | 8 > each R1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group. Preferred betaines are the betaines of C12-C18 dimethyl ammonium hexanoate and the C- | Q-Ci8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Also suitable for use herein are complex betaine surfactants. .

** A ^ ***** M *. * - * * * cf ** p ^ Cationic Surfactants The cationic ester surfactants used in this invention are preferably a water dispersible compound having surfactant properties and comprising at least one ester linkage (i.e. COO-) and at least one cationically charged group. Other suitable cationic ester surfactants, including choline ester surfactants, have been described for example in the U.S. Patents. Nos. 422,8042, 4239660 and 4260529. Suitable cationic surfactants include the quaternary ammonium surfactants selected from alkenyl ammonium or mono C6-C16 surfactants, preferably N-C6-C10 alkyl in which the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Enzymes In one embodiment of the present invention an enzyme is an essential characteristic of the detergent tablet. In other embodiments of the present invention an enzyme is an optional active detergent component. When such enzymes are present, they are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glyco-amylases, amylases, lipases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, ^ T ^ - &2 ^ E ^ Ü pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. Preferred enzymes include protease, lipase, cutinase and / or cellulase, in conjunction with one or more cell wall degrading enzymes vegetable Cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and an activity above 50 CEVU (cellulose viscosity unit). Suitable cellulases are described in the U.S.A. No. 4,435,307, Bargesgoard et al, J61078384 and WO96 / 02653 which describes a fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thievalia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832 and WO 95/26398. Examples of said cellulases are the cellulases produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea.), Particularly the Humicola strain DSM 1800. Other suitable cellulases are the cellulases originated from Humicola insolens having a molecular weight of ab50 KDa, an isoelectric point of 5.5, and containing 415 amino acids, and a ~ 43kD endoglucanase derived from Humicola insolens, DSM 1800, which exhibits cellulase activity; a preferred endoglucanase component has the amino acid sequence described in PCT patent application No. WO 91/17243. Cellulases are also suitable The EGIII cellulases of Trichoderma longibrachiatum described in WO 94/21801, Genencor, published on September 29, 1994, are particularly useful. Cellulases especially suitable are cellulases that have color care benefits. Examples of said cellulases are the cellulases described in the application for European patent No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO 96/34092, WO96 / 17994 and WO 95/24471. Said other cellulases are normally incorporated in the detergent composition at levels of 0.0001% to 2% pure enzyme by weight of the detergent composition. Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, peroxide hydrogen, etc. They are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from substrates during washing operations, to other substrates in the washing 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 described, for example, in the PCT International Application WO89 / 099813, WO 89/09813 and in European Patent Application No. 91202882.6, filed 6 November 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme. Preferred improvers are fentiazine and phenoxasine, 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinopropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringes (substituted C3-C5 alkylsalicylates) and phenols. Percarbonate or sodium perborate are preferred sources of hydrogen peroxide. Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001% to 2% 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 use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent 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-P". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipases ex Pseudomonas gladioli. Lipases especially suitable are lipases such as M1 Lipase ^ and Lipomax ^ (Gist-Brocades) and Lipolase ^ and Lipolase Ultra ^ (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk, and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special type of lipase, ie lipases that do not require interfacial activation. The addition of cutinases to detergent compositions has been described in, for example, WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System), and WO 94/14963 and WO 94/14964 (Unilever). The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Suitable proteases are the subtilisins that are obtained from particular strains of B.subtilis and B.licheniformis (subtilisin BPN and BPN '). Other suitable proteases are obtained from a Bacillus strain, having a maximum activity in the entire pH range of 8 to 12, developed and sold as ESPERASER 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 ALCALASE® DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal manipulated with proteins) from Gist-Brocades. Proteolytic enzymes also include modified bacterial serine proteases, such as those described in the European patent application No. 87303761.8, filed on April 28, 1987 (particularly pages 17, 24 and 98) and which is referred to herein as "Protease B", and in the European patent application EP 199 404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protease which is referred to herein as "Protease A". More preferred is that in the present so-called "Protease C" which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine in the position 123 and alanine replaces threonine at position 274. Protease C is described in EP 90915958.4, which corresponds to WO 91/06637, published on May 16, 1991. Genetically modified variants, particularly protease, are also included herein. C. A preferred protease, referred to as "protease D," is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acids. amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more positions of the amino acid residue equivalent to those selected from the group consisting of +99, +101, +103, +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 in accordance with the numbering of the Bacillus amyloliquefaciens succinysine as described in WO 95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes", which has the EU serial number 08 / 322,677, filed October 13, 1994. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/06637, the BLAP® protease described in WO91 / 02792 and their variants described in WO 95/23221. 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 & amp;; 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 Unilever. Other preferred enzymes include protease enzymes that are a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived by replacing a K ^^^^ A plurality of amino acid residues of a carbonyl hydrolase precursor with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme correspond to the position +210 in combination with one or more of the following 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 subtilisin that occurs naturally from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). The Preferred enzymes of this type include those that have position changes +210, +76, +103, +104, +156, and +166. The proteolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% of pure enzyme by weight of the composition. Amylases (a and / or ß) can be included for the removal of carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO / 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include both a and β-amylases. A-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; / u j? tldeá-Í? E? X.w '~ & To EP 368,341; and in the description of British Patent No. 1, 296,839 (Novo). Other suitable amylases are the amylases of improved stability described in WO94 / 18314, published on August 18, 1994 and WO 96/05295, Genencor, published on February 22, 1996, and the amylase variants having further modification in the progenitor. Immediate, available from Novo Nordisk A / S, described in WO95 / 10603, published April 1995. Also suitable are the amylases described in EP 277 216, WO 95/26397 and WO 96/23873 (all by Novo Nordisk). Examples of commercial α-amylases products are Purafact Ox Am®, from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% greater than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and at a pH value on the scale of 8 to 10, as measured by the Phadebas test of α-amylase activity.

The variants of the above enzymes are suitable, described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher activity level are described in WO95 / 35382. Preferred amylase enzymes include those described in WO95 / 26397 and in co-pending application PCT / DK96 / 00056 by Novo Nordisk. The amylolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. In a particularly preferred embodiment, the detergent tablets of the present invention comprise amylase enzymes, particularly those described in WO95 / 26397 and the co-pending application PCT / DK96 / 00056 by Novo Nordisk in combination with a complementary amylase. By "complementary" means the addition of one or more suitable amylases for detergent purposes. Examples of complementary (a and / or β) amylases are described below. WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S describe cleaning compositions incorporating mutant amylases. Other amylases known to be used in cleaning compositions include α and β-amylases. A-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP 252,666; WO / 91/00353; RF 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1, 296,839 (Novo). Other suitable amylases are the amylases of improved stability described in WO94 / 18314, published August 18, 1994 and WO 96/05295, Genencor, and the amylase variants having additional modification in the immediate parent, available from Novo Nordisk A / S described in WO95 / 10603. Also suitable are the amylases described in EP 277 216, (Novo Nordisk). Examples of commercial α-amylases products are Purafact Ox Am®, from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized 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 on the scale of 8 to 10, measured ® by the Phadebas test of α-amylase activity. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and higher activity level are described in WO95 / 35382.

The preferred complementary amylases for the present invention are the amylases sold under the trademark Purafec Ox AM® described in WO 94/18314, WO95 / 05295 sold by Genencor; Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S and Maxamyl® by Gist-Brocades. Said complementary amylase is generally incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. Preferably a weight ratio of pure amylase enzyme specific to the complementary amylase is comprised between 9: 1 to 1: 9, more preferably between 4: 1 to 1: 4, and more preferably between 2: 1 and 1: 2. The aforementioned enzymes may have any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The origin can also be mesophilic or extremophile (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidic, halophilic, etc.). The purified or non-purified forms of these enzymes can be used. Also included by definition are the mutants of wild enzymes. Mutants can be obtained for example by manipulation of protein and / or genetics, chemical and / or physical modifications of wild enzymes. The common practice is also the expression of the enzyme through a host organism 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 of 0.0001% to 2% active enzyme by weight of the detergent composition. Enzymes can be added as separate individual ingredients (pellets, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (eg cogranulates). Other suitable detergent ingredients that can be added are the enzyme oxidation scavengers described in copending European patent application 92970018.6, filed on January 31, 1992.

Examples of said enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines. A range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694 A to Novo, and E.U.A. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are also described in E.U.A. 4,101, 457, Place et al, July 18, 1978 and in E.U.A. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in E.U.A. 4,261, 868, Hora et al, April 14, 1981. Enzymes to be used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in E.U.A. 3,600,319, August 17, 1991, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U.A. 3,519,570. A Bacillus sp. AC13 useful and which gives proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Bleaching agent A highly preferred component of the active detergent component composition is a bleaching agent. Suitable bleaching agents include chlorine bleaching agents that release oxygen. In a preferred aspect, the bleaching agent that releases oxygen contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxy acid occurs through an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrated bleaches. In an alternative preferred aspect, a preformed organic peroxyacid is incorporated directly into the composition. Also disclosed are compositions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic perhydrate bleaches The active detergent component compositions preferably include a source of hydrogen peroxide, such as a bleach that releases oxygen. Suitable sources of hydrogen peroxide include the inorganic perhydrate salts.

The inorganic perhydrate salts are normally incorporated in the sodium salt form at a level of 1% to 40% by weight, more preferably 2% to 30% by weight and more preferably 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 usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions use a coated form of the material, which provides better storage stability for the perhydrate salt in the granulated product. Sodium perborate may be in the form of the monohydrate of the nominal formula NaB 2 H 2 o 2 or the tetrahydrate Na B 2 H 2 2-3 2-3 H 2. The alkali metal percarbonates, particularly sodium percarbonate, are the perhydrates that are preferred for inclusion in compositions according to the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H2? 2 and is commercially available as a crystalline solid. Sodium percarbonate, being an addition compound of hydrogen peroxide, tends in the solution to release hydrogen peroxide quite rapidly which may increase the tendency for highly localized bleach concentrations to arise. The percarbonate is more preferably incorporated into said coated compositions which provides stability in the product. A suitable coating material that provides stability in the product comprises a mixed salt of a water-soluble alkali metal sulfate and carbonate. Said coatings together with coating processes have been previously described in GB-1, 466,799, granted to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to percarbonate is in the scale of 1: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and more preferably from 1: 49 to 1: 19. Preferably, the mixed salt is sodium sulfate and sodium carbonate which has the general formula Na2SO.n.Na2CO3 in which n is 0.1 to 3, preferably n is 0.3 to 1.0 and more preferably n is 0.2 to 0.5 Another suitable coating material that provides stability in product, comprises sodium silicate with SiO2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 and / or sodium metasilicate, preferably applied to a level of 2% to 10% (usually 3% to 5%) of SiO2 by weight of the salt of t ^^ MW ^ aa ^^ fej ^^ L inorganic perhydrate. Magnesium silicate can also be included in the coating. Coatings containing silicate and borate salts or boric or other inorganic acids are also suitable. Other coatings containing waxes, oils, fatty soaps can also be used advantageously in the present invention. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Peroxyacid bleach precursors can generally be represented as: O II X-C-L where L is a residual group, and X is essentially any functionality, such that in perhydrolysis, the structure of the produced peroxyacid is: II X-C-OOH u? a? »It?The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Residual groups The residual group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: R3 and I I -O- CH = C- CH = CH9 - O- CH = C- CH = CH R3 O Y i 4 ?? i A - O-C = CHR4 v - N - S - CH - R4 'and I II R3 O and mixtures thereof, in which R1 is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain that it contains from 1 to 8 carbon atoms, R ^ is H or R3, R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group.

Any of Rl, R3 and R ^ can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. . ", .." > . .. ¿I know h? *? Ak * á M ~ * a- The preferred solubilizing groups are -S? 3"M +, -C? 2" M +, -SO4" M +, -N + (R3) 4X "and O <- N (R3), and most preferably -S? 3" M + and -C? 2"M +, in the that R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates, including for example benzoyl oxybenzene sulfonate: Also suitable are the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, including for example: Ac = COCH3; Bz = Benzoyl The perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Other perbenzoic acid precursors include the benzoyldiacyl peroxides, the benzoyltetraacyl peroxides, and the compound having the formula: Phthalic anhydride is another perbenzoic acid precursor compound suitable herein: Suitable N-acylated lactam perbenzoic acid precursors have the formula: Wherein n is from 0 to 8, preferably from 0 to 2, and R 6 is a benzoyl group.

Precursors derived from perbenzoic acid The precursors derived from perbenzoic acid provide perbenzoic acids substituted in the perhydrolysis. Suitable substituted perbenzoic acid-derived precursors include any of the perbenzoic precursors described herein in which the benzoyl group is substituted by any non-positively charged (i.e., non-cationic) functional groups including, for example, alkyl groups, hydroxy, alkoxy, halogen, amine, nitrosyl and amide. A preferred class of substituted perbenzoic acid precursor compounds are the substituted amide compounds of the following general formulas: R1- C-N-R2- C- L R1- N-C-R2-C- L O R5 O R5 O O In which R 1 is an aryl or alkaryl group with 1 to 14 carbon atoms, R 2 is an alkarylene group containing 1 to 14 carbon atoms, and R 2 is H or an alkyl, aryl or alkaryl group containing 1 to 4 carbon atoms. to 10 carbon atoms and L can be essentially any residual group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 can be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may originate from synthetic sources or natural sources including for example, tallow grease. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis. Typically, the 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 alkylammonium group, preferably an ethyl or methylammonium 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 an ion of methylsulfate. The peroxyacid precursor compound which will be so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof, as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl or benzoyloxybenzene sulphonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. A preferred cationically substituted benzoyloxybenzen sulfonate is 4- (trimethylammonium) methyl derivative of benzoyloxybenzene sulfonate: A preferred canonically substituted alkyloxybenzen sulfonate has the formula: Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenebenzoyl caprolactams, particularly the trimethylammonium methylenebenzoyl caprolactams: Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenealkyl caprolactams: Where n is from 0 to 12, particularly from 1 to 5. Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethyl ammonium) ethyl sodium 4-sulfophenyl carbonate chloride.

Precursors for bleaching of alkenecarboxylic acid The bleach precursors of alkylpercarboxylic acid form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarboxylic acid precursor compounds of the imide type include the tetraacetylated N-, N, N 1 N 1 alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylcarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Amide-substituted alkylperoxy acid precursors Amide-substituted alkylperoxy acid precursor compounds are also suitable, including those of the following general formulas: R1- C-N-R2- C-L R1- N-C-R2-C-L I I L I I O R 5 O or R 5 O O in which R 1 is an alkyl group of 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms, and R ^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any residual group. R1 preferably contains 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl containing branching, substitution, or both and may originate from synthetic sources or natural sources including, for example, tallow fat. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, Halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Precursors of organic benzoxazine peroxyacid Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: tM Including substituted benzoxazines of the type: Wherein Ri is H, alkyl, alkaryl, aryl, aplakyl, and wherein R 2, R 3, R and R 5 can be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino , alkylamino, COORß (in which Rβ is H or an alkyl group) and carbonyl functions. An especially preferred precursor of the benzoxazine type is: Preformed organic peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, an organic peroxy acid bleach precursor compound, a preformed organic peroxyacid, typically at a level of 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R1- C-N- R2- C-OOH I I R I O R5 O R1- N- C-R2-C-OOH R '? 5 O I O I in which R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group that contains from 1 to 14 carbon atoms, and R ^ is H or an alkyl, aryl or alkaryl containing from 1 to 10 carbon atoms. R1 may be straight or branched chain alkyl containing branching, substitution, or both and may originate from synthetic sources or natural sources including, for example, tallow fat. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substitution groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Means for release rate control A means may be provided for controlling the rate of release of bleaching agent, particularly oxygen bleach to the wash solution. The means for controlling the release rate of the bleach can provide controlled release of peroxide species to the wash solution. Such means could include, for example, control of release of any inorganic perhydrate salt, acting as a source of hydrogen peroxide to the wash solution. Suitable controlled release media may include confining the bleach to any of the compressed or non-compressed portions. Where more than one non-compressed portion is present, the bleach can be confined to the first and / or second and / or optional optionally uncompressed portions. Another mechanism for controlling the rate of release of the bleach can be by coating the bleach with a coating designed to provide release control. The coating may therefore comprise poorly water-soluble material, or be a coating of sufficient thickness so that the dissolution kinetics of the coarse coating provide the rate of controlled release.

The coating material can 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, for example hydrogenated (partially) vegetable oil, soybean oil, cottonseed oil, mono or diglycerides, micro crystalline waxes, gelatin, cellulose, fatty acids and mixtures thereof. Other suitable coating materials may comprise the alkali metal and alkali metal sulfates, silicates and carbonates, including calcium carbonate and silicas. A preferred coating material, particularly for a source of inorganic perhydrate salt bleach, comprises sodium silicate of SiO2: Na2O ratio from 1.8: 1 to 3.0: 1, preferably from 1.8: 1 to 2.4: 1 and / or sodium metasilicate. sodium, preferably applied at a level of 2% to 10%, (usually 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Any inorganic salt coating materials can be combined with organic binder materials to provide inorganic salt / organic binder composite coatings. Suitable binders include the C-? 0-C2o alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C? S-C2o primary alcohol ethoxylates containing from 20 -100. moles of ethylene oxide per mole of alcohol. Other preferred binders include certain polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 x 106 preferably 1,000 to 400,000, more preferably 1,000 to 10,000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride constituting at least 20 mole percent of the polymer are additional examples of polymeric materials useful as binders. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and ethoxylates of C? O-C20 alcohol containing from 5 - 100 moles of ethylene oxide per mole. Additional examples of binders include the mono- and diglycerol ethers of C 0-C 2 o and also the C-α 0-C 2 o fatty acids. Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of suitable binders for use herein. A method for applying the coating material involves agglomeration. Preferred agglomeration procedures include the use of any of the organic binder materials described above. Any conventional agglomerator / mixer can be used including, but not limited to, pan type, rotary drum and vertical mixers.

The molten coating compositions can also be applied either by pouring them on, or by spraying on a movable bed of bleaching agent. Other means to provide controlled release required include mechanical means to alter the physical characteristics of the bleach to control its solubility and release rate. Suitable protocols could include compression, mechanical injection, manual injection, and adjustment of the solubility of the bleaching compound by selection of the particle size of any particulate component. 10 While the choice of particle size will depend both on the composition of the particulate component, and on the desire to fulfill the desired controlled release kinetics, it is desirable that the particle size should be more than 500 microns., preferably having an average particle diameter of 800 to 1200 microns. Suitable protocols for providing the controlled release means include the proper choice of any other components of the detergent composition matrix such that when the composition is introduced into the wash solution the ionic strength environment provided therein permits that controlled release kinetics are achieved required. 'mß * »itíá & **? MáHl0mmSBSk» e »- *** Aw? * n. -As ^ < - »« a & »Bleach Catalyst The compositions described herein which contain bleach as an active detergent component may additionally contain as a preferred component a metal-containing bleach catalyst. Preferably the metal-containing bleach catalyst is a bleach catalyst containing transition metal, more preferably a bleach catalyst containing manganese or cobalt. A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper cations, iron, an auxiliary metal cation having little or no catalytic bleaching activity, such as cations of zinc or aluminum and a sequestrant having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra- (methylene phosphonic acid) and the water soluble salts thereof. Said catalysts are described in the U.S. patent. No. 4,430,243. Preferred types of bleach catalysts include the manganese-based complexes described in the U.S. Patents. No. 5,246,621 and E.U.A. No. 5,244,594. Preferred examples of these catalysts include Mn'V2 (u-0) 3 (1,4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF6) 2, Mnl || 2 (u- O) < | (u-OAc) 2 (1, 4,7-trimethyl-1, 4 I7-triazacyclononane) 2- (Cl? 4) 2, Mn, V4 (u- 0) 6 (1, 4,7-triazacyclononane) 4- (Cl? 4) 2, Mn'nMn '^ u-O)! (u-OA O, 4,7-trimethyl- '"* S 1, 4,7-triazacyclononane) 2- (Cl 4) 3 and mixtures thereof Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl -1,4,7-triazacyclononane and mixtures thereof Bleach catalysts useful in the present compositions may also be selected as is suitable for the present invention For examples of suitable bleach catalysts see U.S. Patent No. 4,246,612 and U.S. Patent No. 5,227,084, See also U.S. Patent No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) ( OCH3) 3_ (PF6) Still another type of bleach catalyst such as that described in US Patent No. 5,160,606 is a water soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-isonitol, lactose, and mixtures thereof. U.S. Patent No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a non- (macro) -cyclic ligand. These ligands are of the formula: In which R1, R2, R3 and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N = C-R2 and R3-C = N-R4 form a five or six member ring . Said ring can be replaced additionally. B is a bridging group selected from O, S, CR5R6, NR7 and C = O, in which R5, R6 and R7 may 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 can be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleach catalysts include complexes of Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) CI2, Di (isothiocyanate) bispyridylamine-cobalt (ll), trisdispyridylamine-cobalt perchlorate (ll), Co (2,2'-bispyridylamine) 2O2CIO4, perchlorate of Bis- (2,2'-bispyridylamine) copper (ll), iron tris (di-2-pyridylamine) perchlorate (II), and mixtures thereof. Preferred examples include binuclear Mn complexed with tetra-N-toothed and bi-N-toothed ligands, including N4Mn "l (u-O) 2Mn'vN4) + and [Bipy2Mnl l l (u-O) 2Mnl b¡py2] - (CIO4) 3.

Although the structures of the manganese complexes bleach catalysts of the present invention have not been elucidated, it can be speculated that they comprise chelators or other hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation . Similarly, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the valence state (+11), (+ III), (+ IV), or (+ V). Due to the six possible points of adhesion of the ligand to the manganese cation, it can be reasonably speculated that multi-nuclear species and / or "cage" structures may exist in the aqueous bleach medium. Whichever way the active Mn ligand species can currently exist, they function in an apparently catalytic manner to provide improved bleaching performance on difficult stains such as tea, ketchup, coffee, wine, juice and the like. Other bleach catalysts are described, for example, in European Patent Application No. 408,131 (Cobalt Complex Catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (Metalloporphyrin Catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), E.U.A. 4,711, 748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), E.U.A. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U.A. 4,728,455 (manganese gluconate catalysts). Other preferred examples include cobalt catalysts (III) having the formula: Co [(NH3) nM'mB'bT ', QqPp] Yy In which the cobalt is in the oxidation state +3, n is an integer from 0 to 5 (preferably 4 or 5, more preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, more preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; what is it 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more selected counterions suitably present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3, more preferably 2 when Y is a charged anion -1), to obtain a balanced charge salt , the preferred Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and in which additionally at least one of the coordination sites adhered to the cobalt is labile under conditions d use of automatic machine for dishwashing and the remaining coordination sites stabilize the cobalt under conditions of automatic machine for dishwashing so that the reduction potential of cobalt (III) to cobalt (II) 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, more preferably 5); M "is a labile buffering portion, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is larger than 1) combinations thereof, m is an integer from 1 to 3 (preferably 1 or 2; more preferably 1); m + n = 6; and Y is a selected counter-current suitably present in a number y, which is an integer from 1 to 3 (preferably 2 to 3, more preferably 2 when Y is a charged anion -1 ) to obtain a balanced charge salt The preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co (NH3) 5CI] Yy, and especially [Co (NH3) 5CI CI2 The compositions of the present invention which use cobalt bleach catalysts (III) having the formula are more preferred: [Co (NH3) n (M) m (B) b] Ty MÍ ^^ & S $ ^ in which the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more selected counterions suitably present in a number and, where y is an integer to obtain a balanced charge salt (preferably y is 1 to 3, more preferably 2 when T is a charged anion -1); and wherein said catalyst additionally has a constant base hydrolysis rate of less than 0.23 M'1 s "1 (25 ° C.) The preferred T is selected from the group consisting of chloride, iodide, 13-1, format, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF4", B (Ph) ", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T can be protonated if there is more than one anionic group in T, for example, HPO 2", HCO 3", H 2 PO 4", etc. Additionally, T can be selected from the group consisting of non-traditional inorganic anions as anionic surfactants ( for example linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or cationic polymers (for example polyacrylates, polymethacrylates, etc.) The M-portions include, but are not limited to, for example , F ', SO4"2, NCS", SCN ". S2O3"2, NH3, PO43", and carboxylates (which preferably are monocarboxylates, but more than one carboxylate may be ^^ "aaM & faith" -tej «&? M" «a? A ^ a = áfe« -t rfliffiráiiiii ff ^^ present in the portion as long as the cobalt binding is only one carboxylate per serving , in which case the other carboxylate in the M-portion may be protonated or in the form of its salt). Optionally, M may be protonated if more than one anionic group exists in M (eg, HPO42", HCO3", H2PO4", 5 HOC (o) CH2C (O) O-, etc.). The preferred M-portions are acidic. substituted and unsubstituted C-? -C3 carboxylic acids having the formulas: RC (O) O- Wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C-? -C30 alkyl (preferably C-? -C? 8), C6-C30 aryl (preferably C6-C? 8) substituted and unsubstituted and C3-C30 (preferably C5-C? 8) substituted and unsubstituted heteroaryl, in which the substituents are selected from the group consisting of -NR'3, -NR'4 +, - 15 C (O) OR ', -OR', -C (O) NR'2, in which R 'is selected from the group consisting of hydrogen and portions of C -? - C6. Said substituted R thus includes the portions - (CH2) nOH and - (CH2) nNR'4 +, in which n is an integer from 1 to 6, preferably from 2 to 10, and more preferably from 2 to 5. The most preferred M are carboxylic acids having the formula Above in which R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C-? 2 alkyl, and benzyl. The most preferred R is methyl. The M-moieties of carboxylic acid included include formic, benzoic, cationic, nonanoic, decanic, dodecanoic, malonic, r | - | - ^ átilirr ^ ¿^: ^^; - 'maleic, succinic, adipic, phthalic, 2-ethylenexanic, naphthenic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic. Portions B include carbonate, di- and higher carboxylates (for example oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (for example glycine, alanine, beta-alanine, phenylalanine). Cobalt bleach catalysts useful herein are known to be described for example together with their base hydrolysis rates in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes," Adv. Inorg. Bioinorg. Mech .. (1983), 2, pages 1-94. For example, Table 1 on page 17, provides the base hydrolysis rates (designated therein as koH) for cobalt pentaamine catalysts that complex with oxalate (kOH = 2.5 x 10-4 m "1 s" 1 (25 ° C)), NCS- (kOH = 5.0 x 10"4 rt? 1 s" 1 (25 ° C)), format (kO = 5.8 x 10"4 m" 1 s "1 (25 ° C) )) and acetate (kO = 9.6 x 10"4 m'1 s" 1 (25 ° C).) The most preferred cobalt catalysts useful herein are the salts of cobalt pentaaminoacetate having the formula [Co (NH3 ) _5? Ac] Ty, where OAc represents an acetate portion, and especially cobalt pentaaminoacetate chloride, [Co (NH3) 5? Ac] Cl2; as well as [Co (NH3) 5OAc] (OAc) 2); [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5? Ac] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2 (here "PAC"). These cobalt catalysts are readily prepared by known processes, as taught for example in the above Tobe article and the references cited therein, in US Patent 4,810,410, to Diakun et al., Issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); v Journal of Phvsical Chemistrv, 56, 22-25 (1952); as well as the synthesis examples provided hereinafter. Cobalt catalysts suitable for incorporation into the detergent tablets of the present invention can be produced in accordance with the synthetic routes described in the U.S. Patents. Nos. 5,559,261, 5,581, 005, and 5,597,936, the disclosure of which is incorporated herein by reference. These catalysts can be co-processed with adjuncts such as to reduce the color impact if desired for product aesthetics, or be included in particles containing enzymes as illustrated here below, or the compositions can be manufactured to contain catalysts. "without stains".

Organic polymeric compound The organic polymeric compounds can be added as preferred components of the detergent tablets according to the invention. By "organic polymeric compound" is meant essentially any organic polymeric compound that is commonly found in detergent compositions having dispersing, anti-redeposition, dirt release or other detergency properties. i. ** ^ J &lM * * 5 * 5A = &2a_.

The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, more preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include homo- or co-polymeric polycarboxylic acids, modified polycarboxylates or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. Polymers of the latter type are described in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight 2,000-10,000 and their copolymers with any other monomer units including modified acrylic, fumaric, maleic, ataconic, aconitic, mesaconic, citraconic and methylenemalonic acids or their salts, maleic anhydride, acrylamide, alkylene, ether. vinyl methyl, styrene and any mixtures thereof. Copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000 are preferred. Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the trademark Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the trademark Acusol 45N, 480N, 460N by Rhon and Hass. Preferred acrylic acid-containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight of acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of substituted acrylic monomer or its salts having the general formula - [CR2-CR -? (CO-O-R3)] - in which at least one of the substituents Ri, R2 or R3 , preferably Ri or R2 is an alkyl or hydroxyalkyl group of 1 to 4 carbons, Rt or R2 may be a hydrogen and R3 may be a hydrogen or alkali metal salt. More preferred is a substituted acrylic monomer in which R-i is methyl, R2 is hydrogen (ie methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid. The polyamine and modified polyamine compounds are useful herein including those aspartic acid derivatives such as those described in EP-A-305282, EP-A-305283 and EP-A-351269. Other optional polymers may be polyvinyl alcohols and modified and unmodified acetates, modified cellulosics and cellulosics, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, modified and unmodified, esters of ethylene or propylene glycol terephthalate or mixtures thereof with polyoxyalkylene units. Suitable examples are described in US Patents Nos. 5,591, 703, 5,597,789 and 4,490,271. gí t.A? 'sPr, ..

Dirt Release Agents Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophilic components consisting essentially of (!) Polyoxyethylene segments with a degree of polymerization of minus 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not encompass any oxypropylene unit unless it is adhered to adjacent portions at each end by ether linkages, or ( iii) a mixture of oxyalkylene units comprising oxyethylene of 1 to 30 oxypropylene units, said hydrophilic segments preferably comprise at least 25% oxyethylene units and more preferably, especially for said components having from 20 to 30 oxypropylene units, at least 50% of oxyethylene units; or (b) one or more hydrophobic components comprising (i) oxyalkylene terephthalate segments of C3, in which, if said hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate: oxyalkylene terephthalate units of C3 is 2: 1 or lower, (ii) ) C4-C6 alkylene segments or C4-C6 oxyalkylene, or mixtures thereof, (ii) segments of poly (vinylester), preferably polyvinylacetate, having a degree of polymerization of at least 2, or (iv) substituents of C1-C4 alkyl ether or C4 hydroxyalkyl ether, or mixtures thereof, in which said substituents are present in the form of C-1-C4 alkyl ether cellulose derivatives or C4 hydroxyalkyl ether, or mixtures thereof. same, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of 200, although higher levels may be used, preferably from 3 to 150, more preferably from 6 to 100. The hydrophobic segments of C4-C6 oxyalkylene include, but are not limited to, blocked end polymeric soil release agents, such as MO3S (CH2) nOCH2CH2O-, where M is sodium and n is an integer of 4-6, as described in U.S. Patent No. 4,721, 580, from January 26, 1988 to Gosselink. The polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene terephthalate oxide, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; see U.S. Patent No. 4,000,093, December 28 to Nicol, et al. Soil release agents characterized by hydrophobic poly (vinyl ester) segments include grafted copolymers of poly (vinylester), for example vinyl C1-C6 esters, preferably poly (vinyl acetate) grafted to polyalkylene oxide base structures, as ^ y? g ^? ^ g ^ ^^^ 2 *? ^ ígg ^^ base structures of polyethylene oxide. See the European patent application, April 22, 1987 to Kud, et al. Another suitable soil release agent is a copolymer having random blocks of ethyleneneterephthalate and polyethyleneneterephthalate oxide (PEO). The molecular weight of this polymeric soil release agent is in the range of 25,000 to 55,000. See U.S. Patent No. 3,959,230 to Hays, May 25, 1976, and U.S. Patent No. 3,893,929 to Basadur, July 8, 1975. Another suitable polymeric soil release agent is a polyester repeat units of ethylene terephthalate units containing 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 of 300-5,000. Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprising an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and terminal portions covalently bonded to the base structure. These soil release agents are fully described in U.S. Patent No. 4,968,451, 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 No. 4,711,730, December 8, 1987 to Gosselink, et al., The blocked end ammonic oligomeric esters of U.S.A. 4,721, 580, from January 26, 1988 to Gosselink, and the oligomeric block polyester compounds of U.S. Patent No. 4,702,857, October 27, 1987 to Gosselink. Other polymeric soil release agents also include the soil release agents of the U.S.A.

No. 4,877,896, from October 31, 1989 to Maldonado et al, which describes anionic terephthalate esters, especially sulfoaroyl, of blocked end. Another soil release agent is an oligomer with repeated units of terephthaloyl units, sulfoisoterephthaloyl units, units oxytyloxy and oxy-1,2-propylene. The repeating units form the base structure of the oligomer and are preferably determined with blocked ends of the modified isethionate. A particularly preferred soiling release agent of this type comprises a sulfosisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1, 2-propyleneoxy units in a ratio of 1.7 to 1.8 and two units of 2- (2-hydroxyethoxy) - blocked end sodium ethanesulfonate.

Heavy metal ion sequestrant The detergent tablets of the invention preferably contain a heavy metal ion sequestrant as an optional component. By heavy metal ion sequestrant herein it means components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating capacity, but a »preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably 0.1% to 10%, most preferably 0.25% to 7.5% and more preferably 0.5% to 5% by weight of the compositions . Heavy metal ion sequestrants, which are acids in nature, having for example functionalities of phosphonic acid and carboxylic acid, can be present either in their acid form or as a complex / salt with a suitable counter cation as an ion of alkali metal or alkali metal, ammonium ion, or substituted ammonium, or any mixtures thereof. Preferably the salts / complexes are hydrosoluble. The molar ratio of said counter cation to the heavy metal sequestrant is preferably at least 1: 1. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylenepoly (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), ethylenediamine (methylene phosphonate), hexamethylenediamine (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamindisuccinic acid or any salt thereof. Especially preferred is ethylene diamine-N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. The compounds Preferred EDDS are the free acid forms and the sodium or magnesium salt or complex thereof.

Crystal Growth Inhibiting Component Detergent tablets preferably contain a crystal growth inhibiting component, preferably an organodisphosphonic acid component, preferably incorporated at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions By organodiaphosphonic acid it means in the present an organodiphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the aminophosphonate organ, which however can be included in the compositions of the invention as heavy metal sequestering components. The organodiphosphonic acid is preferably an organodiphosphonic acid of 1-4, more preferably an organodiphosphonic acid of 2, such as ethylenediphosphonic acid, or more preferably ethane 1-hydroxy-1, 1- acid. t i * &HÍIM¿k¿? .at »diphosphonic (HEDP) and may be present in partially or completely ionized form, particularly as a salt or complex.

Water-soluble sulfate salt The detergent tablet optionally contains a water-soluble sulfate salt. When present, the water-soluble sulfate salt is at a level of 0.1% to 40%, more preferably 1% to 30%, more preferably 5% to 25%, by weight of the compositions. The water-soluble sulfate salt can be essentially any sulfate salt with any countercation. The preferred salts are selected from sulfates of alkali metals or earth-alkaline metals, particularly sodium sulfate.

Alkali metal silicate According to one embodiment of the present invention an alkali metal silicate is an essential component of the detergent tablet. In other embodiments of the present invention the presence of an alkali metal silicate is optional. A preferred alkali metal silicate is sodium silicate having an SiO2: Na2O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, more preferably 2.0. The sodium silicate is preferably present at a level of less than 20%, preferably from 1% to 15%, more preferably from 3% to 12% by weight of SiO2. The alkali metal silicate can be in the form of anhydrous salt or a hydrated salt.

The alkali metal silicate can 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% SiO2 by weight. Sodium metasilicate has a nominal SiO2: Na2O ratio of 1.0. The weight ratio of sodium silicate to sodium metasilicate, measured as SiO 2, is preferably from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, more preferably from 10: 1 to 5: 2.

Colorant The term "colorant", as used herein, means any substance that absorbs specific wavelengths of light from the spectrum of visible light. Said colorants when added to a detergent composition have the effect of changing the visible color and hence the appearance of the detergent composition. The dyes can be, for example, inks or pigments. Preferably the dyes are stable in the composition in which they are to be incorporated. In this way in a high pH composition the dye is preferably alkaline stable and in a low pH composition the dye is preferably stable acid. The compressed and / or uncompressed portion may contain a dye, a mixture of dyes, particles with dye or mixture of particles with dye so that the compressed portion and the uncompressed portion have different visual appearances. Preferably one of ¿J * si¡lfe ^^^ ¿^^ A | any of the compressed portion or the non-compressed portion comprises a colorant. Wherein the non-compressed portion comprises two or more active detergent component compositions, preferably at least one of the first and second and / or subsequent compositions comprises a colorant. Where the first and second and / or subsequent compositions comprise a colorant it is preferred that the colorants have a different visual appearance. Where present, the coating layer preferably comprises a colorant. Where the compressed portion and the coating layer comprise a colorant, it is preferred that the colorants provide a different visual effect. Examples of suitable inks include reactive inks, direct inks, azo inks. Preferred inks include phthalocyanine inks, anthraquinone inks, quinoline inks, monoazo, disazo and polyazo inks. The most preferred inks include anthraquinone, quinoline and monoazo inks. Preferred inks include SANDOLAN E-HRL 180% (trademark) SANDOLAN MILLING BLUE (trademark), TURQUOISE ACID BLUE (trademark) and SANDOLAN BRILLIANT GREEN (trademark), all available from Clariant UK, HEXACOL QUINOLINE YELLOW (trademark) ) and HEXACOL BRILLIANT BLUE (trademark) both available from Pointings, UK, ULTRA MARINE BLUE (trademark) available from Holliday or LEVAFIX TURQUISE BLUE EBA (trademark) available from Bayer, USA. »*. ** & & amp; & amp; The color can be incorporated in the compressed portion and / or non-compressed portion by any suitable method. Suitable methods include mixing all or selected active detergent components with a colorant in a drum or spraying all or selected active detergent components with the colorant in a rotating drum. The colorant when present as a component of the compressed portion is present at a level of 0.001% to 1.5%, preferably from 0.01% to 1.0%, more preferably from 0.1% to 0.3%. When present as a component of the non-compressed portion, the colorant is present at a level from 0.001% to 0.1%, more preferably from 0.005% to 0.05%, more preferably from 0.007% to 0.02%. When present as a component of the coating layer, the colorant is present at a level of 0.01% to 0.5%, more preferably 0.02% to 0.1%, more preferably 0.03% to 0.06%.

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

Organic silver coating agents are described in PCT Publication No. WO94 / 16047 and co-pending European Application No. EP-A-690122. Nitrogen-containing corrosion inhibiting compounds are described in co-pending European application No. EP-A-634,478. The Mn (II) compounds for use in corrosion inhibition are described in European application No. EP-A-672749. The organic silver coating agents 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 a protective coating layer "in use" on any silverware components of the wash load to which the compositions of the invention are being applied. The silver coating agent must therefore have a high affinity for adhesion to solid silver surfaces, particularly when it is present as a component of an aqueous wash and bleach solution with which the solid silver surfaces are being treated. Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. The fatty acid portion of the fatty ester can be obtained from mono- or polycarboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valeric acid, lactic acid, glycolic acid and beta acid. , ß'- díhidroxiisobutírico. Examples of suitable polycarboxylic acids include n-butyl-malonic acid, citric acid, citric acid, maleic acid, malic acid and succinic acid. The fatty alcohol radical in the fatty ester may be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include behenyl, arachidyl, cocoyl, oleyl and lauric alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaepritol, sorbitol or sorbitan. Preferably, the fatty acid and / or fatty alcohol group in the attached fatty ester material has from 1 to 24 carbon atoms in the alkyl chain. The preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters in which the fatty acid portion of the ester usually comprises a selected species of behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. 0 Glycerol esters are also highly preferred. These are mono-, di-, or tri-esters of glycerol and the fatty acids as defined above. '? £ a * iU? i¡ag ?! . Al. ^^^^ Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and tallow propionate. Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan stresses include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomiristate, sorbitan monobehenate, sorbitan monoleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mono- and sorbitan tallow alkyl 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 fully or partially hydrogenated derivatives thereof, any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, colaza oil, grapeseed oil, palm oil and corn oil. .

Waxes, including microcrystalline waxes are organic silver coating agents suitable herein. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise from 12 to 70 carbon atoms. Preferred are paraffin waxes and microcrystalline waxes which are composed of saturated long chain hydrocarbon compounds. Alginates and gelatin are suitable organic silver coating agents herein. Dialkyl amine oxides such as C 2 C 2 C 20 methylamine oxide, and quaternary dialkylammonium compounds and salts, such as C 12 -C 2 met methylammonium halides, are also suitable. Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, polymers of N-oxide polyamine, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and derivatives of Cellulose such as methylcellulose, carboxymethylcellulose and hydroxymethylcellulose are examples of such polymeric materials. Certain perfume materials, particularly those that demonstrate a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein. The polymeric soil release agents can also be used as a suitable organic silver coating agent.

^^ M * ^ S? JigSi l5l ^ kgM ge ^ 6tí r A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms on the scale of 20 to 50; the paraffin oil selected from predominantly branched C25-45 species with a cyclic to non-cyclic hydrocarbon ratio of 1: 10 to 2: 1, preferably 1: 5 to 1: 1 is preferred. A paraffin oil having these characteristics, which has a cyclic to non-cyclic hydrocarbon ratio of 32:68 is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Nitrogen-Containing Corrosion Inhibiting Compounds Suitable nitrogen-containing corrosion inhibiting compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecylimidazole, and those imidazole derivatives described in the Czechoslovak Patent No. 139,279, and British Patent GB-A-1, 137,741, which also describes a method for making imidazole compounds. Also suitable as nitrogen-containing corrosion inhibiting compounds are pyrazole compounds and their derivatives, particularly those wherein pyrazole is substituted at any of positions 1, 2, 3, 4 or 5 by substituents Ri, R2, R3, R4 and R5 wherein R is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any alkyl or hydroxyl of C -? - C20, and R is any of H, NH2 or NO2.

Other corrosion inhibitor compounds Suitable nitrogen containing benzotriazole include 2-mercaptobenzotiazola, 1 -phenyl-5-mercapto-1, 2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, estearoilestereamida, cyanuric acid, aminotriazola, aminotetrazole and indazola. Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or ammonium dihydrogen citrate are also suitable.

Mn (ll) corrosion inhibiting compounds The detergent tablets may contain a corrosion inhibiting compound of Mn (ll). The Mn (ll) compound is preferably incorporated at a level of 0.005% to 5% by weight, more preferably from 0.01% to 1%, more preferably from 0.02% to 0.4% by weight of the compositions. Preferably, the compound of Mn (ll) is incorporated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, more preferably from 1 ppm to 20 ppm by weight of Mn ions (ll) in any bleaching solution. The Mn compound (II) can be an inorganic salt in anhydrous form or in any hydrated form. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate, and manganese chloride. The compound of saiMA '^^ É? < t »m Mn (ll) can be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate. The compound Mn (ll) can be a salt or complex of an organic ligand. In a preferred aspect the organic ligand is a heavy metal ion sequestrant. In another preferred aspect the organic ligand is a crystal growth inhibitor.

Other Corrosion Inhibiting Compounds Other suitable additional corrosion inhibiting compounds include mercapts and diols, especially mercapts with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionephthol, tionalide and thioanthranol. Also suitable are saturated or unsaturated C 12 -C 20 fatty acids, or their salts, especially aluminum tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane antioxidants and others such as beta-hydroxytoluene (BHT) are also suitable. Copolymers of butadiene and maleic acid, particularly those supplied under the reference mark No. 07787 by Polysciences Inc. have been found to be of particular utility as corrosion inhibiting compounds. ^^^^^^ * ^^^ j ^ * ^ 4¿ iffÉBtff? T'i l Hiyg Hydrocarbon oils Another preferred active detergent component for use in the present invention is a hydrocarbon oil, typically predominantly aliphatic hydrocarbon chain long they have a number of carbon atoms on the scale of 20 to 50; the preferred hydrocarbons are saturated and / or branched; the hydrocarbon oil selected from predominantly branched C25-45 species with a cyclic to non-cyclic hydrocarbon ratio of 1: 10 to 2: 1, preferably 1: 5 to 1: 1 is preferred. A preferred hydrocarbon oil is paraffin. A paraffin oil that meets the characteristics as defined above, having a cyclic to non-cyclic hydrocarbon ratio of 32:68 is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Compound soluble bismuth detergent tablets of the present invention suitable for use in methods of dishwashing can contain a compound soluble bismuth preferably present at a level of 0.005% to 20%, more preferably from 0.01% to 5%, more preferably from 0.1% to 1% by weight of the compositions. The water-soluble bismuth compound can be essentially any bismuth salt or complex with essentially any organic or inorganic counter-ion. The preferred bismuth salts are selected from bismuth trihalogenides, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with an organic counter ion. enzyme stabilizing system containing compositions preferred enzyme herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%, more preferably from 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system that is compatible with the detersive enzyme. Said stabilizer systems may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scrubbers and mixtures thereof. Said stabilizer systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Compound dispersing lime soap compositions of active detergent components may contain a dispersant compound lime soap, preferably present at a level of 0.1% to 40% by weight, more preferably 1% to 20% by weight, more preferably 2% to 10% by weight of the compositions. A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. Preferred lime soap dispersant compounds are described in PCT Application No. WO93 / 08877.

Foam suppression system The detergent tablets of the present invention, when formulated for use in compositions for machine washing, preferably comprise a foam suppression system present at a level of 0.01% to 15%, preferably 0.05% at 10%, most preferably 0.1% a % by weight of the composition. Suppression systems foams suitable for use herein may comprise essentially any known antifoaming compound, including, for example, defoamers and antifoams silicone compounds composed of 2-alk? L alkanol. Preferred foam and anti-foam suppression systems are described in PCT Application No. WO93 / 08876 and EP-A-705324.

Polymeric Dye Transfer Inhibitory 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 inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

U S ^^^^^ ^^^^^^^^ Optical brightener suitable for use in laundry washing methods as described herein, also optionally contain detergent tablets of about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: in which R- | it is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholine, chlorine and amino; and M is a salt-forming cation such as sodium or potassium. When in the previous formula R < | is anilino, R is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-α-NN-bis-hydroxyeti -s-triazine) This amino broth is sold commercially under the trade name Tínopal-UNPA-GX by Ciba-Geígy Corporation.The Tínopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the previous formula R- | is anilino, R2 is N-2-hydroxyethyl N-2-methylamino and M is a cation such as sodium, the brightener is disodium salt of 4,4, -bis [(4-anil¡no-6- ( N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula R < | is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is sodium salt of 4,4'-bis [(4- anil¡no-6-s-triazine-morfil¡no-2- il) amino] 2,2, -stilbenedisulfonic. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Clay softening system Detergent tablets suitable for use in laundry cleaning methods may contain a clay softening system comprising a mineral clay compound and optionally a clay flocculating agent. The mineral clay compound is preferably a smectite clay compound. Smectite clays are described in US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patents Nos. 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 Softening Agents Cationic fabric softening agents can also be incorporated into compositions according to the present invention which are suitable for use in laundry washing methods. Suitable cationic fabric softening agents include the non-water soluble tertiary amines or dilarga chain amide materials as described in GB-A-1, 514, 276 and EP-B-0 011 340. The cationic fabric softening agents are incorporated typically at total levels of 0.5% to 15% by weight, usually from 1% to 5% by weight.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes and filler salts, with sodium sulfate being a preferred filler salt. pH of the compositions The detergent tablets of the present invention are preferably not formulated to have unduly high pH, preferably have 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, more preferably from 9.5 to 11.5.

In another aspect of the present invention the compressed and non-compressed portions are formulated to deliver different pH.

Automatic dishwashing method 5 Any suitable methods for automatic dishwashing or cleaning of dirty cutlery are envisaged. An automatic dishwashing method which is preferred comprises treating soiled articles selected from earthenware, glassware, silverware, metal articles, cutlery, and mixtures thereof, with a liquid Water that has dissolved or dispersed therein an effective amount of a detergent tablet according to the invention. For an effective amount of the tablet detergents means from 8g to 60g of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, which are product doses and volumes of typical washing solution commonly employed in conventional automatic dishwashing methods. Preferably the detergent tablets are from 15g to 40g by weight, more preferably from 20g to 35g by weight.

Laundry Method 20 The laundry washing methods of the present invention typically comprise treating laundry with an aqueous wash solution in a washing machine having dissolved or supplied therein an effective amount of a laundry detergent tablet composition. on machine U *? M8i a faith? ttsá ^ tiíiti is ^? ^ m i ^ i i &iiss. washing machine according to the invention. For an effective amount of the detergent tablet composition means from 40g to 300g of product dissolved or dispersed in a wash solution of a volume of 5 to 65 liters, which are typical product doses and volumes of wash solution commonly employed in methods of laundry in conventional washing machine.

In a preferred use aspect a dispensing device is employed in the washing method. The delivery device is loaded with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its volume capacity must be such as to be able to contain enough detergent product as it would normally be used in the washing method. Once the washing machine has been loaded with clothes the supply device containing the detergent product is placed inside the drum. At the start of the wash cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the delivery device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the washing cycle in response to its agitation as the drum rotates and also as a result of its contact with the washing liquid. To allow the release of the detergent product during washing, the device may have a number of openings through the which can pass the product. Alternatively, the device may be made of a material that is permeable to liquid but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing high localized transient concentrations of the product in the drum of the washing machine at this stage of the wash cycle. Preferred delivery devices are reusable and designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Alternatively, the delivery device may be a flexible container, such as a bag or bag. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it may be formed of an insoluble synthetic polymeric material. in water provided with an edge seal or seal designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water-curable closure comprises an adhesive soluble in water. water disposed along and sealing an edge of a sack formed of a waterproof polymeric film such as polyethylene and polypropylene.

EXAMPLES Abbreviations used in the examples In detergent compositions, the abbreviated component identifications have the following meanings: STPP: Sodium tripolyphosphate. Citrate: Trisodium citrate dihydrate Bicarbonate: Sodium hydrogen carbonate. Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate Silicate: Amorphous sodium silicate (Si? 2 ratio: Na2? = 1.6- 3.2 Metasilicate: sodium metasilicate (Si? 2 ratio: Na2? = 1.0) PB1: anhydrous sodium perborate monohydrate. PB4: Sodium perborate tetrahydrate of nominal formula NaBO2.3H2? .H2O2 Plurafac: Ethoxylated / propoxylated C13-C15 fatty alcohol mixed with an ethoxylation degree of 3.8 and an average degree of propoxylation of 4.5, sold under the trademark Plurafac by BASF. ^ ^^^^^ ^^^^^ teg Tergitol: Nonionic surfactant available under the trademark Tergitol 15S9 from Union Carbide. SLF 18: Epoxy-blocked poly (oxyalkylated) alcohol of Example III of WO 94/22800 in which 1,2-epoxydodecane is substituted by 1,2-epoxydekane available under the trademark Polytergent SLF18D from OLIN. TAED: Tetraacetylethylenediamine HEDP: Ethane 1-hydroxy-1,1-diphosphonic acid. DTPMP: Diethylenetriaminpenta (methylene) phosphonate, marketed by Monsanto under the trademark Dequest 2060. PAAC: Salt of pentaamine cobalt acetate (III). BzP: Benzoyl peroxide. Paraffin: Paraffin oil sold under the trademark Winog 70 by Wintershall. Protease: Proteolytic enzyme Amylase: Amylolytic enzyme BTA: Benzotriazole PA30: Polyacrylic acid of average molecular weight of approximately 4,500. 480N: Random copolymer of 7: 3 acrylate / methacrylate, average molecular weight 3,500. Sulfate: Anhydrous sodium sulfate PEG 3000: Polyethylene glycol with molecular weight of approximately 3000 available from Hoechst. PEG 6000: Polyethylene glycol of molecular weight of approximately 6000 available from Hoechst. Sugar: Sucrose domestic. Gelatin: Gelatin Type A, resistance of _65 available from Sigma. CMC: Carboxymethylcellulose Dodecandioic acid: C12 dicarboxylic acid. Adipic acid: C6 dicarboxylic acid. Lauric acid: C12 monocarboxylic acid. pH: measured as a 1% solution in distilled water at 20 ° C.

In the following examples, all levels are cited as% by weight of the compressed portion, the non-compressed portion or the coating layer: EXAMPLE 1 The following illustrates examples of detergent tablets of the present invention suitable for use in a dishwashing machine.

U *? -U ^^^ ¿- & J U -.

The compressed portion is prepared by supplying the composition of active detergent components to a perforating cavity of a modified 12-head rotary tablet press and compresses the composition at a pressure of 13 KN / cm 2. The modified tablet press provides tablets in which the compressed portion has a mold. For the purposes of Example A to F the non-compressed portion is in the form of particles. The non-compressed portion is precisely supplied to the mold of the compressed portion using a nozzle feeder. The non-compressed portion adheres to the compressed portion by coating the non-compressed portion with a coating layer contacting the compressed portion.

EXAMPLE 2 The compressed portion is prepared by supplying the composition of active detergent components to a perforating cavity of a modified 12-head rotary tablet press and compressing the portion at a pressure of 13 KN / cm 2. The modified tablet press provides tablets in which the compressed portion has a mold. For the purposes of Examples G to K the non-compressed portion comprises active detergent components and a binder. The non-compressed portion is then poured into the mold of the compressed portion. The detergent tablet is then subjected to a conditioning step, during which time the non-compressed portion hardens. bJ & 's »¡G? iA -V" ~. «wh jttí áA- a jjcj Hh g yfeaagamM ¿^ ¡^ ^ ^ * se ^ s ^ ifcs¡g »» i ^ M ^ ~ **. * ..- ¿s-. sfe

Claims (31)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent tablet comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion, comprising an active detergent component, further characterized in that the detergent tablet comprises an enzyme.

2. A detergent tablet comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion, comprising an active detergent component, further characterized in that the weight ratio of the compressed portion to the uncompressed portion is greater than 0.5: 1 and the detergent tablet comprises silicate.

3. A detergent tablet comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion, comprising an active detergent component, further characterized in that the weight ratio of the portion (s) compressed to the uncompressed is greater than 0.5: 1 and the detergent tablet has a dissolution rate greater than 0.33 g / min as determined using the SOTAX dissolution test method described herein.

4. - A detergent tablet comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion, comprising an active detergent component, further characterized in that the weight of the detergent tablet is less than 40 g and the detergent tablet has a dissolution rate greater than 0.33 g / min. is determined using the SOTAX dissolution test method described herein.

5. A detergent tablet comprising: (a) a compressed portion comprising an active detergent component; and (b) a non-compressed, non-encapsulating portion, comprising an active detergent component, further characterized in that the compressed portion provides a mold and the non-compressed portion is at least partially contained in the mold.

6. A detergent tablet according to any of claims 1 to 5 further characterized in that the non-compressed portion is in solid, liquid, or gel form.

7. A detergent tablet according to any of the preceding claims comprising a first and a second and optionally subsequent non-compressed portions.

8. A detergent tablet according to claim 7 when dependent on claim 6, further characterized in that the compressed portion provides a plurality of molds and each non-compressed portion is at least partially contained in the mold.

9. - A detergent tablet according to any of claims 7 or 8 further characterized in that at least two of the first, second and optional subsequent uncompressed portions comprise at least one different active detergent component.

10. A detergent tablet according to any of the preceding claims further characterized in that the non-compressed portion is coated with a coating layer.

11. A detergent tablet according to claim 10 further characterized in that the coating layer fixes the non-compressed portion to the compressed portion.

12. A detergent tablet according to claim 10 or 11 further characterized in that the coating layer is water-soluble.

13. A detergent tablet according to any of claims 10 to 12 further characterized in that the coating layer comprises a component that is selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA), polyethylene glycol (PEG) and mixtures thereof.

14. A detergent tablet according to claim 13 further characterized in that the coating layer comprises a component that is selected from the group consisting of adipic acid, lauric acid, suberic acid, zealic acid, bacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof.

15. - A detergent tablet according to any of the preceding claims further characterized in that the non-compressed portion is in the form of particles.

16. A detergent tablet according to any of the preceding claims further characterized in that the non-compressed portion comprises a solidified cast iron.

17. A detergent tablet according to any of the preceding claims further characterized in that the non-compressed portion comprises a binding agent that is selected from the group consisting of sugar, starch, gelatin and organic polymers.

18. A detergent tablet according to any of the preceding claims further characterized in that the compressed portion comprises a compressed active component detergent component.

19. A detergent tablet according to any of the preceding claims further characterized in that the rate of dissolution of the uncompressed portion is greater than the dissolution rate of the compressed portion measured using the SOTAX dissolution test method described in FIG. I presented.

20. A detergent tablet according to any of the preceding claims further characterized in that the rate of dissolution of the compressed portion is greater than the dissolution rate of the non-compressed portion measured using the SOTAX dissolution test method described in FIG. I presented.

21. A detergent tablet according to any of the preceding claims comprising an enzyme further characterized in that the enzyme is selected from the group consisting of amylases, proteases, cellulases, hemicellulases, peroxidases, lipases, phospholipases and mixtures thereof.

22. A detergent tablet according to any of the preceding claims comprising an alkali metal silicate.

23. A detergent tablet according to claim 22 further characterized in that the silicate is a sodium silicate having an SiO2: Na2O ratio of 1.0 to 3.0.

24. A detergent tablet according to any of the preceding claims further characterized in that the detergent tablet additionally comprises a disrupting agent which is a disintegrating agent, an effervescent agent or mixtures thereof.

25. A detergent tablet according to claim 24 further characterized in that the disrupting agent is selected from the group consisting of starch, starch derivatives, alginate, carboxymethylcellulose (CMC) based polymers, sodium acetate, aluminum oxide, carbonate , bicarbonate, carboxylic acids and mixtures thereof.

26. A method for preparing a detergent tablet according to any of the preceding claims, comprising: a) compressing a composition comprising an active detergent component to form a compressed portion; and b) supplying a composition comprising an active detergent component to the compressed portion to form a non-compressed, non-encapsulating portion.

27. A method according to claim 26 further characterized in that the method comprises the steps of: a) compressing active detergent components to form a compressed portion having a mold; and b) supplying a composition comprising active detergent components to the mold. 28.- A method according to any of claims 26 or 27 further comprising a subsequent coating step further characterized in that at least a portion of the non-compressed portion is coated with a coating layer in such a manner that the non-compressed portion it adheres substantially to the compressed portion. 29. A method according to any of claims 26 to 28 further comprising a subsequent conditioning step further characterized in that the non-compressed portion and / or optionally the coating layer hardens. 30. The use of a detergent tablet according to any of claims 1 to 25 in a method for dishwashing. 31. The use of a detergent tablet according to any of claims 1 to 25 in a method for washing fabrics.