MXPA01000577A - Detergent tablet - Google Patents

Abstract

A multi-phase detergent tablet for use in a washing machine, the tablet comprising:a) a first phase in the form of a shaped body having at least one mould therein;and b) a second phase in the form of a compressed body adhesively contained within said mould, wherein the tablet composition comprises one or more detergent actives which is predominantly concentrated in the second phase, and wherein the second phase additionally comprises a binder. The multi-phase tablets provide improved dissolution and cleaning characteristics together with excellent tabletintegrity and strength.

Description

DETERGENT TABLET TECHNICAL FIELD The present invention relates to multi-phase detergent tablets.

BACKGROUND OF THE INVENTION Detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form have several advantages over detergent compositions in the form of particles, such as ease of dosing, handling, transportation and storage. Detergent tablets are most commonly prepared by premixing components of a detergent composition and forming the premixed detergent components in a tablet using any suitable equipment, preferably a tablet press. The tablets are typically formed by compressing the components of the detergent composition, so that the tablets produced are sufficiently solid to be able to withstand handling and transportation without damage. In addition to being solid, the tablets must also dissolve quickly enough so that the detergent components are released into the wash water as soon as possible at the start of the wash cycle. However, there is a dichotomy because as the compression force is increased, the dissolution speed of the tablets is lower. Therefore, the present invention seeks to find a balance between the strength and dissolution of the table. The solutions to this problem, as seen in the prior art, have included compressing the tablets with low compression pressure. However, the tablets obtained in this way, although they have a relatively rapid dissolution rate, tend to be de-oiled, suffering damage and being unacceptable to the consumer. Other solutions have included preparing the connectors using a relatively high compression pressure to achieve the desired level of strength, and comprising a dissolving aid, such as an effervescent agent. The multistage, multi-genie structures described in the prior art are prepared by compressing a first composition in a tableting press to form a first layer substantially in pineapple form. An additional dielectric composition is then supplied to the tablet press on top of the first layer. The second composition is then compressed to form another second layer, substantially flat. In this manner, the first layer is generally subjected to more than one compression because it is also compressed during the compression of the second composition. Typically, the first and second compression forces are of the same order of magnitude. The Applicant has found that when this is the case, because the compression force must be sufficient to join the first and second compositions together, the force used in the first and second compression steps should be on the scale of approximately 4000. to approximately 20,000 kg (assuming a cross section of the space of approximately 10 cm2). A consequence of this is a speed of dissolution plus leniency of the problem. You will hear multi-phase tablets that exhibit differential dissolution are prepared, so that the second layer is compressed at a lower force than the first layer. However, although the rate of dissolution of the second layer is improved, the second layer is comparatively soft with the first layer, and is therefore vulnerable to damage caused by handling and transportation. EP-B-0,055,100 discloses a lavatory block which is formed by combining a body configured of slow dissolution with a table. The lavatory block is designed to be placed in the cisiama of a lavatory, and it dissolves during a period of days, preferably weeks. As a means to reframe the rate of dissolution of the lavatory block, the document teaches mixing one or more solubility control agents. Examples of such solubility control agents are paradichlorobenzene, waxes, long chain fatty acids and alcohols and esters thereof, and fatty alkylamides. Detergent materials for use in laundry applications or for dishwashing must be dissolved substantially within one cycle of the washing machine or dishwashing machine, that is, within 15 to 120 minutes.

BRIEF DESCRIPTION OF THE INVENTION In accordance with a first aspect of the invention, a multi-phase tablet is provided for use in a washing machine, the tablet comprising: (a) a first phase in the form of a shaped body having at least one mold therein; and (b) a second phase in the form of a particulate solid compressed within said mold. In preferred embodiments, the first phase is a compressed shaped body prepared at an applied compression pressure of at least about 40 kg / cm2, preferably at least about 250 kg / cm2, more preferably at least about 350 kg / cm2 (3.43 kN / cm2), even more preferably from about 400 to about 2000, and especially from about 600 to about 1200 kg / cm2 (in the present, the compression pressure is the applied force divided by the cross-sectional area of the tablet in a plane transverse to the applied force - in effect, the cross-sectional area of the die of the rotating press). It is also preferred that the particulate solid of the second phase (the terminology of which is intended to include the possibility of "second" multiple phases, sometimes referred to herein as "optional subsequent phases"), is compressed in said mold to a applied compression pressure less than that applied to the first phase, and preferably at a compression pressure of less than about 350 kg / cm2, preferably in the range of about 40 kg / cm2 to about 300 kg / cm2, and more preferably from about 70 to about 270 kg / cm2, said plates being preferred in the present from the point of view to provide optimum integrity and resistance to the lace (measured, for example, by the bite resistance test of a child [CBS]), as well as dissolution characteristics of the product. The tablets of the invention preferably have a CBS of at least about 6 kg, preferably greater than about 8 kg, more preferably greater than about 10 kg, especially greater than about 12 kg, and more especially greater than about 14 kg, CBS is measured by the US Consumer Product Safety Commission Test Specification. Also, the compression pressures applied to the first and second phases will generally be at a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1. Thus, in accordance with a further aspect of the invention, a multi-phase detergent tablet is provided for use in a washing machine, the assembly comprising: a) a first phase in the form of a compressed shaped body having at least minus a mold therein, the shaped body being prepared at a compression pressure of at least about 350 kg / cm2; and b) a second phase in the form of a particulate solid compressed within said mold, the second phase being compressed at a pressure of less than about 350 kg / cm2. In other preferred embodiments, the second phase is in the form of a shaped or compressed body contained adhesively, for example, by physical or chemical adhesion, within at least one mold of the first body. It is also preferred that the first and second phases are at a weight ratio relative to each other, for example, at least about 6: 1, preferably at least about 10: 1; and that the tablet composition contains one or more detergent-containing agents (eg, enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, etc.) that are predominantly concentrated in the second phase, for example, that at least about 50%, preferably at least about 60%, especially about 80% by weight of the active agent (based on the actual weight of the active agent in the freezer) is in the second phase of the schedule. Again, said compositions are optimal for strength, dissolution, cleaning and pH regulation of the table, providing, for example, tablet compositions capable of dissolving in the aqueous solution to supply at least 50%, preferably at least 60% , and more preferably at least 80% by weight of the detergent active agent to the washing solution of 10, 5, 4 or even 3 minutes of the start of the washing procedure. Thus, in accordance with another aspect of the present invention, a multi-phase detergent tablet is provided for use in a washing machine, the tablet comprising: a) a first phase in the form of a shaped body having at least one a mold therein, and b) a second phase in the form of a particulate solid compressed within said mold, and wherein the tablet comprises at least one detergent-active agent and is formulated so that at least 50%, of preference at least 60%, more preferably at least 80% by weight of! Detergent active agent is supplied to the wash within the first 10 minutes, preferably within the first 5 minutes, and more preferably within the first 3 minutes of the washing procedure. An additional benefit of the invention is the ability to achieve differential dissolution of the phases, so that one phase of the table will significantly dissolve before the other phase, and can even be dissolved essentially completely until the other phase has been removed. dissolved. This is particularly valuable for the differential supply of antigenic agents.

In this manner, in accordance with another aspect of the invention, a multi-phase detergent structure is provided comprising: a) a first phase in the form of a shaped body that has at least one mold therein, and b) a second phase in the form of a compressed body contained adhesively within said mold, and wherein the tablet composition comprises one or more detersive agents which are concentrated predominantly in the second phase, and wherein the second phase additionally comprises a dissolution agent . In accordance with a further aspect of the invention, there is provided a detergent table of multi-phase phases comprising: a) a first phase in the form of a shaped body that has at least one mold therein, and b) a second phase in the form of a compressed body adhesively contained within said mold, wherein the tablet composition comprises one or more fatty acid agents which are predominantly concentrated in the second phase, and wherein the second phase additionally comprises an agglutinate. Conveniently, one or more active detergent agents are selected from enzymes, bleach, bleach activators, bleach catalysts, surfactant agents, chelating agents, criolis growth inhibitors, and mixtures thereof, the active agents of the enzyme being particularly preferred to intensify the cleaning performance during the most initial stage of the cold water washing or cleaning operation. Therefore, highly preferred for use herein, are the enzyme detergent active agents, and especially enzymes and enzyme mixtures which comprise one or more enzymes having increased or optimum activity on the 25 ° C temperature scale. 55 ° C and at a pH value on the scale of 8 to 10 (for example, Naialase). In this manner, in accordance with a further aspect of the invention, a multi-phase detergent structure is provided comprising: a) a first phase in the form of a shaped body that has at least one mold therein, and b) a second phase in the form of a compressed body contained adhesively within said mold, and wherein the second phase additionally comprises an enzyme.

DETAILED DESCRIPTION OF THE INVENTION One object of the present invention is to provide a fuel economy that is not only strong enough to withstand handling and transportation, but also at least a significant portion of it dissolves rapidly in the wash water providing rapid delivery of the agent active detergent. It is preferred that at least one phase of the melt dissolve in the wash water within the first ten minutes, preferably five minutes, more preferably four minutes of the laundry cycle of a laundry washing machine or for the washing of food. crockery Preferably, the washing machine is a laundry washing machine or for the washing of dishes. The time within which the multi-stage table or one phase of the same or an active detergent component dissolves, is determined in accordance with DIN 44990 using a dishwashing machine available from Bosch in the normal program of avail- 65 ° C with water hardness at 18 ° H, using a minimum of six replicates or a sufficient number to ensure that it is reproducible. The multi-phase detergent tablet of the present invention comprises a first phase, a second phase and optionally subsequent phases. The first phase is in the form of a shaped body of degenerate composition comprising one or more detergent components as described below. Preferred detergent components include detergency builder, bleach, enzymes, and insensitivity agent. The components of the detergent composition are mixed together, for example, by mixing dry components or spraying liquid components. The components are then formed in a first phase using any suitable equipment, but preferably by compression, for example, in a table dam. Alternatively, the first phase can be prepared by extrusion, molding, etc. The first phase may take a variety of geometric shapes such as spheres, cubes, etc., but the preferred embodiments have a generally axially symmetric shape with a cross section generally round, square or reciargular. The first phase is prepared, so that it comprises at least one mold on the surface of the configured body. The mold or the molds can also vary in size and shape and in their location, orientation and topology with respect to the first phase. For example, the mold or the molds can be generally circular, square or oval in cross section; they may form an internally closed cavity or depression in the surface of the shaped body, or they may extend between unconnected regions of the body surface (eg, axially opposed surfaces) to form one or more topological "holes" in the shaped body; and they may be arranged axially or otherwise arranged symmetrically with respect to the first phase, or may be arranged asymmetrically. In a preferred embodiment, the mold is formed using a specially designed tablet press, wherein the surface of the punch that comes in contact with the detergent composition is configured so that when it comes into contact and press the composition degenases, it presses a mold or molds multiples in the first phase of the multi-phase matrix. Preferably, the mold will have an interiorly concave or generally concave surface to provide improved adhesion to the second phase. Alternatively, the mold can be formed by compressing a preformed body of detergent composition annuously disposed about a central dye, thereby forming a shaped body that forms a mold in the form of a cavity that axially exudes in opposite opposing surfaces of the body. . The methods of the invention also include one or more additional steps prepared from a composition or compositions comprising one or more detergent components as described below. At least one phase (hereinafter referred to as the second phase) preferably is in the form of a particulate solid (the term encompassing powders, granules, agglomerates and other particulate solids including mixtures thereof with liquid agro-liquids, meltable solids , sprinkles, etc.) compressed in / from one or more molds of the first phase of the detergent tablet, so that the second phase takes on itself the shape of a shaped body. Other optional steps include one or more compositions in the form of a separate layer or layers. Preferred detergent components include aglylains, coloranids, de-urgency improvers, surface-active agents, dissolving agents and enzymes, in particular amylases and proteases. In another preferred aspect of the present invention, the second phase and optionally subsequent phases comprise a dissolving agent which can be selected from a disinfection agent or an effervescent agent. Suitable disintegrating agents include agents that swell by cooling in water or facilitating the ingress and / or outflow of water to form channels in the oxygen compartment. Any known disinfection or effervescence agent suitable for use in laundry or dishwashing applications is contemplated for use herein. Suitable disintegrating agents include starches (such as natural, modified and pregelatinized starches, for example, those derived from corn, rice and potato starch), starch derivatives such as U-Sperse (tradename), Primojel (tradename) ) and Explotab (trade name), celluloses, microcrystalline celluloses and cellulose derivatives such as Arbocel (tradename) and Vivapur (tradename), both available from Retienmaier, Nymcel (tradename), available from Metsa-Serla, Avicel (name commercial), Lattice NT (trade name) and Hanfloc (trade name), alginates, trihydrate acetate, burqueiferous, carbonate monohydrate of formula Na C03.H20, hydrated STPP with a phase I content of at least about 40%, carboxymethylcellulose (CMC), polymers based on CMC, sodium acetate and aluminum oxide. Suitable effervescent agents are those that produce a gas upon contact with water. Suitable effervescent agents may be species that emit oxygen, nihorogen dioxide or carbon dioxide. Examples of preferred effervescent agents may be selected from the group consisting of perborate, percarbonate, carbonate or bicarbonate in combination with carboxylic acids or other acids such as citric, sulphamic, malic or maleic acid. The components of the detergent composition are mixed together, for example, by mixing dry components and mixing or spraying liquid components. The components of the second phase and the optionally subsequent phases are then fed into the mold provided by the first phase, and retained therein. The preferred embodiment of the present invention comprises two phases: a first phase and a second phase. The first phase will normally comprise a mold, and the second phase will normally consist of a single active detergent composition. However, it is envisaged that the first phase may comprise more than one mold, and that the second phase may be prepared from more than one active detergent composition. Furthermore, it is also envisaged that the second phase may comprise more than one acylated fatty composition contained in a mold. It is also envisaged that various acivive detergent compositions will be contained in separate molds. In this way, chemically sensitive detergent components can be separated to prevent any loss of performance caused by components that react together and potentially become inactive or depleted. In a preferred aspect of the present invention, the first and second phases and / or optionally subsequent phases, may comprise an aglylaine. When present, the binder is selected from the group consisting of organic polymers, for example polyethylene and / or polypropylene glycols, especially those of molecular weight 4000, 6000 and 9000, paraffins, polyvinylpyrrolidone (PVP), especially PVP of molecular weight 90,000, polyacrylates , sugars and derivatives of sugar, starch and starch derivatives, for example hydroxypropylmethylcellulose (HPMC) and carboxymethylcellulose (CMC); and inorganic polymers such as hexameiaphosphate. Agglifinancing is valuable for the integrity of the board, and because it helps achieve the differential dissolution of the first and second phases as described below. In a preferred aspect of the present invention, the first phase weighs more than about 3 g, preferably more than about 4 g, more preferably more than about 5 g. More preferably, the first phase weighs about 10 g of about 30 g, still more preferably about 15 g to about 25 g, and most preferably about 18 g to about 24 g. The second phase and the optionally subsequent phases weigh less than 4 g. More preferably, the second phase and / or the optionally subsequent phases weigh between about 0.1 g and about 3.5 g, preferably between about 1 g and about 3.5 g, more preferably from about 1.3 g to about 2.5 g. In another embodiment of the present invention, a barrier layer comprising a barrier layer composition is located between the first and second phases and / or optionally subsequent phases, or indeed between the second phase and the optionally subsequent phases. This barrier layer composition comprises at least one binder selected from the group as described above. The advantage of the presence of the barrier layer is to avoid or reduce the migration of the components from one phase to another phase, for example, from the first phase in the second phase and / or the optionally sub-sequential phases, and vice versa. The components of the second phase and the optionally subsequent phases are preferably compressed at a very low compression force with respect to the compression force that is normally used to prepare tablets. In this manner, one advantage of the present invention is that because a low compressive force is used, heat, strength or chemically sensitive detergent components can be incorporated into the detergent table without sustaining the concurrent loss of performance commonly encountered when incorporated. said components in the tablets. Alternatively, the second phase or optionally sub-sequential phases may be compressed at the same compression force or compression force greater than the first phase to achieve differential dissolution of the phases as described below. An additional advantage of the present invention is the improved protection of the second phase against damage caused, for example, during handling and transportation. As described above, multi-phase detergent tablets have been prepared wherein the second layer is compressed at a lower compression force than the first layer. However, although the rate of dissolution is improved, the second layer of these fables becomes vulnerable to damage, tending to disintegrate or fragment after contact. However, the slightly compressed phases of the detergent tablets of the present invention are protected within the mold provided by the first phase of the detergent tablet. Yet another advantage of the present invention is the ability to prepare a multi-phase detergent tablet, wherein a phase can be designed to dissolve, preferably significantly before it receives phase. In the present invention, it is preferred that the second phase and the optionally subsequent phases are dissolved before the first phase. In accordance with the preferred weight scales described above, it is preferred that the first phase dissolve in 5 to 20 minutes, more preferably 10 to 15 minutes, and that the second phase and / or optionally lesser phases dissolve in less than 5 minutes, more preferably less than 4.5 minutes, most preferably less than 4 minutes. In altered form, the second phase can be dissolved after the first phase or other phases, for example, when it is desired to provide cleaning or rinsing benefits towards the end of the washing operation. The time in which the first and second phases and / or the optionally subsequent phases dissolve, are independent of each other. Thus, in a particularly preferred aspect of the present invention, the differential dissolution of the phases is achieved. A particular benefit of being able to achieve differential dissolution of the multi-phase detergent tablet is that a component that is chemically inaccurated by the presence of another component can be separated into a different phase. In this case, the component that is inacíivated is preferably located in the second phase and the optionally sub-sequential phases. Yet another advantage of the present invention is improved adhesion between the phases of the multiple phase interface. It is thought that improved adhesion is achieved by reducing the exposure of the second phase, in comparison with the multi-phase tablets known in the art, resulting in the variables of the present invention which are less suscep tible to suffer fra cras throughout The condensation line between the phases.

Procedure Multi-stage detergent tablets are prepared using any suitable equipment, for example, a Courio and R253. Preferably, the materials are prepared by compression in a tableting press capable of preparing a table comprising a mold. In a particularly preferred embodiment of the present invention, the first phase is prepared using a specially designed tablet press following the procedure described below. The press punchers of the press are modified, so that the surface of the punch that enters into a vacuum with the detergent composition has a convex surface. A first dielectric composition is supplied in the die of the tableting press, and the punch is made to descend so that it enters into a vacuum and then compresses the detergent composition to form a first phase. The first detergent composition is compressed using an applied pressure generally of at least about 250 kg / cm2, preferably between about 350 and about 2000 kg / cm2, more preferably from about 500 to about 1500 kg / cm2, most preferably about 600 to approximately 1200 kg / cm2. The punch is then elevated, exposing the first phase that contains a mold. A second detergent composition and optionally sub-standard detergent compositions are then supplied in the mold. The punch of the specially designed press table is then lowered a second time to slightly compress the second detergent composition and the optionally-described compositions below to form the second phase and the optionally sub-sequential phases. In another embodiment of the present invention, where an optional subsequent phase is present, the optionally subsequent phase is prepared in an optionally subsequent compression step substantially similar to the second compression step described above. The second detergent composition and the optionally subsequent detergent compositions are compressed at a pressure preferably less than about 350 kg / cm 2, more preferably from about 40 to about 300 kg / cm 2, most preferably from about 70 to about 270 kg / cm 2. After compression of the second detergent composition, the punch is raised a second time, and the multi-phase detergent tablet is ejected from the tablet press.

DETERGENT COMPONENTS The first and second phases and / or the optionally subsequent phases of the multi-phase detergent tableau disclosed herein are prepared by compression of one or more compositions comprising acrid detergent components. Suitably, the compositions used in any of these phases may include a variety of different denergent components including builders, surfactants, enzymes, bleach agents, alkalinity sources, dyes, perfume, lime soap dispersants, organic polymeric compounds which include polymeric agents inhibitors of the transfer of coloranids, inhibitors of the growth of chrysalis, sequestrants of heavy metal ions, salts of ion ions, enzyme stabilizers, corrosion inhibitors, supressors of foam, solvents, softening agents of fabrics, optical and hydrophobic brighteners. The preferred detergent components of the first phase include a dewatering enhancer compound, an active agent, an enzyme and a bleaching agent. The highly preferred detergent components of the second phase include builder, enzymes, crystal growth inhibitors and dissolution agents and / or binders.

Means of detergency compound The tablets of the present invention preferably contain a builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight, more preferably 20% to 60% by weight of the composition of active detergent components.

Water soluble builder compound Suitable hydrosoluble builder compounds include the water soluble monomeric polycarboxylates or their acid forms, the homo or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated one from the other by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates which contain a carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, iartaric acid, aric acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. The polycarboxyiates which contain the carboxy groups include, in particular, water-soluble cityrates, aconitraids and ciphaconazoles, as well as succinate derivatives such as the carboxymyloxysuccinyls described in Brifanic No. 1, 379, 241, the amino acids described in British Pat. No. 1. , 389,732 and the aminosuccinaios described in the Dutch application 7205873 and the oxy oxycarboxylate materials such as 2-oxa-1, 1, 3-propanfricarboxilafos described in British Patent No. 1, 387,447. The polycarboxylates which contain four carboxy groups include the oxydisuccinates described in British Pat. No. 1, 261, 829, 1, 1, 2,2-eneocarboxylates, 1,1, 3,3-propanecarboxylates and the 1, 1, 2, 3-propanetracarboxylates. Polycarboxylates containing sulphides include the sulfosuccinate derivatives described in British Patents Nos. 1, 398, 441 and 1, 398, 422 and the US Pat. No. 3,936,448 and the sulfonated pyrolysed grades described in British Patent No. 1, 439,000. The alicyclic and heyerocyclic polycarboxylates include cyclopeniane-cis, cis, cis, -yiaracarboxylanes, cyclopeniaadienidopeniacarboxylairs, 2,3,4,5-tefrahdrofuran-cis, cis, cis, -tearycarboxylairs, 2,5-fetrahydrofuran-cis-dicarboxylanes, 2,2,5,5-Feirahydrofuranoteiracarboxylaps, 1, 2,3,4,5,6-hexanohexacarboxylates and carboxymethyl derivatives of hydrocarbon alcohols such as sorbitol, mannitol and xylitol. The aromatic polycarboxylates include melific acid, pyromellitic acid and the phthalic acid derivatives described in British Patent 1, 425, 433. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, particularly citrates. The original acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example, mixtures of citric acid or of citrate / citric acid are also contemplated as useful deficiency enhancers. Borehole dewatering improvers can also be used, as well as builders that contain borehole-forming materials that can produce borax under detergent storage or washing conditions, but are not preferred under wash conditions below 50 ° C. , especially below 40 ° C. Examples of carbonation detergency builders are the alkali metal and alkaline earth metal carbonates which include sodium carbonate and dicarbonate and mixtures thereof with ul? Raphine calcium carbonate as described in German Patent Application No. 2,321,001, published on November 15, 1973.

The highly preferred builders compounds for use in the present invention are the water soluble phosphate builders. Specific examples of phosphate builders are alkali metal tripolyphosphates, sodium pyrophosphate, potassium and ammonium, sodium and potassium pyrophosphate and ammonium, sodium and potassium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization varies from approximately 6 to 21, and salts of phytic acid. Specific examples of water-soluble phosphate builders are alkali metai tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization it varies from about 6 to 21, and the salts of phytic acid.

Partially soluble or insoluble detergency meavator compound The ingredients of the present invention may contain a partially soluble builder compound or insoiubie. 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 dewatering enhancers include crystalline silicates such as those described, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline sodium silicate laminates of the general formula: NaMSix? 2+? VH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and e is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "leaf" structure, such as the so-called d-scribed structure, such as those 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 is preferably 2. The most commonly preferred chrysotamic sodium silicate compound is the formula d-Na2Si2? -5, known as NaSKS-6 (trade name), available from Hoechsí AG. The crystalline sodium silicate silicate material is preferably present in granular detergent compositions as a material! in particles in minute mixture with a solid, water-soluble ionizable material as described in the patent application of PCT No.

Wo92 / 18594. The solid, water-soluble ionizable material is selected from organic acids, salts of organic and inorganic acids and mixtures thereof, with cyclic acid being preferred. Examples of widely hydrosoluble dewatering enhancers include sodium aluminosilicaria. Suitable aluminosilicates include the aluminosilicate zeolies which have the unit cell formula Naz [(Al? 2) z (Si? 2) and] -xH2 ?, where z and y are integers of at least 6; the molar ratio of z: y is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing 10% to 28%, more preferably 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably derived in synthetic form. The syllable crystalline aluminosilicate ion exchange materials are available under the designations Zeoiia A, Zeoliia B, Zeoiita X, Zealite HS and mixtures thereof. A preferred method for synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14 (2), 110-116), where the author describes a method for preparing colloidal aluminosilicate zeolites. The aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles have a size of more than 1 μm in diameter, and no more than 5% of the particles have a diameter of less than 0.05 μm. Preferably, the aluminosilicate zeolite particles have an average particle diameter of enine. 0. 01 μm and 1 μm, more preferably between 0.05 μm and 0.9 μm, most preferably between 0.1 μm and 0.6 μm. Zeolite A has the formula: Na12 [(AI02) i2 (Si? 2) i 2] -xH2? where x is from 20 to 30, especially 27. Zeolite X has the formula: Na86_ (l? 2) 86 (Si? 2) i 06] '276H2 ?. Zeolite MAP, as described in EP-B-384,070 is a zeolite builder that is preferred herein. The aluminosilicate zeolites that are preferred are the colloidal aluminosilicate zeolites. When employed as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide a higher builder performance in terms of providing improved spot removal. The higher detergency builder performance is also observed in terms of reduced fabric fouling and improved fabric whiteness maintenance; Problems that are believed to be associated with detergent compositions with poorly improved detergency. A surprising finding is that mixed deosergent compositions of aluminosilicate zeolite comprising colloidal zeolite A and colloidal Y zeolite provide equal calcium ion sequestration performance against an equal weight of zeolite A commercially available. Another surprising finding is that the mixed detergent compositions of aluminosilicate zeolite, described above, provide improved yield of sequestration of magnesium ions against an equal weight of commercially available zeolite A.

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

Non-ionic non-ionic agent Essentially any non-surface active agent can be included Ionic for detersive purposes in the detergent tablet. Preferred and non-limiting classes of suitable nonionic surfactants are given below.

Nonionic surfactant of ethoxylated alcohol The condensation products of alkyloxyxylation 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.

Blocked exorem alkyl-alkoxylate surfactant A suitable blocked end alkyl akoxylation surfactant is the poly (oxyalkylated) alcohols represented by the formula: R1O [CH2CH (CH3) 0]? [CH2CH20] and [CH2CH (OH) R2] (I) wherein Ri is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably of at least 20. Preferably, the oxidizing agent of formula I, has at least 10 carbon atoms in the terminal epoxy unit [CH 2 CH (OH) R 2 ] 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 13 of October 1994, by Olin Corporation.

Ethoxylated poly (oxyalkylated) alcohols Preferred surfactants for use in the present include the ether-blocked poly (oxyalkylated) alcohols having the formula: R 10 [CH 2 CH (R 3) 0] x [CH 2] kCH (OH) [CH 2 ] jOR2 wherein R1 and R2 are linear or branched, unsaturated or unsaturated, aiiphatic or aromatic hydrocarbon radicals, 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, wherein when x is 2 or more, 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 linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals, 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 alkyneoxy units as described above. 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 greater 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 (oxyalkylated alcohol) surfactants are those in which k is 1 and j is 1 such that the surfactants have the formula: R10 [CH2CH (R3) 0] xCH2CH (OH) CH2OR2 wherein R1, R2 and R3 are as defined above and x is an integer with an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18. The surfactants are more preferred in which R1 and R2 they are in the range of 9 to 14, R3 is H forming ethyleneoxy and x is in the range of 6 to 15. The blocked ether poly (oxyalkyl ether) surfactants comprise three general components, ie a linear or branched alcohol, a alkylene oxide and a blocked end of alkyl ether. The alkyl ether and the alcohol serve as a hydrophobic portion, soluble in oil, of the molecule while the alkylene oxide group forms the hydrosoluble, hydrophilic portion of the molecule. These surfactants exhibit significant improvements in film formation and stain removal and greasy stain removal characteristics, when used in conjunction with high turbidity point insensitivity agents, 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 amorphous agents of poiy (oxyalkylated) ether of blocked ether are described below: Preparation of alkylglycidyl ether of Cip / A fatty alcohol of C12 / 14 (100.00 g, 0.515 mol), and tin chloride (IV) (0.58 g, 2.23 mmoies, available from Aldrich) are combined in a three-necked round bottom flask necks of 500 ml, equipped with a condenser, argon intake, additional funnel, magnetic stirrer and inferna temperature probe. The mixture is heated to 60 ° C. Medium drip epichlorohydrin (47.70 g, 0.515 moles, available from Aldrich) is added 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 brought with a 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) while mechanically agitated. After the addition is complete, the mixture is heated at 90 ° C for 1.5 hours, cooled, and filtered with the help of ethanol !. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO, filtered and concentrated. The distillation of! Oil at 100-120 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

Cw / ii alkyl alcohol surfactant preparation blocked at the ends with Neodol® 91-8 ether (20.60 g, 0.0393 moles ethoxylated alcohol available from Shell Chemical Co. and tin (IV) chloride (0.58 g, 2.23 mmoies) 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 / alkyglycidyl 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. Pass through a 2.54 cm pad of silica gel 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 produce the ten agent bioactive as an oil.

Nonionic Isonioactive Agent of Epoxylated / Propoxylated Fatty Alcohol The ethoxylated fatty alcohols of C6-C? S and the mixed C6-C? -ioxylated ethoxylated / propoxylated fatty alcohols are suitable surfactants for use herein, particularly when they are water-soluble. Preferably the ethoxylated fatty alcohols are the ethoxylated fatty alcohols of C-io-C-iß with an ethoxylation degree of from 3 to 50, more preferably those are the C2-C- | 8 epoxidized fatty alcohols 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 some of the commercially available surfactants Pluronic ™, marketed by BASF.

Nonionic EQ condensation products with propylene oxide / ethylene diamine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine are suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylene diamine 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 Nonionic Surfactants System In a preferred embodiment of the present invention, the detergent tablet comprises a system of mixed nonionic surfactants comprising at least one low-cloud point nonionic surfactant and a nonionic allyl surfactant. turbidity point. "Stiffness point", as used in the present, is a well-known property of the nonionic surfactant which is the result of the surfactant becoming less soluble with an increase in temperature, the temperature at which it is observable the appearance of a second phase referred to as "point of turbulence" (See Kirk Oíhmer's 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, especially ethoxylated nonionic surfactants derived from primary alcohol, and reverse block polymers of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). In addition, said low-cloud point non-ionic surfactants include, for example, ethoxylated / propoxylated alcohol (for example Poly-Tergent® SLF 18 from Olin Corporation), epoxy-blocked poly (oxyalkylated) alcohols (for example, non-toxic series). ionic Poly-Tergent® SLF 18B from Olin Corporation, as described for example in WO 94/22800, dated October 13, 1994 by Olin Corporation), and epoxy-blocked poly (oxyalkylated) surfactants. The nonionic surfactants may optionally contain propylene oxide in a quantity 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, issued September 16, 1980, Builloty, incorporated herein by reference. The low-cloud point nonionic surfactants additionally comprise a polymeric block composite of polyoxyethylene, polyoxypropylene. The polyoxyethylene-polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glyceroi, trimefilpropane and ethylene diamine as the initiating reactive hydrogen compound. Some of the surfactant agent block polymer compounds designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® by BASF-Wyandoite Corp., Wyandoite, 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 of more than 40 ° C, preferably more than 50 ° 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-point cloudiness nonionic surfactant further has a hydrophilic-lipophilic balance value ("HLB; see Kirk Othmer hereinbefore) within the range of 9 to 15, preferably 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 Cg / non-Cn / 15 branched alcohol, 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.

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 anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of íaurida methyl, alkyl succinates and sulfosuccinates, monoésferes of sulfosuccinate (especially monoésíeres C-j2_Ci 8 saturated and unsaturated) diesters of sulfosuccinate ( especially saturated and unsaturated CQ-C- | 4 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and hydrogenated resin acids and resin acids present in or derived from tallow oil. Íensioacíivo agent sulfate anionic Anionic sulfate suitable for use in the present invention surfactants include linear alkyl and branched primary and secondary alkyl ethoxy, oleilglicerolsuifatos fatty acid ether sulfates oxide alquilfenoleíileno, acyl sulfates (C5- Ci7) -N-alkyl (CrC4) glucamine and acyl (C5-C17) -N-hydroxyalkyl (Cr C2) glucamine, and alkylpolysaccharide sulphates such as alkyl polyglucoside sulfates (non-sulphonated nonionic compounds are described herein) . Surfactants Alkyl is preferably selected from alkyl Cio-C-ISS linear and branched primary, most preferred from the alkyl C11-C15 branched chain and alkyl C12-C14 straight chain. Alkylphospholipid surfactants are preferably selected from the group consisting of the alkylsuiphates of C] Q-C < \ Q that have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule.

Most preferably, the tensioacíivo agent alquileíoxisuifato is a alquilsulfaío of C-i-i-C-is more preferred alkylsulfate Cn-C 5, which has been ethoxylated with from 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkylsulfate and alkyletosulfuric surfactants. Such mixtures have been described in PCT application No. WO 93/18124.

Agent íensioactivo anionic sulfonate anionic suitable sulfonate for use in the preseníe invention tensioacfivos agents include salts of linear alkylbenzene C5-C20, alquiléstersulfonatos, alcansulfonaíos C6-C22 primary or secondary olefinsulfonaíos C6-C2, sulfonated polycarboxylic acids , alkyl glycerol sulfonates, fatty acid acyl glycerol sulphonates, fatty acid oleyl glycerol sulfonates and any of mixtures thereof. Íensioactivo agent anionic carboxylate Anionic carboxylate surfactants suitable include alquiietoxicarboxilatos, the alkylpolyethoxypolycarboxylate surfactants and soaps os ( "alquiicarboxilos"), especialmeníe certain secondary soaps as described in to present invention.

Suitable acylethoxycarboxyiates include those with the formula RO (CH2CH20) xCH2C00"M + in which R is an alkyl group of Cß a C-J S, x is in the range of 0 to 10, and the distribution of eioxylate is equal to that, on a basis by weight, the quantity of material in which x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula RO- (CHR ^ -CHR2-0) -R3 in which R is an alkyl group of Cg a C-] 8. x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group which consists of hydrogen, substituted or unsubstained hydrocarbon having 1 to 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include the secondary soap sensory agents containing a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use in the present invention are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl- 1 -nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Schedule alkali metal sarcosine surfactant. Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R ") CH2COOM, in which R is a linear or branched C5-C-17 alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristoyl or oleoyl methylsarcosinates in the form of their sodium salts.

Amphoteric Surfactant Amphoteric surfactants suitable for use in the present invention include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) xN ° (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 4 is an alkylene or a 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§ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of C-i n-C-is and the acylamido-dimethiamine oxide of C? N-Ci8- A suitable example of an alkylamphecarboxylic acid is Miranol ™ C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Iensioactive Agent Zwiuraionic surfactants can also be incorporated into the detergent compositions of the present invention. 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 sulfain and beiraine insensitivity agents are examples of zwitterionic surfactants that can be used in the present invention. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- in which R is a hydrocarbon group of C6-C-J8, each R1 is typically C1-C3 alkyl, and R2 is a C-1-C5 hydrocarbyl group. The preferred betaines are the betaines of dimethyl-ammonium hexanoate of C ^ -C ^ and the acylamidopropane (or eiano) dimethyls (or diethyl) betaines of C ?; o-Ci8- Also suitable for use in the present invention are complex betaine surfactants.

Cationic Surfactants The cationic ester surfactants used in this invention preferably compounds that can be dispersed in water having surfactant properties and comprising at least one ester bond (i.e., -COO-) and at least one cationically loaded group. Other suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in U.S. Patents. Nos. 422,8042, 4239660 and 4260529. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono-N-alkyl or alkenylammonium surfactants of Cß-C-iß, preferably mono-N-alkyl or C6-C6 alkenyl ammonium, in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups.

Enzymes Enzymes are preferred detergent components of the first phase and particularly of the second and / or optionally additional phases. When such enzymes are present, they are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esserases, cuinases, pecphinases, queraanases, reductases, oxidases, phenoloxidases, lipoxygenases, iigninases, pullulanases, tanases, penfosanases, malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. Preferred enzymes include protease, amylase, lipase, peroxidase, cutinase and / or cellulase, in conjunction with one or more plant cell wall degradation enzymes. The 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 greater than 50 CEVU (cellulose viscosity unit). Suitable cellulases are described in the patents of E.U.A. No. 4,435,307, Barbesgoard et al !, J61078384 and WO96 / 02653, which describes fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thievalia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable ceiulases 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 DSM 1800 strain of Humicola. Other suitable cellulases are the cellulases originated from Humicola insolens which have a molecular weight of approximately 50 KDa, an isoelectric point of 5.5, and which contain 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. Also suitable cellulases are EGl i cellulases from Trichoderma longibrachiatum described in WO 94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are cellulases which have color care benefits. Examples of said cellulases are the cellulases described in European patent application 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, W096 / 17994 and WO 95/24471. Said cellulases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. The peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, 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 bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO89 / 099813, WO 89/09813 and European Patent Application No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on 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 syringates (C3-C5 alkylsalicylates) substituted) and phenols. Percarbonate or sodium perborate are preferred sources of hydrogen peroxide. Said celluoses 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 may be included in the detergent compositions of the present invention include lipases. Iipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, such as those described in the 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 Pharmaceuticai Co. Lid., Nagoya, Japan, under the tradename 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. lipolyticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are the ® ® ® 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 political enzymes described in the documents 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] that can be considered as a special type of lipase, namely 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 '). A suitable protease is obtained from a Bacillus strain, having a maximum activity on the entire pH scale of 8 to 12, developed and sold ® as ESPERASE by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, by Novo. Other suitable proteases include KANNASE®, ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal manipulated with proteins) from Gist-Brocades. The proteophytic 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. Protease B ", and in the European patent application EP 199 404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine protease that is referred to herein as" Protease A ". More preferred is the 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, corresponding to WO 91/06637, published on May 16, 1991. Also included in the present genetically modified variants, particularly of Protease C. A preferred protease referred to as "Protease D", is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydroxyse by substituting a different amino acid for the amino acid residue in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more positions of the amino acid residue e quivalents 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 according to the numeration of the Bacillus amyloliquefaciens sustilisina as described in WO 95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Composites Comprising Protease Enzymes", which has the US 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 and the BLAP® protease described in WO91 / 02792 and its 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 different enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinase recombinase-type protease for detergents suitable in the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

Other preferred protease enzymes include protease enzymes that are a variant of carbonylhydrolase having an amino acid sequence that is not found in nature, which is derived by replacing a plurality of amino acid residues replaced in the precursor enzyme corresponding to the position +210 in combination with one or more of the following residuals: +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 the subtilisin of Bacillus amyloliquefaciens which occurs naturally or to equivalent amino acid residues in other carbonylhydrolases or sublysins (such as subtilisin of Bacillus lentus). Preferred enzymes of this type include those with position changes of +210, +76, +103, +104, +156 and +166. The proteolytic enzymes are incorporated in the denergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, most preferably from 0.005% to 0.1% pure enzyme by weight of the composition. Amylases (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 to be used in cleaning compositions include α and β-amyiases. A-amylases are known in the art and include those described in the patent of E.U.A. No. 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1, 296,839 (Novo). Additional suitable amylases are the amylases of improved stability described in W094 / 18314, published on August 18, 1994 and WO 96/05295, Genencor, published on February 22, 1996, and the amylase variants which have additional modification in the parent. immediate, available from Novo Nordisk A / S and 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 Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, Naialase® all available from Novo Nordisk A / S Denmark. Document W095 / 26397 describes other suitable amylases: α-amylases characterized in that they have 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 test ® Phadebas of α-amylase activity. Other amylolitic enzymes with improved properties with respect to the level of acfivity and the combination of stability and higher level of activity are described in W095 / 35382.

Preferred amylase enzymes include those described in W095 / 26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. 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%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. In a particularly preferred embodiment, the delergent tablets of the present invention comprise amylase enzymes, particularly those described in W095 / 26397 and co-pending application by Novo Nordisk PCT / DK96 / 00056 in combination with a complementary amylase. By "complementary" is meant the addition of one or more suitable amylases for detergency purposes. Examples of complementary amylases (a and / or β) 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; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of the British Patent No. 1, 296,839 (Novo). Additional suitable amylases are amylases of improved stability described in W094 / 18314 and WO 96/05295, Genencor, and the amylase variants having further modification in the immediate parent, available from Novo Nordisk A / S and described in WO95 / 10603 . Also suitable are the amylases described in EP 277 216 (Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. W095 / 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 a value of ® pH on the scale of 8 to 10, measured by the Phadebas test of a-amylase activity. Variants of suitable anterior enzymes are described in W096 / 23873 (novo Nordisk). Other amylocytic enzymes with improved properties with respect to the level of activity and the combination of increased stability and level of activity are described in W095 / 35382. Preferred complementary amylases for the present invention are the amylases sold under the trade name Purafect Ox Am® described in WO / 94/18314, WO / 96/05295 sold by Genencor; Termamyi®, Ban®, Fungamyl® Natalase® 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%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. Preferably, a ratio of pure amylase-specific enzyme to complementary amylase is between 9: 1 and 1: 9, most preferably between 4: 1 and 1: 4, and most 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 extremophilic (psychrophilic, psychrotrophic, erymophilic, barophilic, alkiophilic, acidic, halophilic, etc). The purified or non-purified forms of these enzymes can be used. Also included by definition are the mutani of native enzymes. Mutants can be obtained, for example by genetic or protein manipulation, chemical or physical modifications of native enzymes. The common practice is also the expression of the enzyme through host organisms where 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% of the 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 cogranulated materials). Other suitable detergent ingredients that may be added are the enzyme oxidation scavengers described in the co-pending European patent application 92970018.6, filed on January 31, 1992. Examples of said enzyme oxidation scavengers are the ethoxylated tetraethylenepolyamines. A range of enzyme materials and means for their incorporation into synthetic detergent compositions is 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 and others. Enzymes are also described in E.U.A. 4,101, 457, Place y oíros, July 18, 1978 and in E.U. 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. The enzymes that will be used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in E.U.A. 3,600,319, August 17, 1991, Gedge et al., EP 199,405 and EP 200,586, 29 de ocfubre 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 detergent component composition is a bleaching agent. Suitable bleaching agents include chlorine and oxygen release bleaching agents.

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

Inorganic perhydrate whiteners The compositions of the detergent components preferably include a source of hydrogen peroxide, such as an oxygen release bleach. Suitable sources of hydrogen peroxide include the inorganic perhydrate salts. The inorganic perhydrate salts are normally incorporated in the form of the sodium salt at a level of from about 1% to 40% by weight, most preferably from about 2% to 30% by weight and still most preferably of 5% by weight. 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydric salts are usually the alkali metal salts. The inorganic perhydrate sai 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 that provides better storage stability for the perhydrate salt in the granulated product. The sodium perborate may be in the form of the monohydrate of the nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20. The alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates for inclusion in the compositions according to the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2NaB02C03.3H2 2 2, and is commercially available as a crystalline solid. Sodium percarbonate, being an addition compound of hydrogen peroxide, during dissolution tends to release hydrogen peroxide rapidly which may increase the tendency of high localized bleach concentrations to rise. The percarbonate is preferably incorporated in said compositions in a coated form which provides stability in the product. A suitable coating material that provides product stability comprises mixed salt of a sulfate and alkali metal carbonate hydrosolubie. Said coatings together with the coating processes have been previously described in GB-1, 466,799, assigned to Interox on March 9, 1977. The weight ratio of the mixed salt to percarbonate coating material is in the scale of 1: 200 at 1: 4, most preferably from 1: 99 to 1: 9, and still most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the general formula Na2S04.n.Na2C03, wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2. to 0.5. Another suitable coating material that provides stability to the product, comprises sodium silicate of SiO2: Na2 ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied at a level from 2% to 10% (usually from 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings containing silicate and borate salts or boric acids or inorganic acids are also suitable. Other coatings containing waxes, oils, fatty soaps may also be used in the present invention. The potassium peroxymonosuiphate is another inorganic perhydrate salt of usefulness 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. Generally peroxyacid bleach precursors can be represented as O II X-C-L in which L is a leaving group and X is essentially any functionality, so that in perhydrolysis, the structure of the produced peroxyacid is O II X- C- OOH The peroxy acid-based bleach precursor compounds are preferably incorporated at a level of 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-acyl or O-acyl groups, which may be selected from a wide variety of classes. Suitable forms include anhydrides, esters, imides, lactams and adived 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.

Outgoing groups The outgoing group, hereinafter referred to as group L, must be reactive enough for the perhydrolysis reaction to occur within the optimal time frame (eg, a wash cycle). Without However, if L is very reactive, this activator will be difficult to stabilize for used in a bleaching composition.

The preferred L groups are selected from the group consisting of: R3 and -0-CH = C-CH = CH_ -0-CH = C-CH = CH_ and mixtures thereof, in which R ^ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R3 is an alkyl chain containing 1 to 8 carbon atoms, R4 is H or R3, R5 is an alkenyl chain containing 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R ^, R3 and R4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S03"M +, -C02" M +, -S04"M +, -N + (R3) 4X" and O ^ N (R3), and most preferably -SOs'M + and -C02"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 cation , ammonium or substituted ammonium, with sodium and potassium being preferred, and X is a halide, hydroxide, methylsuiphate 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 N-benzoyl substituted ureas. Suitable imidazole perbenzoic acid precursors include N-benzoi! 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 benzoyl diacylperoxides, the benzoyl tephra-acylperoxides, and the compound having the formula: The italic anhydride is another perbenzoic acid precursor compound suitable in the present invention: Suitable N-acylated lactam perbenzoic acid precursors have the formula: wherein n is from 0 to 8, preferably from 0 to 2, and R is a benzoyl group.

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 in the present invention in which the benzoyl group is substituted essentially with any functional group with non-positive charge (ie, non-cationic) 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 R -N-C-R2-C- L II I «= II U II II O R5 O or R5 O O wherein R1 is an aryl or alkaryl group having 1 to 14 carbon atoms, R2 is an arylene or alkarylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or aarilyl group containing 1 to 10 carbon atoms and L can be essentially any leaving 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 which contains branching, suspension, or both and which can be obtained 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 substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in tota !. 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 portion 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. The cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as a halogenide ion or a meiilsulfate ion. The peroxyacid precursor compound to be cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof, as described above in the present invention. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as later described in the present invention. Cationic peroxyacid precursors are described in the patents of E.U.A. Nos. 4,904,406; 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium-substituted alkyl or benzoyloxybenzene sulphonates, the N-acylated caprofoctams and the monobenzoyltetraacetyl glucose benzoyloperoxides. A cationically substituted benzoyloxybenzene sulfonate which is preferred is the 4- (trimethylammonium) methyl derivative of benzoyloxybenzenesulfonate: A preferred cationically substituted alkyloxybenzenesulfonate has the formula: Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenebenzoyl caprolactams, particularly methylenebenzoyl-caprolactam trimethylammonium: Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenealkyl caprolactams: wherein n is from 0 to 12, particularly from 1 to 5. Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) -ylsilyl 4-sulfophenyl carbonate chloride.

Precursors of bleaching based on aganelpercarboxylic acid The bleach precursors based on alkylpercarboxylic acid form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarboxylic acid precursor compounds of the imide type include the N, N, N1, N1-tetraacetylated alkynediamines 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. Particularly preferred is the α-acetylelylenediamine (TAED). Other preferred aiquilpercarboxylic acid precursors They include 3,5,5-trimethylhexanoyloxybenzenesulfonation sodium (iso-NOBS), sodium nonanoyloxybenzenesulfonation (NOBS), sodium acetoxybenzenesulfonate (ABS) and penia-acetylglucose.

Precursors of alkylperoxy acid substituted with amide The precursor compounds of aliphatic acid substituted with amide are also suitable, including those of the following general formulas: R1- C-N-R2-C-L R1- -N-C-R2-C-L II I? II Ul II O R5 O or R5 O O wherein R is an alkyl group of 1 to 14 carbon atoms, R is an alkylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any outgoing group. R1 preferably contains from 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 which may be obtained 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 substitute groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in each. Amide-whitening bleaching compounds of this type are described in EP-A-0170386.

Benzoxa organic peroxyacid precursors Also suitable are the benzoxa type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: including the substituted benzoxas of the type: wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2, R 3, R and R 5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR6 (in which cua R is H or an alkyl group) and carbonyl functions. An especially preferred precursor of the benzoxa type is: Preformed organic peroxyacid The peroxy acid organic bleaching system may contain, in addition to, or as an alternative to, a precursor bleach precursor compound based on organic peroxyacid, 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 II I? II OR R5 O or R1- N- C- R2- C- OOH A II II R5 O O wherein R1 is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl containing from 1 to 10 carbon atoms. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R 1 may be straight or branched chain alkyl, substituted aryl or alkylaryl containing branching, suspension, or both and may be obtained 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 substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in tofal. The organic peroxyacid compounds substituted with amide of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tera-acyl peroxides, especially diperoxydecanedioic acid, diperoxyteiradecanedioic acid, and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is a preferred organic peroxyacid in the present invention. Also suitable in the present invention are monoperazelaic and diperazelaic acid, monobrasilic and diperbrasilic acid and N-phthaloylaminoperoxycaproic acid.

Means of Velocity of Convealed Release A means may be provided to control the rate of release of the bleach agent, particularly oxygen bleach, in the wash solution. The means for controlling the rate of release of the bleach can produce the controlled release of peroxide species in the wash solution. Such means may include, for example, the coniration of the release of any inorganic perhydrate salt that acts as a source of hydrogen peroxide in the wash solution. Another mechanism for controlling the rate of bleach release may be by replacing the bleach with a coating designed to provide controlled release. Therefore, the coating may for example comprise a poorly water-soluble material, or be a coating of sufficient thickness so that the dissolution kinetics of the coarse coating provides the rate of controlled release. The coating material can be applied using various methods. Any coating material is typically present in a weight ratio of coating material: bleach from 1: 99 to 1: 2, preferably from 1:49 to 1: 9. Suitable coating materials include triglycerides (e.g., partially hydrogenated vegetable oil, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixture thereof. Other suitable coating materials may comprise the sulfates, silicates and metacarbonates; alkaline and alkaline earth, including calcium carbonate and silicas. A preferred coating material, particularly for a source of inorganic perhydrate salt bleach, comprises sodium silicate of Si02: Na20 ratio from 1.8: 1 to 3.0: 1, preferably 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 S02 by weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating. Any inorganic salt coating material can be combined with organic binder materials to provide combined coatings of inorganic salt / organic binder. Suitable binders include the C10-C2o alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole of alcohol, and preferably the C ?5-C20 primary alcohol ethoxylates containing from 20 to 100 moles of oxide of ethylene 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 1000 to 400,000, preferably 1000 to 10,000. Copolymers of maieic anhydride with ethylene, methyvinyl ether or methacrylic acid, with maleic anhydride comprising at least 20 mole percent of the polymer, are additional examples of the polymeric materials useful as binders. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the aforementioned C10-C2o alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole. Additional examples of binders include the mono- and digi-ether ethers! and also the fatty acids of C? 0-C20. Cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, and homo- and co-polymeric polycarboxylic acids or their salts are other examples of suitable binders for use herein.

A method for applying the coating material includes agglomeration. Preferred agglomeration procedures include the use of any of the organic binder materials described above. Any conventional agglomerator / mixer can be used, including without limitation the types of pan, rotary drum and vertical mixer. Molten coating compositions can also be applied, either by voiding or sprayed on a moving bed of bleaching agent. Other means to provide the required controlled release include mechanical means to alter the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols would 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. Although the choice of particle size will depend both on the composition of the particulate component and the need to achieve the desired kinetics of controlled release, it is desirable that the particle size be greater than 500 microns, preferably with an average particle diameter of 800. at 1200 microns. Additional protocols for providing the controlled release means include the proper choice of any other component of the detergent composition maize, so that when the composition is introduced into the wash solution, the ionic strength medium provided therein allows achieve the controlled release kinetics required.

Metal Containing Bleach Catalyst The compositions described herein which contain a bleaching agent as a detergent component, may additionally comprise as a preferred component, a metal-containing bleach catalyst. Preferably, the metal-containing bleach catalyst is a bleach catalyst containing transition metai, more preferably a bleach catalyst containing manganese or cobalt. A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation with defined bleaching catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no catalytic bleaching activity, such as zinc or aluminum cations and a sequestering agent having defined stability constants for the auxiliary and caphalyic cations, particularly ethylenediamine-acetic acid, ethylenediaminetetra (methylene phosphonic acid) and the water-soluble salts thereof. Said catalysts are described in the patent E.U.A. 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-friazacyclononane) 2- (PF6) 2, n "l2 (uO)? (U -OAc) 2 (1, 4,7-trimetiM, 4,7-triazacyclononane) 2- (CI04) 2, Mn? V4 (u-0) 6 (1, 4,7-triazacyclononane) 4- (CI04) 2 , Mn '"Mnlv4 (u-0)? (u-0Ac) 2 (1, 4,7-trimethyl-1, 4,7-idiazacyclononane) 2- (CI04) 3 and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use in the present invention include 1, 5,9-trimethyl-1, 5,9-iazazacyclododecane, 2-methyl-1, 4,7-iazazacyclononane, 2-mephi-1, 4,7- triazacyclononane, 1, 2,4,7-tetramethyl-1, 4,7-iazacyclononane and mixtures thereof. Bleach catalysts useful in the compositions of the present invention may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Patent No. 4,246,612 and U.S. Pat. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416, which teaches mononuclear manganese (IV) complexes as Mn (1), 4,7-urea-1, 4,7-triazacyclononane) (OCH 3) 3 _. (PF 6). Even another type of bleaching catalyst, as described in the patent of E.U.A. No. 5,114,606 is a water-soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, duisitol, mannitol, xylitol, arabitol, adonitol, meso-eriiritol, meso-inositol, lactose, and mixtures thereof.

US Pat. 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. Said ligands are of the formula: R2 R3 R1 - N = C - B - C = N - R4 wherein R1, R2, R3 and R4 can each be selected from H, substituted alkyl and aryl groups in a tai form that each R1-N = C-R2 and R3-C = N-R4 form an annulus of five or six members. Said ring may be further substituted. B is a bridging group selected from O, S, CR5R6, NR7 and C = 0, in which R5, R6 and R7 can each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazoi, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. The ligand 2,2'-bispyridylamine is particularly preferred ligand. Preferred bleach catalysts include Co-, Cu-, Mn-, Fe-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl 2, d (isocyanoate) bispyridylamine-cobalt (i), trisdipyridylamine-cobalt (II) perchlorate, Co (2) 2'-bispyridylamine) 2? 2C04., Bis- (2,2'-bispyridylamine) copper (II) percyrate, tris (di-2-pyridylamine) iron (II) perchlorate, and mixtures of them.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-toothed ligands, including N4Mn '"(u-0) 2Mnl N4) + and [Bipy2Mnlll (u-0) 2Mnlvbipy2] - (CI04) 3. Although the structures of the manganese bleach catalyst complexes of the present invention have not been elucidated, it can be speculated that these comprise chelates or other hydrated coordination complexes resulting from the interaction of the carboxyl and nitrogen atoms of the ligand with manganese cation Similarly, the oxidation state of manganese cation is unknown during the cata lytic process with certainty, and may be the valence state (+ ll), (+ III), (+ IV) or (+ V) Because of the six possible points of adhesion of the ligand to the manganese cation, it can reasonably be speculated that there could be muiti-nuclear species and / or "cage" esignuities in the aqueous bleaching medium. way that they can really exist active Mn ligand species, these function in a seemingly catalytic manner to provide improved bleaching performance on difficult soils such as tea, cappuccino, coffee, wine, juice and the like. Other bleach catalysts are described, for example, in the European patent application Publication No. 408,131 (Cobalt Complex Catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (Metalloporphyrin Catalysts), the U.S.A. 4,728,455 (manganese catalyst / multideniary ligand), the US patent. 4,711, 748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), patenye E.U.A. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), the patent E.U.A. 4,626,373 (manganese / ligand catalyst), patent E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt co-builder catalyst), Canadian patenie 866,191 (salts conferring transitions metals), US Pat. 4,430,243 (co-builders with manganese cations and non-catalytic metai cations) and the E.U.A. 4,728,455 (manganese gluconate catalysts). Other preferred examples include cobalt catalysts (III) which have the formula: CoKNHsJnM'rnB'bT'tQqPplYy in which the cobalt is in the oxidation state +3, n is an integer from 0 to 5 (preferably 4 or 5); most preferred 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; more preferred 1); B 'represents a bidentate gando; b is an integer from 0 to 2; T 'represents an iodinated ligand; í is 0 or 1; Q is an estradiid ligand; q is 0 or 1; P is a peniatened ligand; p is 0 or 1; and n + m + 2b + 3í + 4q + 5p = 6; Y is one or more selected coniraions suitably present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3, most preferred 2 when Y is an anion with charge -1), to obtain a salt with Balanced load, the preferred Y are selected from! group consisting of chloride, nitrate, niirium, sulfate, citrate, acetate, carbonace, and combinations thereof; and wherein additionally at least one of the coordination sites adhered to the cobalt is labile under the conditions of use of dishwashing and the remaining coordination sites stabilize the cobalt under tabletop washing conditions so that the reduction potential from cobalt (lll) to cobalt (II) under alkaline conditions is less than 0.4 vols (preferably less than 0.2 volts) against a normal hydrogen electrode. Preferred cobalt catalysts of this type have the formula: [Co (NH3) n (') m] Yy in which n is an integer from 3 to 5 (preferably 4 or 5, preferably 5); M 'is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, preferably 1); m + n = 6; and Y is a suitably selected counterion that is present in a number and, the quai is an ether of 1 to 3 (preferably 2 to 3, preferably 2 when Y is an anion with charge -1) to obtain a salt with balanced charge . The preferred cobalt catalyst of this type useful in the present invention are the cobalt pentaamincloride salts having the formula [Co (NH3) 5CI] Yy, and especially [Co (NH3) 5Cl] CI2. More preferred are compositions of the present invention which utilize cobalt bleach catalysts (III) which have the formula: [Co (NH3) n (M) m (B) b] Ty in which cobalt is in the state oxidation +3; n is 4 or 5 (preferably 5); M is one or more igandos coordinated to cobalt through a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt by two sii; 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 properly selected counterions present in a number y, where y is an integer to obtain a sai with a balanced charge (preferably and is 1 to 3, most preferred 2 when T is an anion with a charge of -1); and wherein said catalyst additionally has a hydrolysis rate constant in basic medium of less than 0.23 M "1 s" 1 (25 ° C). Preferred T's are selected from the group consisting of chloride, iodide, I, formate, nitrate, nitrite, sulfate, sulfite, citraio, acetate, carbonate, bromide, PF6", BF4", B (Ph) ", phosphate, phosphite, silicate, tosylate, measulfonate, and combinations thereof Optionally, T may be protonated if there is more than one anionic group in T, for example, HP0 2", HC03", H2P0", etc. Additionally, T can be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (for example linear alkylbenzenesulfonates (LAS), alkyl sulphates (AS), alkyl ethoxy sulfonates (AES), etc.) and / or anionic polymers (eg polyacrylates) , polymethacrylates, etc.). The M portions include, but are not limited to, for example, F ", S04" 2, NCS ", SCN". S203"2, NH3, P043", and carboxylates (which are preferably monocarboxylates, but more than one carboxylate may be present in the portion as long as the cobalt linkage is solely by one carboxylate per portion, in which case the other carboxylate in the M portion it may be protonated or in the form of its salt). Optionally, M can be protonated if there is more than one anionic group in M (for example, HP0 2", HC03", H2P0", HOC (0) CH2C (0) 0-, etc.) The preferred M-portions are substituted and unsubstituted C1-C30 carboxylic acids having the formulas: RC (0) 0-in which R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C1-C30 alkyl (preferably CiC-ia), substituted or unsubstituted C6-C30 aryl (preferably C6-C18) and C3-C30 heeroaryl (preferably C5-C-? 8) substituted and unsubstituted, in which the substituents are selected from the group consisting of -NR'3, -NR '+, -C (0) OR' , -OR ', -C (0) NR'2, in which R' is selected from the group consisting of hydrogen and portions of C? -C6, said R substituted RI includes therefore the - (CH2) nOH and - (CH2) nNR'4 +, in which n is an integer from 1 to 6, preferably from 2 to 10, and more preferred from 2 to 5. The most preferred M are carboxylic acids having the above formula in the which R is selected from the group consisting of hydrogen, methyl or, ethyl, propyl, straight or branched C 12 alkyl, and benzyl. The most preferred R is methyl. Formulated carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphinate, oleic, palmitic, iridiate, tartaric, stearic, buiric, cyclic. , acrylic, aspartic, fumaric, iauric, linoleic, lactic, malic, and especially acetic acid. Portions B include carbonate, dicarboxylates 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-based bleach catalysts useful in the present invention are known, being described for example together with their rates of hydrolysis in basic medium 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 hydrolysis rates in basic medium (designated therein as k0H) for pentaamincobane catalysts complexed with oxalation (k0H = 2.5 x 10"4 M" 1 s "1 (25 ° C)), NCS- (kOH = 5.0 x 10-4 M "1 s" 1 (25 ° C)), formate (kOH = 5.8 x 10"4 M" 1 s "1 (25 ° C)) and acetate (kOH = 9.6 x 10"4 M" 1 A (25 ° C)). The most preferred cobalt catalysts useful in the present invention are the cobalt pentaaminoacetate salts having the formula [Co (NH3) 5OAc] Ty, in which OAc represents an acetamide portion, and especially cobalt penyaaminoacetate chloride, [Co (NH3) 5OAc] CI2; as well as [Co (NH3) 5OAc] (OAc) 2); [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2 ("PAC" in the present invention). These cobalt catalysts are easily prepared by known methods, such as those taught for example in the previous Tobe article and the references cited therein, in the patent document.

E.U.A. 4,810,410, to Diakun and others, issued March 7, 1989, J. Chem.

Ed. (1989), 66 (12), 1043-45; The Synítesis and Characferizaíion of Inorganic Compounds, W.L. Joliy (Prenfice-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Syníhesis, 173-176 (1960); and Journal of Phvsical Chemisíry, 56, 22-25 (1952); as well as the synthesis examples provided later in the present. Suitable cobalt-based catalysts for incorporation into the detergent tablets of the present invention can be produced in accordance with the synthetic routes described in the patents E.U.A. Nos. 5,559,261, 5,581, 005 and 5,597,936, the disclosures of which are incorporated in the present invention for reference. These catalysts can be co-processed with adjunct materials so that the color impact is reduced, if desired, for the aesthetic appearance of the product, or they can be included in particles containing enzymes as illustrated below in the present invention, or The compositions can be manufactured to contain "specks" of catalyst.

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 commonly found in detergent compositions having dispersing agents, anti-redeposition agents, soil release agents or other detergency properties. The organic poiimeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferred from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include the water-soluble homopolymer or copolymeric polycarboxylic acids, the modified polycarboxylates or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are described in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight from 2,000-10,000 and their copolymers with any of the other monomer units including acrylic acid, fumaric, maleic, iyaconic, aconitic, mesaconic, cyrazole and methylenemalonic modified or their salts, maleic anhydride, acrylamide , alkylene, vinyl methyl ether, styrene and any of the mixtures thereof. Copolymers of acrylic acid and maieic anhydride having a molecular weight of 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 Rohm and Hass. Preferred acrylic acid-containing copolymers include those which serve 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 - [CR-CR? (CO-0-R3)] - in which at least one of the substituents Ri, R2 or R3, preferably Ri or R2 is an alkyl or hydroxyaikyl group of 1 to 4 carbon atoms, Ri or R2 can be a hydrogen and R3 can be a hydrogen or an alkali metal salt. More preferred is a substituted acrylic monomer in which R1 is methyl, R2 is hydrogen (ie methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500 and contains from 60% to 80% by weight of acrylic acid and from 40% to 20% by weight of mephacrylic acid. The polyamine and modified polyamine compounds are useful in the present invention including those obtained from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351269.

Other optional polymers can be both modified and unmodified polyvinyl alcohols and acetates, cellulosic materials and modified cellulosic materials, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, modified and unmodified, esters of ethylene glycol terephthalate or propylene glycol or mixtures thereof. with polyoxyalkylene units. Suitable examples are described in US Patents Nos. 5,591, 703, 5,597,789 and 4,490,271.

Dirt Free Agencies Suitable polymeric dirt release agents include those dirt releasing agents that are: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2. , or (ii) segments of oxypropylene or polyoxypropylene with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not encompass any oxypropylene unit unless it is attached to adjacent portions at each end by ether-type bonds, or (iii) ) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophilic segments preferably comprising at least 25% oxyethylene units and more preferred, especially for such components having from 20 to 30 oxypropylene units, minus 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) oxyalkylene terephthalate segments of C, in which, if said hydrophobic components also comprise oxyethylene urethathate, the ratio of oxyethylene terephthalate: oxyalkylene terephthalate units of C3 is 2: 1 or less, (ii) segments of C4-C6 or oxyalkylene of C-C6, or mixtures thereof, (iii) segments of poly (vinyl ester), preferably polyvinyl acetate, which have an degree of polymerization of at least 2, or (iv) subsitutes of Cr C alkyl ether or hydroxyalkyl ether of C, or mixtures thereof, in which said sucfituyenf.es are present in the form of alkyl ether cellulose derivatives of CC or hydroxyalkylene ether of C4, or mixtures thereof, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a) (!) Will have a degree of polymerization of 200, although higher levels, preferably from 3 to 150, more preferred from 6 to 100 may be used. The hydrophobic segments of C4-oxyalkylene C6 include, but are not limited to, polymeric soil releasing agent end blockers, such as M03S (CH2) nOCH2CH2? -, in which M is sodium and n is an ether of 4-6, a! as described in US Pat. No. 4,721, 580, issued January 26, 1988 to Gosselink. Useful polymeric soil release agents present therein include also cellulose derivatives such as cellulose hydroxy ether polymers, copolymer blocks of ethylene ethernephthalate 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 in the present invention also include those that are selected from the group consisting of C-α-C aikyl cellulose and C hydroxy-cyanyl cellulose; see U.S. Patent No. 4,000,093, issued December 28, 1976 to Nicol, et al. Dirt release agents characterized by hydrophobic poly (vinyl ester) segments include grafted copolymers of poly (vinyl ester), for example vinyl esters of C? -C6, preferably poly (vinyl acetate) grafted to base structures of poiyalkylene, such as polyethylene oxide base structures. See the European Patent Application 0 219 048 published on April 22, 1987 to Kud, et al. Another suitable soil release agent is a copolymer which has random blocks of ethylene terephthalate and polyethylene terephthalate oxide (PEO). The molecular weight of this polymeric soil release agent is in the range of, 000 to 55,000. See US Pat. No. 3,959,230 to Hays, issued May 25, 1976, and US Patent No. 3,893,929 to Basadur, issued July 8, 1975. Another suitable polymeric dirt releasing agent is a polyester with units repeating units of ethylene terephthalate containing 10-15% by weight of June terephthalate units with 90-80% by weight of polyoxyethylene terephthalate units, obtained 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 repeat units and terminal portions linked by covalent bonds to the base structure. These dirt-releasing agents are fully described in U.S. Patent No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric dirt releasing agents include the polyester polymers of US Patent No. 4,71 1, 730, issued December 8, 1987 to Gosselink, et al, the blocked end anionic oligomeric esters of the US patent. No. 4,721, 580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent No. 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric soil release agents also include the soil release agents of U.S. Patent No. 4,877,896, issued October 31, 1989 to Maidonado et al, which discloses anionic, especially sulfoaroyl, blocked end esters of terephthalate. Another dirt releasing agent is an oligomer with repeated units of terephthaloyl units, sulfoisoferephthaioyl units, oxyethyleneoxy units and oxy-1,2-propylene. The repeating units form the base structure of the oligomer and are preferably terminated with modified isethionic acid blockers. A particularly preferred soiling agent of this type comprises a suifisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8 and two 2- (2-h) eximetic blockers. sodium hydroxyoxide).

Heavy metal ion sequestering The variables of the invention preferably confer as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant in the present invention compounds that act to sequester (chelate) heavy metali ions. These components may also have the ability to chelate calcium and magnesium, but preferably they show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level from 0.005% to 20%, preferably from 0.1% to 10%, more preferred from 0.25% to 7.5% and more preferred still from 0.5% to 5% by weight of The compositions. The heavy metal ion sequestrants, which are acidic in nature, having for example functional groups of phosphonic acid or carboxylic acid, can be present in their acid form or as a compound / salt with an appropriate countercation such as an ion. of alkali or alkali metal, of ammonium or of substituted ammonium or any of the mixtures thereof. Preferably any of the salts / complexes are soluble in water. The molar ratio of said countercatalyst to the heavy metal meta sequestrant preferably is at least 1: 1. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates and nitrilohymethyl phosphonates. Preferred among the above species are diethylenetriamine (methylene phosphonate), ethylene diamine (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxyethylene 1,1 diphosphonane. Other kidnappers of mete ion! Suitable heats for use in the present invention include nitriloyriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaceic acid, ethylenediamine disuccinic acid, eiienediaminediglularic acid, 2-hydroxypropylenediamindisuccinic acid or any of the salts thereof. Especially preferred is the ethylene diamine N, N'-disuccinic acid (EDDS) or the alkali metal, me alkaline ferric, ammonium or substituted ammonium salts thereof, or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.

Crystal Growth Inhibitor Component Detergent tablets preferably contain a crystal growth inhibiting component, preferably an organodisphosphonic acid component, preferably incorporated at a level of 0.01% to 5%, more preferred from 0.1% to 2% by weight. weight of the compositions. By "organodiphosphonic acid" is meant in the present invention an organodiphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes organo-aminophosphonates, which however can be included in the compositions of the invention as heavy metal sequestering components. The organodiphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferred a C2 diphosphonic acid, such as ethylene diphosphonic acid, or more preferred still ethan-1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or completely ionized form, particularly as a sai or complex.

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

Alkali metal silicate A preferred component of the tablet of the present invention is an alkali metal silicate. A preferred alkali metal silicate is sodium silicate having an SiO2: Na2? Ratio. from 1.8 to 3.0, preferably from 1.8 to 2.4, more preferred 2.0. The sodium siiicate 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 either anhydrous salt or a hydrated salt. The alkali metal silicate may also be present as a component of an alkalinity system. Preferably the alkalinity system also contains sodium mefasilicate, present at a level of at least 0.4% S02 by weight. Sodium metasilicate has a nominal Si? 2: Na20 ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO2, is preferably from 50: 1 to 5: 4, more preferred from 15: 1 to 2: 1, more preferred even from 10: 1 to 5: 2 Dye The term "dye", as used in the present invention, means any substance that absorbs specific wavelengths of light from the spectral visible light. Said colorani when added to a parent composition have the effect of changing the visible color and therefore the appearance of the detergent composition. The coloraníes can be for example feints or pigments. Preferably the dyes are stable in the composition in which they are to be incorporated. In this way, in a composition with high pH, the dye is preferably stable in an alkaline medium and in a composition with a low pH the dye is preferably stable in an acidic medium. The first and / or second and / or optionally additional phases may contain a dye, a mixture of dyes, particles with dye or mixture of particles with dye in such a way that the various phases have different visual appearances. Preferably any of the first or second phases comprises a colorant. Where both the first phase and the second phase and / or the subsequent phases comprise a dye, it is preferred that the dyes have a different visual appearance. Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline, monoazo, disazo and poiiazo dyes. The most preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred colorants 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. The dye can be incorporated into the phases by any suitable method. Suitable methods include mixing all active or selected detergent components with a colorant in a drum or sprinkling all detergent components active or those selected with the colorant in a rotating drum. When the dye is present as a component of the first phase it is present at a level of 0.001% to 1.5%, preferably from 0.01% to 1.0%, most preferred from 0.1% to 0.3%. When present as a component of the optional second and / or additional phases, the colorant is generally present at a level of 0.001% to 0.1%, more preferred of 0.005% to 0.05%, more preferred of 0.007% to 0.02% .

Corrosion inhibiting compound The tablets of the present invention which are 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 compounds of Mn (ll), particularly salts of Mn (ll) of organic ligands. Organic silver coating agents are described in PCT publication No. WO94 / 16047 and European co-pending application No.

EP-A-690122. Nitrogen-containing corrosion inhibiting compounds are described in co-pending European application No. EP-A-634,478. The Mn (ll) compounds which are used to inhibit corrosion are described in European application No. EP-A-672 749. The organic silver coating agent can be incorporated at a level of 0.05% to 10%, of preference of 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 of the silver article 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 of adhesion towards the surfaces of solid silver, particularly when it is present as a component of an aqueous bleaching and washing solution with which the solid silver surfaces are being treated. . Organic silver coating agents suitable in the present invention include fatty acid esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. The fatty acid portion of the fatty acid 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, isobuiric acid, valeric acid, iactic acid, glycolic acid and ß, ß acid. '-dihydroxy-isobutyric acid. Examples of suitable polycarboxylic acids include n-buyne-malonic acid, isocyclic acid, cyclic acid, maieic acid, malic acid and succinic acid. The root! of alcohol! of fatty acid in the fatty acid ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty acid alcohols include behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, digiicerol, xylitol, sucrose, erythritol, peniaeritrifol, sorbiol or sorbitan. Preferably, the fatty acid and / or fatty acid alcohol group in the attached fatty acid ester material has from 1 to 24 carbon atoms in the alkyl chain. Preferred fatty acid esters in the present invention 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, oieic acid, palmitic acid or myristic acid. Glycerol esters are also highly preferred. These are the mono-, di-, or tri-esters of glycerol and the fatty acids as defined above. Specific examples of fatty acid alcohol esters for use in the present invention include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and seboyl propionate. Fatty acid esters useful in the present invention include: monopalmitate of xyloioli, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbiyan palm, sorbiyan monaurate, sorbiyan monomyrisia, sorbifan monobehenate, sorbiyan monoleate, sorbiyan dilaurate, sorbitan dis-sate, sorbiyan dibehenate, sorbitan dioleate, and also mono- and di-esters of tallowalkylsorbiyan. The glycerol monoesiearafo, the glyceroi mono-oleate, the glycerol monopalmitafo, the glycerol monobehenate, and the giiceroi distearade are preferred glycerol esters in the present invention. Suitable organic silver coating agents include triglycerides, mono or diglycerides, and fully or partially hydrogenated derivatives thereof and any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, oil, and oil. of corn. Waxes, including microcrystalline waxes are organic silver coating agents suitable in the present invention. Preferred waxes have a melting point in the innervation of 35 ° C to 1 10 ° C and generally comprise from 12 to 70 carbon atoms. Preferred are paraffin waxes of the paraffin type and microcrystallines which are composed of saturated long chain hydrocarbon compounds. Alginates and gelatin are suitable organic silver coating agents in the present invention. Also suitable are dialkylamine oxides such as the C 2 -C 0 -alkylamine oxides, and the dialkylammonium quaternary compounds and salts, such as the methylammonium halides of suitable organic organism coating agents include certain materials polymeric 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-vinylimidazoi, and derivatives of Cellulose such as methylcellulose, carboxymethylcellulose and hydroxymethylcellulose are examples of such polymeric materials. Certain perfume materials, particularly those that demonstrate high susi-ability to metal surfaces, are also useful as organic silver coating agents in the present invention. Agents that release polymeric dirt can also be used as an organic sheeting agent.

A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of 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 that meets these characteristics, which has a cyclic to non-cyclic hydrocarbon ratio of 32:68 is sold by Winfershall, Salzbergen, Germany, under the trade name WINOG 70.

Nifrogenated Corrosion Inhibiting Compounds Suitable nitrogenous corrosion inhibiting compounds include imidazoi and derivatives thereof such as benzimidazo !, 2-heptadecylimidazole, and those imidazole derivatives disclosed in the Czechoslovakia Patent No. 139,279 and in the British Patent GB-A- 1, 137, 741, which also describes a method for making imidazole compounds. Also suitable as nitrogenous corrosion inhibiting compounds are pyrazole compounds and their derivatives, particularly those in which pyrazole is substi tuted at any of positions 1, 2, 3, 4 or 5 with substituents Ri, R2, R3, R4 and R5 in which R is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of C1-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or N02.

Other suitable nitrogenous corrosion inhibiting compounds include benzofriazole, 2-mercaptobenzoyiazole, 1-phenyl-5-mercapto-1, 2,3,4-tetrazole, thioneiide, morpholine, melamine, distearyamine, stearoyl-stearamide, cyanuric acid, aminotriazoi, aminofeiazole and indazole. . Also suitable are nitrogen compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or hydrogen ammonium hydroxide.

Corrosion inhibiting compounds of Mn (ll) The delergent variables can contain a corrosion inhibiting compound of Mn (ll). The Mn compound (ll) is preferably incorporated at a level of 0.005% to 5% by weight, more preferred from 0.01% to 1%, more preferred still from 0.02% to 0.4% by weight of the compositions. Preferably, the compound of Mn (ll) is incorporated at a level that provides from 0.1 ppm to 250 ppm, more preferred from 0.5 ppm to 50 ppm, more preferred still from 1 ppm to 20 ppm by weight of Mn ions (cf. ) in any bleaching solution. The Mn compound (II) can be an inorganic salt in anhydrous form or in any of the hydrated forms. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The compound of Mn (ll) can be a salt or compound of an organic fatty acid such as manganese acetate or manganese spheroid. The compound of 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 corrosion inhibiting compounds include mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionephthol, fionalide and thioanthranol. Also suitable are saturated or unsaturated C10-C20 fatty acids, or their salts, especially aluminum istearate.

Also suitable are the hydroxy fatty acids of C 2 -C 0, or their salts. Phosphonated okadecane and other antioxidants such as behydroxytoluene (BHT) are also suitable. It has been found that butadiene and maleic acid copolymers, particularly those supplied under the trademark No. 07787 by Poiysciences Inc., are of particular utility as corrosion inhibiting compounds.Hydrocarbon Oils Another preferred detergent component to be used in the present invention is a hydrocarbon oil, typically predominantly long chain aliphatic hydrocarbons having a number of carbon atoms in the range of 20 to 50; The preferred hydrocarbons are saurated and / or branched; the preferred hydrocarbon oil is selected from predominantly branched C2 -45 species with a ratio of cyclic to non-cyclic hydrocarbons from 1: 10 to 2: 1, preferably from 1: 5 to 1: 1. 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.

Water-soluble Bismuth Compound Tablets of the present invention suitable for use in dishwashing methods may contain a bismuth hydrosoluble compound, preferably present at a level of 0.005% to 20%, more preferred from 0.01% to 5% , more preferred still from 0.1% to 1% by weight of the compositions. The water-soluble bismuth compound can be essentially any sau or bismuth complex with essentially any organic or inorganic counter-anion. Preferred inorganic bismuth salts are selected from the bismuth trihalogenides, bismuth nitrate and bismuth phosphate. Acetate and bismuth citrate are preferred salts with an organic counter anion.

Enzyme Silanizer System Preferred enzyme containing compositions in the present invention can comprise from 0.001% to 10%, preferably from 0.005% to 8%, more preferred from 0.01% to 6% by weight of an enzyme stabilizer system. The enzyme-biasing system can be any sizing system that is comparable to the detersive enzyme. Said stabilizer systems may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boric acid, chlorine bleach scrubbers and mixtures thereof. Said stabilizer systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap dispersing compound The boards of the present invention may contain a lime soap dispersing compound, preferably present at a level of from 0.1% to 40% by weight, more preferred from 1% to 20% by weight, more preferred still from 2% to 10% by weight of the compositions. A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or fatty acid amides caused 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 of 0.05% to 10%, more preferred from 0.1% to 5% by weight of the composition. Foam suppression systems suitable for use in the present invention can comprise essentially any known antifoam compound, including, for example, antifoam silicone compounds and 2-alkyl and alkanol amphoteric compounds. Preferred foam suppression systems and antifoam compounds are disclosed in PCT Application No. WO93 / 08876 and in EP-A-705324.

Polymeric Dye Transfer Inhibitor Agents The detergent tablets of the present invention 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..

Optical brightener Detergent tablets suitable for use in laundry washing methods as described in the present invention also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful in the present invention include those having the structural formula: wherein R-i is selected from anilino, N-2-bis-hydroxy-yl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethio, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula Ri is anilino, R2 is N-2-bis-hydroxiefile and M is an ional cation as sodium, the brightener is acid 4,4'-bis [(4-anilino-6- (N-2- bis-hydroxyethyl) -s-γ-azin-2-y) amino] -2,2'-esfiibendisulfonic acid and disodium salt. This particular kind of brightener is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporaíion. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation tai as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino -6- (N-2-hydroxyethy-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbendisuiphonic. This particular kind of brightener is marketed under the trade name Tinopai 5BM-GX by Ciba-Geigy Corporation. When in the above formula Rj is anilino, R2 is morphino and M is a cayion such as sodium, the brightener is the sodium sai of 4,4'-bis [(4-anilino-6-morphiiino-s-triazin-2) acid. -yl) amino] 2,2'-stybenedisuonic. This particular kind of brightener is marketed under the trade name Tinopai 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 clay mineral compound and optionally a clay fioculation agent. The clay mineral compound is preferably a smectite clay compound. The 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 which are suitable for use in laundry washing methods can also be incorporated into the compositions according to the present invention. Suitable cationic fabric softening agents include water-insoluble tertiary amines or long double-chain amide materials such as those described in GB-A-1 514 276 and EP-B-0 011 340. Cationic softening agents of fabrics are typically incorporated at total levels of 0.5% to 15% by weight, usually from 1% to 5% by weight.

Other Optional Ingredients Other suitable ingredients to be included in the compositions of the invention include perfumes and filler salts, with sodium sulfate being the preferred filler salt. pH of the compositions The detergent tablets of the present invention are preferably not formulated to have an unduly high pH, preferably having a pH, measured as a 1% solution in distilled water, from 8.0 to 12.5, more preferred from 9.0 to 11.8, more preferred still from 9.5 to 11.5.

Automatic dishwashing method Any of the methods suitable for automatic dishwashing or the cleaning of dirty cutlery are envisaged. A preferred dishwashing method includes treating soiled items selected from earthenware, glassware, silverware, metalware, cutlery., and mixtures thereof, with an aqueous liquid having dissolved or dispersed therein an effective amount of a detergent tablet in accordance with the invention. An effective amount of the detergent tablet means from 8g to 60g of product dissolved or dispersed in a wash solution with a volume of 3 to 10 liters, which are typical product washings and wash solution volumes commonly employed in washing methods. automatic of conventional tableware. Preferably the detergent tablets are from 15 g to 40 g in weight, more preferred from 20 g to 35 g in weight.

Laundry Method The machine washing methods of the present invention typically comprise treating the laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a laundry detergent tablet composition. in machine according to the invention. An effective amount of the detergent tablet composition means from 40g to 300g of product dissolved or dispersed in a wash solution with a volume of 5 to 65 liters, which are typical product doses and volumes of wash solution commonly employed in conventional methods. of washing clothes in machine. In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to directly infuse the product into the drum of the washing machine. start of! wash cycle. Its volume capacity must be such that it can contain enough detergent production as would normally be used in the washing method. Once the washing machine has been loaded with clothes, the dispensing device containing the detergent product is placed inside the machine. At the beginning of the wash cycle of the washing machine, water is injected into the drum and the drum rotates periodically. The design of! The dispensing device should be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water. To allow the release of the detergent product during the washing, the device may have a number of openings through which the product can pass. Alternately, the device may be made of a material that is permeable to liquid but impermeable to solid production, which will allow the production to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing high localized and transient concentrations of the product in the drum of the washing machine at this stage of the wash cycle. Preferred dispensing devices can be reused and are 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 dispensing device may be a flexible container, such as a bag or sack. The bag may be made of a fibrous structure covered with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. In an amatory form, it may be formed of a synthetic polymeric material. It is soluble in water provided with an edge seal or seal designed to break in the aqueous medium as described in the published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing an edge of a bag formed from a polymeric water impermeable film such as polyethylene or polypropylene.

EXAMPLES Abbreviations used in the examples In the detergent compositions, the abbreviated component identifications have the following meanings: STPP: Sodium tripolyphosphate. Bicarbonate: Baking soda. Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate Silicate: Amorphous sodium silicate (Si? 2 ratio: Na2? = 2.0) SKS-6: Crystalline layered silicate of the formula d-Na2Si2? 5 PB1: Anhydrous sodium perborate monohydrate. Nonionic: Nonionic surfactant of ethoxylated / propoxylated C13-C15 fatty acid alcohol mixed with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trademark Plurafac by BASF.

TAED: Teira-acetylethyndiiamine HEDP: 1-Hydroxy-1,1-diphosphonic acid. PAAC: Sai of pentaamine cobalt acetate (III). Paraffin: Paraffin oil sold under the trademark Winog 70 by Wintershall. Proiease: Proteolytic enzyme Amiiase: BSA amylolytic enzyme: Benzotriazoi Sulfate: Anhydrous sodium sulfate PEG 3000: Polyethylene glycol of molecular weight of approximately 3000 available from Hoechst. PEG 6000: Polyethylene glycol of molecular weight of approximately 6000 available from Hoechst. pH: measured as a 1% solution in distilled water at 20 ° C.

In the following examples, all levels are cited as% by weight.

EXAMPLES I-VI The multi-phase table compositions are prepared as follows. The composition of the acidic detergent ingredients of phase 1 is prepared by mixing the liquid and granular components and then passing them to the die of a rotating stirrer. The tablet includes a punch modified in an appropriate manner to form the mold. The cross section of! given is approximately 30 x 38 mm. The composition is then subjected to a compression force of 940 Kg / cm 2 and the punch is raised to expose the first phase of the tablet containing the mold on its upper surface. The detergent active ingredient composition of phase 2 is prepared in a similar manner and passed to the die. The particulate active ingredient composition is then subjected to a compression force of 170 Kg / cm 2, the punch is raised and the multi-phase table is expelled from the table. The resulting tablets are dissolved or disintegrated in a washing machine as described above in a period of 12 minutes, phase 2 of the tablets dissolving in a period of 5 minutes. The tablets provide excellent dissolving and cleaning characteristics together with adequate integrity and resistance.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - A multi-phase detergent machine for use in a washing machine, the table comprising: a) a first phase in the form of a shaped body that has at least one mold therein; b) a second phase in the form of a compressed body adhesively contained within said mold, wherein the composition of the tablet comprises one or more detergent actives which is predominantly concentrated in the second phase, and wherein the second phase further comprises a binder.

2. A multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a shaped body having at least one mold therein, the shaped body being prepared at a pressure of compression of at least about 350 kg / cm2; and b) a second phase in the form of a compressed body adhesively contained within said mold, wherein the composition of the tablet comprises one or more detergent actives which is predominantly concentrated in the second phase, and wherein the second phase further comprises a binder.

3. A multi-phase detergent tablet according to any of the preceding claims, further characterized in that one or more detergent actives are selected from enzymes, bleaches, bleach activators, biancation catalysts, surfactants, quelators, inhibitors, growth of crystals and mixtures of them.

4. A multi-phase detergent tablet according to any of the preceding claims, further characterized in that the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers.

5. A multi-phase detergent tablet according to any of the preceding claims, further characterized in that it additionally comprises a barrier phase between the first and second phases.

6. A multi-phase detergent tablet according to claim 5, further characterized in that the barrier layer comprises a binder applied in liquid form.

7. A washing method in a washing machine that comprises loading in one washing machine one or more multi-phase detergent tablets according to any of the preceding claims.

8. A method according to claim 7, further characterized in that the multi-phase degender board dissolves or disintegrates in less than 15 minutes in a dishwashing machine according to the dissolution test method described herein.