MXPA01007413A

MXPA01007413A - Detergent tablet

Info

Publication number: MXPA01007413A
Application number: MXPA/A/2001/007413A
Authority: MX
Inventors: Eric Tcheou; Christopher James Binder; Neil Joseph Lant; Joanne Louise Whitaker
Original assignee: Christopher James Binder; Neil Joseph Lant; Eric Tcheou; The Procter & Gamble Company; Joanne Louise Whitaker
Priority date: 1999-01-23
Filing date: 2001-07-20
Publication date: 2002-06-05

Abstract

A detergent tablet for use in a washing machine, the tablet having one or more phases at least one of which is in the form of a compressed particulate solid comprising:a) a polymeric disintegrant having a particle size distribution such that at least 90%by weight thereof has a particle size below about 0.3 mm and at least 30%by weight thereof has a particle size below about 0.2 mm;and b) a water-soluble hydrated salt having a melting point in the range from about 30°C to about 95°C. The detergent tablets display improved dissolution, strength and long-term storage characteristics.

Description

DETERGENT TABLET TECHNICAL FIELD The present invention relates to detergent tablets. In particular, it relates to multi-phase and single-phase detergent tablets having improved strength, especially in long-term storage, together with excellent dissolution characteristics.

BACKGROUND OF THE INVENTION Detergent compositions in the form of tablets are known in the art. It is understood that detergent compositions in tablet form maintain various advantages over detergent compositions in the form of particles, such as ease of dosing, handling, transport 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. Tablets are typically formed by compressing the components of the detergent composition, so that the reduced tablets are strong enough to be able to withstand handling and transportation without being damaged. In addition to being strong, the tablets must also dissolve fast 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 while the compression force increases, the speed of dissolution of the tablets becomes slower. On the other hand, a low compression force improves the dissolution, but at the expense of the resistance of the tablet. This problem is compounded by the fact that conventional tablet compositions have relatively low long-term storage stability characteristics and, to compensate for this, they must be made to a higher compression specification. Therefore, the present invention seeks to provide compositions having improved tablet dissolution characteristics and which, at the same time, provide excellent long-term storage stability characteristics in terms of strength and strength. Polymeric disintegrants and hydrosoluble hydrated salts such as sodium acetate trihydrate are known components in tablet compositions. However, it has been found that mixtures of polymeric disintegrants of defined particle size distribution together with certain hydrosoluble hydrated salts, are particularly beneficial for improving the dissolution behavior of detergent tablets, while at the same time, providing excellent characteristics of strength and strength during long-term storage.

Therefore, the present invention provides multi-phase and single-phase detergent tablets for use in automatic dishwashing, laundry, automatic etc, and which exhibit improved long-term storage, strength and dissolution characteristics. Particularly preferred herein are tablet compositions formulated for use in automatic dishwashing machines.

BRIEF DESCRIPTION OF THE INVENTION According to a first aspect of the invention, a detergent tablet is provided for use in a washing machine, the tablet has one or more phases at least one of which is in the form of a compressed particulate solid comprising: a) a polymeric disintegrant having a particle size distribution so that at least 90% by weight thereof has a particle size of less than about 0.3 mm and at least 30% by weight thereof has a lower particle size to approximately 0.2 mm; and b) a hydrosoluble hydrated salt having a solubility in distilled water of at least about 25 g / 100 g at 25 ° C. In preferred embodiments, the polymeric disintegrants have a particle size distribution so that at least 90% by weight thereof has a particle size of less than about 0.25 mm and at least 50% by weight thereof has a size of particle less than about 0.2 mm. further, the preferred disintegrants have a particle size distribution so that at least 90% by weight thereof has a particle size greater than about 0.05 mm, preferably greater than about 0.075 mm. Generally speaking, tablet disintegrating agents can be described as materials that improve the rate of dissolution of the tablet in the wash solution. Polymeric disintegrants suitable for use herein include polymers that expand upon contact with water, as well as those that facilitate the ingress and / or exit of water by forming channels in the detergent tablet. Certain polymeric disintegrating agents for use herein may also act as tablet binders, in other words, they act to increase the strength of the tablet as well as increase the rate of dissolution. Preferred polymeric disintegrants for use herein include starch and cellulose as well as derivatives thereof, alginates, sugars, polyvinylpyrrolidones, expandable clays, and mixtures thereof. Examples of a suitable disintegrating agent include starch and cellulose based materials such as Arbocel (tradename), Vivapur (tradename), both available from Rettenmaier, Nymcel (tradename) available from Metsa-serla, burkeite, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose , intertwined celluloses such as interlaced carboxymethylcellulose (CMC), dextrans, interlaced polyvinylpyrrolidones. Of these, Vivapur and in particular, Vivapur G200 (a microcrystalline cellulose having an average particle size of 0.18 mm) is particularly preferred from the viewpoint of providing an improved dissolution rate and tablet strength, as well as stability excellent storage. The hydrosoluble hydrated salt, on the other hand, is preferably soluble to the extent of at least about 40 g / 100 g, most preferably at least about 60 g / 100 g of distilled water at 25 ° C. In addition, the hydrosoluble hydrated salt preferably has a melting point in the range from about 30 ° C to about 95 ° C, most preferably from about 30 ° C to about 75 ° C. Preferred hydrosoluble hydrated salts are selected from hydrates of sodium acetate, sodium metaborate, sodium orthophosphate, sodium diacid phosphate, disodium phosphate, sodium potassium tartrate, potassium aluminum sulfate, calcium bromide, nitrate. of calcium, sodium citrate, potassium citrate and mixtures thereof. Particularly suitable materials include sodium acetate trihydrate, sodium metaborate tetrahydrate or octahydrate, sodium orthophosphate dodecahydrate, sodium dihydrogen phosphate, di-, hepta- or dodecahydrate disodium phosphate, sodium-potassium tartrate tetrahydrate, potassium sulfate- aluminum dodecahydrate, calcium bromide hexahydrate, tripotassium citrate monohydrate, calcium nitrate tetrahydrate and sodium citrate dihydrate. In preferred embodiments, the hydrosoluble hydrated salt is selected from water soluble mono, di, tri and tetrahydrate salts, and mixtures thereof. Especially preferred herein are the acetate trihydrate acetate, tripotassium citrate monohydrate, mixed alkali metal citrates containing at least one potassium ion and mixtures thereof.

Sodium acetate trihydrate and tripotassium citrate monohydrate are highly preferred. In the preparation of detergent tablets of the invention, the particulate solid comprising polymeric disintegrant and hydrated salt will normally be compressed at a pressure of at least about 10 kg / cm 2, preferably at least about 40 kg / cm 2, most preferably at least about 250 kg / cm2, and especially at least about 350 kg / cm2. In general, the detergent tablets of the invention contain from about 0.5% to about 10%, preferably from about 0.8% to about 5%, most preferably from about 1% to about 3% by weight of each one of the polymeric disintegrant and the hydrosoluble hydrated salt. The detergent tablets of the invention include single-phase tablets as well as multi-phase tablets. The multi-phase detergent tablets suitable herein, typically comprise a first phase in adhesion contact with one or more second phases (sometimes referred to herein as "optional subsequent phases"). In preferred embodiments, the first phase is a shaped and compressed body prepared at an applied compression pressure of at least about 250 kg / cm2, preferably about 350 kg / cm2 (3.43 kN / cm2 or 34.3 MPa), most preferably from about 400 to about 2000 kg / cm2, and especially from about 600 to about 1200 kg / cm2, (the compression pressure in the present is the applied force divided by the cross-sectional area of the tablet in a transverse plane to the applied force, in fact, the cross-sectional area of the die of the rotating press). On the other hand, the second phase is preferably formed with a compression pressure of less than about 350 kg / cm2, preferably in a range of about 40 kg / cm2 to about 300 kg / cm2, and most preferably up close from 70 to about 270 kg / cm2. In addition, in preferred embodiments, the first phase is formed by compression at a pressure greater than that applied to the second phase. In these embodiments, the compression pressures applied to the first and second phases will generally be at a ratio of less than about 1.2: 1, preferably at least about 2: 1, most preferably at least about 4: 1. The polymeric disintegrant and hydrated salt defined herein will normally be incorporated as part of the first phase, although they may also be included in the second phase and in subsequent optional phases. Although the use of simple multi-layer tablets is contemplated herein, it is preferred from the standpoint of optimum product integrity, strength (measured, for example with the child bite resistance test [CBS]) and dissolution characteristics multi-phase tablets comprising a first phase in the form of a shaped body having at least one mold therein, and a second phase in the form of a particulate solid compressed within said mold. Said modalities are sometimes referred to herein as "mold" modalities. The tablets of the invention, both the mold and other embodiments, will preferably have a CBS of at least about 6 kg, preferably more than about 8 kg, most preferably more than about 10 kg, especially more than about 12 kg , and much more especially closer to 14 kg, CBS being measured by the US Consumer Product Safety Commission Test Specification. In the multi-phase embodiments of the present invention, it is also preferred that the first and second phases of the present are in a relatively high weight ratio to each other, for example, at least about 6: 1, preferably at least less near 10: 1; also that the composition of the tablet contains one or more detergent actives (eg enzymes, bleaches, bleach activators, bleach catalysts, surfactants), chelating agents, etc.) which predominantly concentrate in the second phase, for example, at least about 50%, preferably at least about 60%, especially about 80% by weight of the active ingredient (based on weight total of the active ingredient in the tablet) is in the second phase of the tablet. Again, such compositions are optimal for the characteristics of resistance, dissolution, cleaning and pH regulation for the tablet, providing, for example, tablet compositions capable of dissolving in washing solutions so as to provide at least 50%, preferably at least 60%, and most preferably at least 80% by weight of the active detergent to the washing solution within 10, 5, 4 or even 3 minutes from the start of the washing process. The compositions of the present invention preferably include an effervescent agent, such agents being received in combination with polymeric disintegrants and a water soluble salt from the viewpoint of providing optimum characteristics of the dissolution and strength tablet. Thus, in accordance with another aspect of the invention, a detergent tablet is provided for use in a washing machine, the tablet having one or more phases at least one of which is in the form of a compressed particulate solid comprising: a) a polymeric disintegrant; b) a water-soluble hydrated salt having a solubility in distilled water of at least about 25 g / 100 g at 25 ° C, and optionally c) an effervescence agent.

DETAILED DESCRIPTION OF THE INVENTION An object of the present invention is to provide a detergent tablet that is not only strong enough to withstand handling and transportation, but also at least a significant portion of which dissolves rapidly in the wash water providing a rapid supply of the detergent active. . It is preferred that at least one phase of the tablet is dissolved in the wash water in the first ten minutes, preferably five minutes, most preferably four minutes of the washing cycle of an automatic dishwasher or a laundry washer. Preferably the washing machine is an automatic dishwasher or a clothes washer. The time within which the multi-phase tablet or one phase of an active detergent component dissolves is determined in accordance with DIN 44990 using a dishwasher available from Bosch in the normal washing program at 65 ° C with a hardness of water at 18 ° H using a minimum of six replicates or a sufficient number to ensure reproducibility. The detergent tablets of the present invention comprise a first phase and, the multi-phase tablet embodiments, also comprise optional second and subsequent phases. The first phase is in the form of a shaped body of a detergent composition comprising one or more detergent components as described below. Others other than the polymeric disintegrants and hydrated salt defined herein, are preferred detergent components of the first phase which include other builders, bleach, enzymes, effervescent agents and surfactant. The components of the detergent composition are mixed by, for example, mixing dry components or spraying liquid components. The components are then formed in a first phase using any compression equipment, but preferably in a tablet press. In mold modalities, the first phase is prepared so that it comprises at least one mold on the surface of the shaped body. In a preferred embodiment, the mold is created using a specially designed tablet press, wherein the surface of the punch that contacts the detergent composition has a shape such that when it contacts and presses the detergent composition it depresses a mold, or Multiple molds in the multi-phase or first-phase detergent tablet.

Preferably, the mold will have a generally concave surface to provide improved adhesion to the second phase. The tablets of the invention may also include one or more additional phases 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 takes the form of a particulate solid (the term encompassing powders, granules, agglomerates and other particulate solids including mixtures thereof with liquid binders, meltable solids , sprinkles, etc.) compressed as a layer in / into 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. Preferred detergent components include binders, colorants, builders, surfactants, dissolving agents and enzymes, in particular amylases and proteases. Suitable effervescent agents are those that produce a gas, especially oxygen, nitrogen dioxide, or carbon dioxide, upon contact with water. Examples of suitable effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate or bicarbonate in combination with inorganic acids such as sulfamic acid and / or carboxylic acids such as citric, malic or maleic acid, and mixtures thereof. The components of the detergent composition are mixed together, for example, premixing dry components and mixing, or preferably spraying the liquid components. The components of the second phase and the optional subsequent phases are then compressed to form one or more layers, or fed and retained within the mold provided by the first phase. Preferred mold embodiments of the present invention comprise 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 an individual active detergent composition. However, it is contemplated 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. In addition, it is also contemplated that the second phase may comprise more than one active detergent composition contained within a mold. It is also contemplated that various active detergent compositions are contained in separate molds. In this way, potential and chemically sensitive detergent components can be separated to avoid any loss of performance caused by components that react together and potentially become inactive or deplete. In a preferred aspect of the present invention, the first second and / or subsequent optional stages may comprise a non-disintegrating binder, i.e., a material that increases the strength of the tablet without increasing the rate of dissolution of the tablet. Preferred non-disintegrating binders are selected from polyethylene and / or polypropylene glycols, for example polyethylene and / or polypropylene glycols having an average molecular weight of from about 1000 to about 12,000, especially those of molecular weight 4000, 6000 and 9000. The binders do not Polyethylene glycol disintegrants are highly preferred herein. In a preferred aspect of the present invention, the first phase weighs more than about 4 g. Most preferably, the first phase weighs from 10 g to 30 g, most preferably from 15 g to 25 g, and especially from 18 g to 24 g is preferred. The second phase and the optional subsequent phases weigh less than 4 g. Most preferably, the second phase and / or optional subsequent phases weigh between 1 g and 3.5 g, most preferably from 1.3 g to 2.5 g. Detergent tablets are prepared using any suitable tableting equipment. Preferably, the multi-phase tablets are prepared by compression in a tablet press capable of preparing a tablet comprising a mold. In a particularly preferred embodiment of the present invention, the first phase is prepared using a specially designed tablet press. The punches of this tablet press are modified, so that the surface of the punch that comes into contact with the detergent composition has a convex surface. A first detergent composition, which includes the polymeric disintegrant, defined in the present invention and the hydrated salt, is supplied in the die of the tableting press, and the punch is caused to descend to make contact and then compress the detergent composition to form a first phase. The first detergent composition is compressed using an applied pressure of at least 250 kg / cm2, preferably between 350 and 2000 kg / cm2, most preferably from 500 to 1500 kg / cm2, most preferably from 600 to 1200 kg / cm2. The punch is then raised, exposing the first phase that contains a mold. A second detergent composition and optional subsequent detergent compositions are then supplied in the mold. The punch of the specially designed tablet press is then lowered a second time to slightly compress the second detergent composition and the optional subsequent detergent compositions to form the second phase and optional subsequent phases. In another embodiment of the present invention, where an optional subsequent phase is present, the optional subsequent phase is prepared in an optional subsequent compression step substantially similar to the second compression step described above. The second detergent composition and optional subsequent detergent compositions are compressed at a pressure preferably less than 350 kg / cm2, most preferably from 40 to 300 kg / cm2, most preferably from 70 to 270 kg / cm2. 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. Multilayer or single layer tablets can be prepared without molds in a similar manner, except by using a tablet punch having a flat surface. The detergent tablets of the invention are prepared by compressing one or more compositions comprising active detergent components. Suitably, the compositions may include a variety of different detergent components including detergent builder compounds, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfume, lime soap dispersants, organic polymeric compounds including agents polymeric dye transfer inhibitors, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilizers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes. The proportions of these active components by weight of the corresponding composition of the active detergent components are given below, unless otherwise indicated. In multi-phase tablets, the highly preferred detergent components of the first phase include a builder compound, a surfactant, an enzyme and a bleaching agent. The detergent components that are greatly preferred for the second phase include builder, enzymes and dissolution agent. Suitable detergency builders for use herein include water-soluble builders such as citrates, carbonates and polyphosphates, for example, sodium tripolyphosphate and sodium tripolyphosphate hexahydrate.; and insoluble or partially water-soluble builders such as layered crystalline silicates (see EP-A-0164514 and EP-A-0293640) and aluminosilicates, including zeolites A, B, P, X, HS and MAP. The builder is typically present at a level of from about 1% to about 80% by weight, preferably from about 10% to about 70% by weight, most preferably from about 20% to about 60% by weight of the composition. Amorphous sodium silicates having an SiO2: Na20 ratio of 1.8 to 3.0, preferably 1.8 to 2.4, more preferred 2.0 may also be used in the present invention, although from the standpoint of long-term storage stability, they prefer compositions containing less than 22%, preferably less than about 15% total silicate (amorphous and crystalline). Suitable surfactants herein include anionic surfactants, such as alkyl sulfates, alkyl ether sulphates, alkylbenzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulfonates, alkyleoxycarboxylates, N-acyl sarcosinates, N-acyltaurates and alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is of C5-C20, preferably linear or branched C10-C18; cationic surfactants such as choline esters (see US-A-4228042, US-A-4239660 and US-A-4260529) and N-alkyl or alkenyl monoammonium surfactants from Cede, where the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups; low and high cloud point nonionic surfactants, and mixtures thereof, including nonionic alkoxylated surfactants (especially ethoxylates derived from primary alcohols of Ce-C-ts), ethoxylated-propoxylated alcohols (example, Poly-Tergent® SLF18 from Olin Corporation), epoxy-blocked poly (oxyalkylated) alcohols (for example, Poly-Tergent® SLF18B from Olin Corporation - see WO-A-94/22800), poly (oxyalkylated alcohol) surfactants blocked with ether, and polyoxyethylene-polyoxypropylene block polymer compounds such as PLURONIC®, REVERSED PLURONIC® and TETRONIC® from BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric surfactants such as amine oxides and alkyl amphocarboxylic surfactants such as Miranol ™ C2M; and zwitterionic surfactants such as betaines and sultaines; and mixtures thereof. Suitable surfactants herein are described, for example, in US-A-3,929,678, US-A-4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874 . Surfactants are typically present at a level of from about 0.2% to about 30% by weight, most preferably from about 0.5% to about 10% by weight, and most preferably from about 1% to about 5% by weight of the composition. In the preferred dishwashing aspect of the present invention, the level of surfactant is generally from about 1% to about 5% by weight of the composition. Suitable enzymes herein include bacterial and fungal cellulases, such as Carezyme and Celluzyme (Novo Nordisk A / S); peroxidases; lipases such as Amano-P (Amano Pharmaceutical Co.), M1 Lipase® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo); cutinases; proteases such as Esperasen Alcalase®, Durazym® and Savinase® (Novo) and Maxatase®, Maxacal®, Properase® and Maxapem® (Gist-Brocades); and α and β-amylases such as Purafect Ox AmR (Genencor) and Termamyl®, BanR, Fungamyl®, Duramyl® and Natalase® (Novo); and mixtures thereof. Enzymes are preferably added herein as pellets, granulates or cogranulates at levels typically in the range of about 0.0001% to about 2% by weight of pure enzyme of the composition. Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium mono- and tetrahydrate perborate, and sodium percarbonate optionally coated to provide controlled release rate (see, for example, GB-A-1466799 on sulphate / carbonate coatings) , preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and / or bleach catalysts containing transition metal (especially manganese or cobalt). The inorganic salts of perhydrate are typically incorporated at levels in the range of from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight, and most preferably from about 5% to about 25% by weight of the composition. Preferred peroxyacid bleach precursors for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzenesulfonate and pentaacetylglucose; pemonanoic acid precursors such as 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS) of sodium and sodium nonanoyloxybenzenesulfonate (NOBS); amide-substituted alkyl peroxyacid precursors (see EP-A-0170386); and benzoxazine peroxyacid precursors (see EP-A-0332294 and EP-A-0482807). Bleach precursors are typically incorporated at levels in the range of about 0.5% to about 25%, preferably from about 1% to about 10% by weight of the composition, while the preformed organic peroxyacids are typically incorporated at in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of the composition. Preferred bleach catalysts for use herein include manganese triazacyclononane and related complexes (see US-A-424'6612 and US-A-5227084); bispyridylamine Co, Cu, Mn and Fe and related complexes (see document US-A-5114611); and cobalt pentaamine acetate (III) and related complexes (see document (US-A-4810410) Other suitable components herein include organic polymers having dispersing, anti-redeposition, dirt release, and other properties of detergency, at levels of from about 0.1% to about 30%, preferably from about 0.5% to about 15%, especially from about 1% to about 10% by weight of the composition is preferred. Preferred herein include acrylic acid containing polymers such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid / maleic acid copolymers such as Sokalan CP5 and acrylic acid / methacrylic acid copolymers Preferred dirt release polymers herein include alkyl and hydroxyalkyl celluloses (see US-A-4,000,0 93), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on esters of ethylene glycol terephthalate, propylene glycol, and mixtures thereof. Heavy metal sequestrants and crystal growth inhibitors are suitable for use herein at levels generally of from about 0.005% to about 20%, preferably from about 0.1% to about 10%, most preferably about 0.25. % to about 7.5%, and especially from about 0.5% to about 5% by weight of the composition, for example diethylenetriamine penta (methylenephosphonate), ethylenediamine tetra (methylenephosphonate), hexamethylenediamine tetra (methylenephosphonate), ethylene diphosphonate, hydroxyl- ethylene-1, 1-diphosphonate, nitrilotriacetate, ethylenediaminetetraacetate and ethylenediamine-N, N'-disuccinate, in their salt and free acid forms. The compositions herein, especially for use in dishwashing, may contain a corrosion inhibitor such as organic silver coating agents at levels of from about 0.05% to about 10%, preferably about 0.1% at about 5% by weight of the composition (especially paraffins such as Winog 70 marketed by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibiting compounds (for example, benzotriazole and benzimidazole, see GB-A-1137741) and Mn (ll), particularly Mn (ll) salts of organic ligands, at levels of from about 0.005% to about 5%, preferably from about 0.01% to about 1%, most preferably from about 0.02% to about 0.4 % by weight of the composition. Other suitable components herein include dyes, water-soluble bismuth compounds such as bismuth acetate and bismuth citrate at levels of from about 0.01% to about 5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scrubbers at levels of from about 0.01% to about 6%, lime soap dispersants (see WO-A-93/08877), suppressants foam (see WO-A-93/08876 and EP-A-0705324), polymeric agents inhibitors of dye transfer, optical brighteners, perfumes, fillers and clay, and cationic fabric softeners. The detergent components suitable for use herein are described in detail in the appendix to the description (Ref: ADW1 L). 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, most preferred from 9.0 to 11.8. , very much preferred from 9.5 to 11.5.

A preferred automatic dishwashing method comprises treating soiled articles 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 8 g to 60 g of product dissolved or dispersed in a washing solution with a volume of 3 to 10 liters, these are product doses and volumes of typical washing solution commonly employed in washing methods automatic of conventional tableware. Preferably the detergent tablets are from 15 g to 40 g by weight, especially from 20 g to 35 g by weight. The machine washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of the compositions described herein. An effective amount of the detergent tablet composition means 40 g to 300 g 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 methods conventional washing of 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 introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its volume capacity must be such that it can contain sufficient detergent product as would normally be used in the washing method. To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device may be made of a material that is permeable to liquid but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing high localized 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 coated with a waterproof protective material to retain the contents, such as that described in EP-A-0018678. Alternatively, it may be formed of a synthetic polymeric material insoluble in water. water provided with an edge seal or seal designed to rupture in the aqueous medium as described in EP-A-0011500, EP-A-0011501, EP-A-0011502 and EP-A-0011968. A convenient form of brittle closure in water comprises a water soluble adhesive disposed along and which seals an edge of a sack formed from a waterproof polymeric film, such as polyethylene or polypropylene.

EXAMPLES Abbreviations used in the examples In the detergent compositions, the abbreviated identifications of the components have the following meanings: STPP: Sodium tripolyphosphate. Bicarbonate: Baking soda. Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate Citrate: Tripotassium citrate monihydrate Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0 ratio) SKS-6: Crystalline stratified silicate of formula d-Na2S? 2? 5 PB1: Anhydrous sodium perborate monohydrate. Nonionic: Mixed ethoxylated / propoxylated C13-C15 fatty acid alcohol 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: Tetra-acetylethylenediamine HEDP: 1-hydroxy-1,1-diphosphonic acid.

PAAC: Cobalt acetate (III) pentaamine salt. Paraffin: Paraffin oil sold under the trademark Winog 70 by Wintershall. Protease: Proteolytic enzyme Amylase: Amylolytic enzyme BTA: Benzotriazole Sulfate: Anhydrous sodium sulfate Triacetate: Vivapur G200 sodium trihydrate acetate: Microcrystalline cellulose having an average particle size of 0.18 mm PEG 400: Polyethylene glycol of molecular weight of approximately 400 available from Hoechst. PEG 4000: Polyethylene glycol with molecular weight of approximately 4000 available from Hoechst.

In the following examples, all levels are cited as parts by weight: EXAMPLES l-VI Next, the detergent tablets of the present invention suitable for use in a dishwashing machine are illustrated.

IV V VI Phase 1 STPP 9.6 1 1.5 Silicato 1.7 0.67 1.6 1.0 1.0 2.4 SKS-6 2.5 1.5 2.3 2.25 Carbonate 5.00 2.74 3.5 3.59 4.10 5.25 HEDP 0.25 0.18 0.18 0.28 0.28 0.28 PB1 3.5 2.45 2.45 3.68 3.68 3.68 PAAC 0.002 0.002 0.002 0.003 0.004 0.004 Triacetate 0.5 0.6 0.5 0.4 0.8 0.5 Vivapur G200 0.75 0.7 0.65 0.8 0.4 0.75 Amylase 0.148 0.110 0.110 0.252 0.163 0.163 Protease 0.06 0.06 0.06 0.09 0.09 0.09 Non-ionic 0.90 0.80 0.80 1.20 1.20 1.20 PEG 4000 0.4 0.26 0.26 0.38 0.39 0.39 BTA 0.01 0.04 0.04 0.06 0.06 Paraffin 0.16 0.10 0.10 0.15 0.15 0.15 Perfume 0.02 0.02 0.02 0.013 0.013 0.013 Sulfate 0.502 0.05 2.843 Total (g) 15.9 19.83 10.27 14.64 14.63 29.3 Phase 2 Amylase 0.30 0.35 0.25 0.30 0.35 0.25 Protease 0.25 0.22 0.30 0.25 0.22 0.30 Citric acid 0.3 0.30 0.3 0.30 Sulfamic acid 0.3 0.3 Bicarbonate 0.92 0.45 0.45 1.09 0.45 0.45 Carbonate 0.55 0.55 Silicate 0.64 0.64 CaCl2 0.07 0.07 PEG 400 0.15 PEG 4000 0.08 0.06 0.06 0.06 0.06 0.06 Total (g) 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g The tablet compositions are prepared as indicated below. The composition of the active detergent ingredients of phase 1 is prepared by mixing the liquid and granular components and then passing to the die of a conventional rotary press. The press includes an appropriately shaped punch to form the mold. The cross section of the die 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 tablet is ejected from the tablet press. The resulting tablets show improved dissolution, strength and long-term storage characteristics.

EXAMPLES VII-XII The detergent tablets of the present invention suitable for use in a dishwashing machine are illustrated below.

VIII VIII IX XI XII Phase 1 STPP 9.6 11.5 Silicato 1.7 0.67 1.6 1.0 1.0 2.4 SKS-6 2.5 1.5 2.3 2.25 Carbonate 5.00 2.74 3.5 3.59 4.10 5.25 HEDP 0.25 0.18 0.18 0.28 0.28 0.28 PB1 3.5 2.45 2.45 3.68 3.68 3.68 PAAC 0.002 0.002 0.002 0.003 0.004 0.004 Citrate 0.5 0.6 0.5 0.4 0.8 0.5 Vivapur G200 0.75 0.7 0.65 0.8 0.4 0.75 Amylase 0.148 0.110 0.110 0.252 0.163 0.163 Protease 0.06 0.06 0.06 0.09 0.09 0.09 Non-ionic 0.90 0.80 0.80 1.20 1.20 1.20 PEG 4000 0.4 0.26 0.26 0.38 0.39 0.39 BTA 0.01 0.04 0.04 0.06 0.06 Paraffin 0.16 0.10 0.10 0.15 0.15 0.15 Perfume 0.02 0.02 0.02 0.013 0.013 0.013 Sulfate 0.502 0.05 2.843 Total (g) 15.9 19.83 10.27 14.64 14.63 29.3 Phase 2 Amylase 0.30 0.35 0.25 0.30 0.35 0.25 Protease 0.25 0.22 0.30 0.25 0.22 0.30 Citric acid 0.3 0.30 0.3 0.30 Sulfamic acid 0.3 0.3 Bicarbonate 0.92 0.45 0.45 1.09 0.45 0.45 Carbonate 0.55 0.55 Silicate 0.64 0.64 CaCl2 0.07 0.07 PEG 400 0.15 PEG 4000 0.08 0.06 0.06 0.06 0.06 0.06 Total (g) 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g The tablet compositions are prepared in the same manner as examples from I to VI. The resulting tablets show improved dissolution, strength and long-term storage characteristics.

Appendix for description Detergency builders Water soluble builder compound Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two separate carboxyl radicals one of 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 containing 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, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in GB-A-1, 379,241, the lactoxysuccinates described in GB-A -1,389,732 and the aminosuccinates described in NL-A-7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanedicarboxylates described in GB-A-1, 387,447. The polycarboxylates containing four carboxy groups include the oxydisuccinates described in GB-A-1, 261, 829, 1, 1, 2,2-ethanetetracarboxylates, 1,1, 3,3-propane tetracarboxylates and the 1, 1, 2 , 3-propanotetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in GB-A-1, 398,421, GB-A-1, 398,422 and US-A-3,936,448 and the sulfonated pyrolysed citrates described in GB-A-1. 439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis, -tetracarboxylates, cyclopentadienidopentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis, -tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2, 2,5, 5-tetrahydrofuranotetracarboxylates, 1, 2,3,4,5,6-hexanohexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives described in GB-A-1, 425, 433.

Of the above, polycarboxylates that are preferred 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 citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent or washing storage conditions, can also be used, but are not preferred under washing conditions below 50 ° C, especially below 40 ° C. Examples of carbonate builders are the alkali metal and alkaline earth metal carbonates which include carbonate and sodium sesquicarbonate and mixtures thereof with ultrafine calcium carbonate., as described in DE-A-2,321, 001. The builders compounds for which there is great preference for use in the present invention are water-soluble phosphate builders. Specific examples of phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization varies from about 6 to 21, and the salts of phytic acid.

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

Meanstock of partially soluble or insoluble detergent composition The compositions herein may contain a partially soluble or insoluble builder compound. The partially soluble or insoluble builder compounds are particularly suitable for use in tablets prepared for use in laundry cleaning methods. Examples of partially water-soluble builders include crystalline layered silicates as described, for example, in EP-A-0164514 and EP-A-0293640. Preferred are the crystalline sodium silicate laminates of the general formula: NaMSix? 2+? yH2? 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 structure d-stratified, such as those described in EP-A-0164514 and EP-A-0293640. 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 crystalline layered sodium silicate compound by which it is preferred has the formula d-Na 2 Si 2? -5, known as NaSKS-6 (tradename), available from Hoechst AG. The crystalline layered sodium silicate material can be added, especially in granular detergent compositions, as a particulate material in intimate admixture with a solid, water-soluble ionizable material as described in WO-A-92/18594. The solid and water-soluble ionizable material is selected from organic acids, salts of organic and inorganic acids and mixtures thereof, with citric acid being preferred. Examples of widely water-soluble detergency builders include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having the unit cell formula Naz [(Al? 2) z (Si? 2) y]. x ^ O, where z and y are integers of at least 6; the molar ratio of zay is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and preferably is crystalline, containing 10 % to 28%, most preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites may be naturally occurring materials, but preferably are derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof. A preferred method for synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14 (2), 110-116), where the author describes a method for preparing colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles will 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 between 0.01 μm and 1 μm, most 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 [(AIO2) 12 (S¡O2) 12]. XH2O where x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(Al? 2) 86 (SiC >2) 06] - "276 H2O The zeolite MAP, as described in EP-B-384,070 is a zeolite builder suitable for use herein The aluminosilicate zeolites that are preferred are the zeolites of Colloidal aluminosilicate When used as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide a greater builder performance in that they provide improved stain removal, reduced fouling in fabrics, and improved maintenance of whiteness in the fabrics Colloidal zeolite A and colloidal Y zeolite mixtures are also suitable herein, providing excellent sequestration performance of calcium and magnesium ions.

Surface-active agent Suitable surfactants are selected from anionic, non-ionic, cationic, ampholytic 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 in character. Foaming caused by the surfactant systems used in laundry cleaning methods does not have to be suppressed to the same extent as is required for dishwashing. A typical list of anionic, nonionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in US-A-3,929,678. A listing of suitable cationic surfactants is given in US-A-4,259,217. A listing of surfactants typically included in automatic dishwashing detergent compositions is given, for example, in EP-A-0414 549 and in WO-A-93/08876 and WO-A-93/08874.

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

Locked-end alkoxylated surfactants Suitable alkylated alkoxylated surfactants are poly (oxyalkylated) alcohols represented by the formula: R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] and [CH 2 CH (OH) R 2] (I) wherein R 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, most preferably 1; and y is an integer having a value of at least 15, most preferably at least 20. Preferably, the surfactant of formula I has at least 10 carbon atoms in the terminal epoxide unit [CH2CH (OH) R2].

Suitable surfactants of formula I, according to the present invention, are the nonionic surfactants POLY-TERGENT® SLF-18B from Olin Corporation, as described in, for example, WO-A-94/22800.

Polyphoxyalkylated Alcohols) Blocked With Ether Preferred surfactants for use herein include poly (oxyalkylated) alcohols blocked with ether having the formula: R 1 O [CH 2 CH (R 3) O]? [CH 2] kCH (OH) [CH 2] jOR 2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30, where when x is 2 or more, R3 can be the same or different ykyj are integers having an average value of 1 to 12, and most preferably 1 to 5 R1 and R2 are preferably aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 6 to 22 carbon atoms, with 8 to 18 carbon atoms being preferred. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms is preferred for R3. Preferably, x is an integer having an average value of 1 to 20, most 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 alkylenoxy 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 only as an example 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 having a low cloud point, less than 20 ° C. These low cloud point surfactants can be used in conjunction with a high cloud point surfactant as described in detail below to obtain superior fat cleansing benefits. 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: R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2 in where 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 still most preferably from 6 to 18. Especially preferred are the surfactants in which R1 and R 2 is on the scale of 9 to 14, R 3 is H forming ethyleneoxy and x is on a scale of 6 to 15. Blocked ether poly (oxyalkylated alcohol) surfactants comprise three general components, i.e., a linear or branched alcohol , an alkylene oxide and a blocked end of alkyl ether. The alkyl ether and alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the water-soluble, hydrophilic portion of the molecule. These surfactants exhibit significant improvements in film formation and stain removal characteristics, as well as removal of greasy stains, when used in conjunction with high cloud point surfactants, relative to conventional surfactants. Generally speaking, the blocked ether poly (oxyalkylene) alcohol 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.

Non-ionic surfactants of ethoxylated / propoxylated fatty alcohol The ethoxylated fatty alcohols of Cß-C-is and the ethoxylated / propoxylated fatty alcohols of Cß-C-is mixed 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-Cis with an ethoxylation degree of 3 to 50, especially those are the ethoxylated C12-C18 fatty alcohols with an ethoxylation degree of 3 to 40. it prefers that 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 condensates nonionic 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 exhibit insolubility in water. Examples of compounds of this type include some of the Pluronic ™ surfactants, commercially available from BASF.

EO nonionic condensation products with propylene oxide / ethylene diamine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic 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 mixed nonionic surfactant system comprising at least one low-cloud point nonionic surfactant and a high non-ionic surfactant. turbidity point. "Turbidity point", as used herein, is a well-known property of the nonionic surfactant which is the result of the surfactant becoming less soluble by increasing the temperature, the temperature at which the occurrence is observable of a second phase referred to as "cloud point" (See Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed. Vol. 22, pages 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 most preferably less than 10 ° C. Typical low cloud point nonionic surfactants include alkoxylated nonionic surfactants, especially ethoxylates derived from primary alcohol, and reverse block polymers of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). In addition, said non-ionic low-cloud point surfactants include, for example, ethoxylated / propoxylated alcohol (for example Poly-Tergent® SLF 18 from Olin Corporation), poly (oxyalkylated) alcohols blocked with epoxy (for example the non-ionic series). Poly-Tergent® SLF 18B from Olin Corporation, as described for example in WO-A-94/22800, and poly (oxyalkylated) alcohol surfactants blocked with ether.The nonionic surfactants may optionally contain propylene oxide in an amount of up to 15% by weight Other preferred nonionic surfactants can be prepared by the process described in US-A-4,223,163 The low-cloud point nonionic surfactants additionally comprise a polymeric polyoxyethylene block composite, polyoxypropylene. The polyoxyethylene-polyoxypropylene block polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylpropane and ethylene diamine as the initiating reactive hydrogen compound. Some of the surfactant block polymer compounds designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are also suitable herein. 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 most preferably more than 60 ° C. Preferably the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average base. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell). It is also preferred for purposes of the present invention that the high-cloud point nonionic surfactant also has a hydrophilic-lipophilic balance value ("HLB").; see Kirk Othmer, already cited) 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 or preferably branched chain secondary fatty alcohol containing from 6 to 20 carbon atoms (Cd-C2o alcohol), including secondary alcohols and branched chain primary alcohols. . Preferably the high-cloud point nonionic surfactants are ethoxylated or branched secondary alcohols, most preferably branched ethoxylates of Cg.no Cu / 15 mixed, condensed with an average of 6 to 15 moles, preferably 6 to 12 moles, and most 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 relative to the average.

Anionic surfactants Essentially any anionic surfactants useful for detersive purposes are 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 isethionates such as acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C 12 -C 18 monoesters), sulfosuccinate diesters (especially saturated and unsaturated C6-C14 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.

Sulphonic Anionic Surfactants Anionic sulfate surfactants suitable for use in the present invention include linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty acid oleyl glycerol sulfates, alkylphenolthylene oxide ether sulphates, acyl sulfates (C5-) C) -N-alkyl (CrC4) glucamine and acyl (C5-C?) -N-hydroxyalkyl (C? -C2) glucamine, and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (unsulfated compounds are described herein) non-ionic). The alkyl sulfate surfactants are preferably selected from linear and branched primary C 10 -C 18 alkyl sulfates, more preferred from the branched chain C 11 -C 15 alkyl sulphates and the C 2 -C 20 alkyl sulphates? of linear chain. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulphates, which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is a C 11 -C 18 alkyl sulfate, most preferably C 11 -C 15 alkyl sulfate, which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule. Mixtures of alkyl sulfate and alkyl ethoxy sulfate surfactants are also suitable herein (see WO-A-93/18124).

Anionic Sulfonate Surfactants The sulfonic anionic surfactants suitable for use in the present invention include the salts of C5-C20 linear alkylbenzenesulfonates, alkyl ether sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids. , alkyl glycerol sulfonates, fatty acid acyl glycerol sulfonates, fatty acid oleyl glycerol sulfonates, and any of mixtures thereof.

Carboxylate anionic surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxypolycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps as described in the present invention. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH20) xCH2C00-M + in which R is an alkyl group of CQ at C-J 8, x is in the range from 0 to 10, and the ethoxylate distribution is such that, on a basis by weight, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR- | -CHR2-O) -R3 in which R is an alkyl group of CQ to C- | 8 > * is from 1 to 25, R- | and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. 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 acid -1 -nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactants 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-C17 alkyl or alkenyl group, R1 is a C-1-C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Amphoteric Surfactants Amphoteric surfactants suitable for use in the present invention include the amine oxide surfactants and the 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; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ^ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of C-IQ-C S and β-acrylamidodimethylamine oxide of CJ Q-c18. A suitable example of an alkylaminocarboxylic acid is Miranol ™ C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ .

Zwitterionic surfactants Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used in the present invention. Suitable betaines are those compounds having the formula: R (R ') 2N + R2C00- in which R is a hydrocarbyl group of C6-C- | 8 > each R "1 is typically C1-C3 alkyl, and R ^ is a C1-C5 hydrocarbyl group.The preferred betaines are the betaines of C12-C8 dimethyl-ammonium hexanoate and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C | o-Ci8 - Complex betaine surfactants are also suitable for use in the present invention.

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 linkage (i.e., -COO-) and at least one group cationically charged. Other suitable cationic ester surfactants, including choline ester surfactants, have been described for example in the following documents US-A-4228042, US-A-4239660 and US-A-4260529. Suitable cationic surfactants include quaternary ammonium surfactants selected from C6-C6 mono-N-alkyl or aicylammonium surfactants, preferably mono-N-alkyl or alkenyl ammonium C-6-C? or, in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups.

Enzymes Enzymes suitable for use herein include cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases , pentosanas, 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. 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 US-A-4,435,307, J61078384 and WO-A-96/02653, which describe fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thievalia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-OS-2,247,832 and WO-A-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; an endoglucanase component that is preferred has the amino acid sequence described in WO-A-91/17243. Also suitable cellulases are the EGIII cellulases of Trichoderma longibrachiatum described in WO-A-94/21801. Particularly suitable cellulases are cellulases that have color care benefits. Examples of said cellulases are the cellulases described in the European patent application No. 91202879.2. Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO-A-91/17244 and WO-A-91/21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO-A-96/34092, WO-A-96/17994 and WO-A-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. In WO-A-89/099813, WO-A-89/09813 and in European patent applications EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on February 20, 1996 detergent compositions containing peroxidase are described. The laccase enzyme is also suitable. 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-A-94 / 12621) and substituted syringates (substituted C3-C5 alkylsalicylates) and phenols. Percarbonate or sodium perborate are preferred sources of hydrogen peroxide. Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the composition. Other preferred enzymes that may be included in the detergent compositions of the present invention include lipases. The lipase 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 GB-A-1, 372.034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the 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 lipases such as M1 Lipase and Lipomax ® (Gist-Brocades) and Lipolase and Lipolase Ultra (Novo), which have been found to be very effective when used in combination with the compositions of the present invention . Also suitable are the lipolytic enzymes described in EP 258 068, WO-A-92/05249, WO-A-95/22615, WO-A-94/03578, WO-A-95/35381 and WO-A- 96/00292. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special type of lipase, namely lipases which do not require interfering activation. The addition of cutinases to detergent compositions has been described in for example, WO-A-88/09367; WO-A-90/09446, WO-A-94/14963 and WO-A-94/14964. 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 strain of Bacillus, having a maximum activity in the entire pH range 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 proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application No. 87303761.8 (particularly pages 17, 24 and 98) and which is referred to herein as "Protease B", and in the application European Patent EP-A-0199 404, which relates to a modified bacterial serine protease which 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-A-91/06637. Also included herein are genetically modified variants, particularly of Protease C. A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived of a precursor carbonyl hydrolase substituting a different amino acid for the amino acid residue in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206 , +210, +216, +217, +218, +222, +260, +265, and / or +274 according to the numeration of Bacillus amyloliquefaciens sustilysin as described in WO-A-95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes", that you in serial number US 08 / 322,677, filed on October 13, 1994. Also suitable for the present invention are the proteases described in EP 251 446 and WO-A-91/06637 and the BLAP® protease described in US Pat. WO-A-91/02792 and its variants described in WO-A-95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO-A-93/18140 A. Enzymatic detergents comprising protease, one or more other different enzymes and a reversible protease inhibitor are described in WO-A-92/03529 A. When desired, a protease is available which has decreased adsorption and increased hydrolysis as described in WO-A-95/07791. A recombinant trypsin-like protease for detergents suitable herein is disclosed in WO-A-94/25583. Other suitable proteases are described in EP-A-516 200. 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 position +210 in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222 , wherein the numbered positions correspond to the naturally occurring subtilisin of Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonylhydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those with position changes +210, +76, +103, +104, +156 and +166. The proteolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, most preferably from 0.005% to 0.1% pure enzyme by weight of the composition. Amylases (a and / or ß) can be included for the removal of carbohydrate-based stains. WO-A-94/02597 describes cleaning compositions incorporating mutant amylases. See also WO-A-95/10603. Other amylases to be used in cleaning compositions include and β-amylases. A-amylases are known in the art and include those described in US-A-5,003,257; EP-A-252,666; WO-A-91/00353; FR-A-2,676,456; EP-A-0285,123; EP-A-525,610; EP-A-0368,341; and in GB-A-1, 296,839. Other suitable amylases are the amylases of improved stability described in WO-A-94/18314 and WO-A-96/05295, and the amylase variants having further modification in the immediate parent, available from Novo Nordisk A / S and described in WO-A-95/10603. Also suitable are the amylases described in EP-A-0277216, WO-A-95/26397 and WO-A-96/23873. Examples of commercial a-amylases products are Purafect Ox Am® by Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, Natalase® all available from Novo Nordisk A / S Denmark. WO-A-95/26397 describes other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% greater than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and at a pH value on the scale of 8 to 10, as measured by the Phadebas test of a-amylase activity. Suitable are the variants of the above enzymes, described in WO-A-96/23873. Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher activity level are described in WO-A-95/35382. Preferred amylase enzymes include those described in WO-A-95/26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. The amylolytic enzymes are incorporated in detergent compositions 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 compositions of the present invention comprise amylase enzymes, particularly those described in WO-A-95/26397 and co-pending application by Novo Nordisk PCT7 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. WO-A-94/02597 and WO-A-95/10603 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-A-91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and GB-A-1,296,839. Other suitable amylases are the amylases of improved stability described in WO-A-94/18314 and WO-A-96/05295, and the amylase variants having further modification in the immediate parent, available from Novo Nordisk A / S, described in WO-A-95/10603. Also suitable are the amylases described in EP 277 216. 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. WO-A-95/26397 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 pH value on the scale of 8 to 10, as measured by the Phadebas test of a-amylase activity.

Variants of suitable prior enzymes are described in WO-A-96/23873.

Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher activity level are described in WO-A-95/35382. Preferred complementary amylases for the present invention are amylases sold under the trade name Purafect Ox Am® described in WO-A-94/18314, WO-A-96/05295 sold by Genencor; Termamyl®, Ban®, Fungamyl® Natalase® and Duramyl®, all available from Novo Nordisk A / S and Maxamyl® by Gist-Brocades. The complementary amylase is generally incorporated in detergent compositions 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 enzyme specific to the complementary amylase is comprised between 9: 1 and 1: 9, preferably between 4: 1 and 1: 4, and 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, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc). The purified or non-purified forms of these enzymes can be used. Also included by definition are mutants 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.

Enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the 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 can be added are the enzyme oxidation scavengers which are described in co-pending European patent application 92970018.6 filed on January 31, 1992. Examples of such 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-A-9307263, WO-A-9307260, WO-A-8908694, and US-A-3,553,139. Enzymes are also described in US-A-4,101,457 and in US-A-4,507,219. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in US-A-4,261,868. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in US-A-3,600,319, EP-A-0199405 and EP-A-0200586. Enzyme stabilization systems are also described, for example, in US-A-3,519,570. A Bacillus sp. AC13 useful and which gives proteases, xylanases and cellulases, is described in WO-A-9401532.

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. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Mineral inorganic perhydrate blangadants. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, a coated form of the material that provides better storage stability is used. The sodium perborate may be in the form of the monohydrate of the nominal formula NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O. Alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates for inclusion herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, 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 coated form, which provides stability in the product. A suitable coating material that provides product stability comprises mixed salt of a water-soluble alkali metal sulfate and carbonate. Said coatings together with the coating processes have been previously described in GB-A-1, 466,799. The weight ratio of the mixed salt to percarbonate coating material is on a scale of 1: 200 to 1: 4, most preferably from 1: 99 to 1: 9, and preferably from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the general formula Na2SO4.n.Na2CO3, wherein n is 0.1 to 3, preferably n is 0.3 to 1.0 and most preferably n is 0.2. to 0.5. Another suitable coating material that provides stability to the product, 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, preferably applied at a level from 2% to 10% (usually from 3% to 5%) of S¡O2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings containing silicate and borate salts or boric or other inorganic acids are also suitable. Other coatings containing waxes, oils, fatty soaps can also be advantageously used within the present invention. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the compositions herein.

Peroxyacid blanket 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 OR 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 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 classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups The leaving group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, it will be difficult to stabilize this activator for use in a bleaching composition. The preferred L groups are selected from the group consisting of: and mixtures thereof, in which R "1 is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group.

Any of R1, 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.

Preferred solubilizing groups are -SO3"M +, -CO2" M +, -SO "M +, -N + (R3) 4X_ and O <--N (R3) 3, and most preferably -SO3'M + and -CO2" M + , wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator, and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium being preferred, and X is a halide, hydroxide, methylisulfate 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 benzoylation agents, including for example: Ac = COCH3; Bz = Benzoyl The perbenzoic acid precursor compounds of the metric type include N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable midazole perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Other perbenzoic acid precursors include the benzoyl diacylperoxides, the benzoyl tetra-acylperoxides, and the compound having the formula: Phthalic anhydride is another perbenzoic acid precursor compound suitable herein: Suitable N-acylated lactam perbenzoic acid precursors have the formula: wherein n is from 0 to 8, preferably from 0 to 2, and R6 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 essentially substituted 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: 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 alkaryl 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, substitution, 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 total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis.

Typically, the cationic peroxyacid precursors are formed by substituting the peroxyacid 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 for example a halide ion or a metisulfate ion. The peroxyacid precursor compound which is to be so 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 alkylcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described below in the present invention. Cationic peroxyacid precursors are described in US-A-4,904,406; US-A-4,751, 015; US-A-4,988,451; US-A-4,397,757; US-A-5,269,962; US-A-5, 127,852; US-A-5,093,022; US-A-5, 106,528; GB-A-1, 382.594; EP-A-0475512, EP-A-0458396 and EP-A-0284292; and in JP 87-318,332. Suitable cationic peroxyacid precursors include any of the alkyl or benzoyloxybenzene sulphonates substituted with ammonium or alkylammonium, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose.

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-trimethyl ammonium) ethyl sodium 4-sulfophenyl carbonate chloride.

Precursors of bleaching based on alkylpercarboxylic 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 metric type include the N, N, N1, N1-tetraacetylated alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetra-acetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (so-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Precursors of allylperoxy-substituted amide The amide-substituted alkylperoxy acid precursor compounds are also suitable, including those of the following general formulas: R -C- N- R2- C- L R1- N-C- R ^ -C- L II O ?? R '= 5 O R • «II 5 O ?? or wherein R1 is an alkyl group of 1 to 14 carbon atoms, R2 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 substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Benzoxazine organic peroxyacid precursors Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: including the substituted benzoxazines of the type: wherein R is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2, R 3, R 4 and R 5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COORß (in which Re is H or an alkyl group) and carbonyl functions. An especially preferred precursor of the benzoxazine type is: Preformed organic peroxyacid A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: 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. R1 may be straight or branched chain alkyl, substituted aryl or alkylaryl containing branching, substitution, 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 total. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic 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.

Controlled release rate means A means can be provided to control the rate of release of the bleaching 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, controlling the release of any inorganic perhydrate salt that acts as a source of hydrogen peroxide in the wash solution. Suitable controlled release media may include confining the bleach to a portion of the coition. Another mechanism for controlling the rate of release of the bleach can be by coating the bleach with a coating designed to provide controlled release. Thus, the coating may comprise, for example, 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 alkali metal and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas. A preferred coating material, particularly for a source of inorganic perhydrate salt bleach, comprises sodium silicate of ratio S02: Na2O 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 of 2% to 10% (usually 3% to 5%) of SiO2 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 inorganic salt / organic binder coatings. Suitable binders include alcohol ethoxylates of C10.C20 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 maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride constituting 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 C? 0-C20 e alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole. Additional examples of binders include the mono- and diglycerol ethers and also the C? 0-C2o fatty acids. The cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and the homo- and co-polycarboxylic acids or their salts are other examples of binders suitable 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 coitions 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 release rate. 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 on 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 to 1200 microns. Additional protocols for providing the controlled release means include the proper choice of any other component of the detergent composition matrix, such 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 blanching catalyst The compositions described herein which contain a bleaching agent may additionally comprise a metal-containing bleach catalyst. Preferably, the metal-containing bleach catalyst is a bleach catalyst containing transition metal, preferably a bleach catalyst containing manganese or cobalt. A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation with defined bleach 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 sequestrant having defined stability constants for the auxiliary and catalytic metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and the water-soluble salts thereof. Said catalysts are described in US-A-4,430,243. Preferred types of bleach catalysts include the manganese-based complexes described in US 5,246,621 and US 5,244,594. Preferred examples of these catalysts include Mn? V (u-0) 3 (1, 4,7-trimetyl-1, 4,7-triazacyclononane) 2- (PF6) 2, Mn "12 (u-0) 1 (u-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CIO) 2, Mnlv (uO) e (1, 4,7-triazacyclononane) 4- (CIO4) 2, Mn "lMnlv4 (uO) 1 (u-OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CIO 4) 3 and mixtures thereof. Others are described in EP-A-0549,272. Other ligands suitable for use in the present invention include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,7-triazacyclononane, 2-methyl-1, 4,7- triazacyclononane, 1, 2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof. For other examples of suitable bleach catalysts see US-A-4,246,612 and US-A-5,227,084. See also US-A-5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3- (PF 6).

Even another type of bleach catalyst, as described in US-A-5,114,606 is a water-soluble manganese complex (III) and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least three C groups. -OH consecutive. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof. US-A-5, 114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a non- (macro) -cyclic ligand. These ligands are of the formula: R2 R3 R1 - N = C - B- C = N- R4 wherein R1, R2, R3 and R4 can each be selected from H, alkyl and aryl groups substituted in such a way that each R1-N = C-R2 and R3-C = N-R4 form a ring of five or six members. Said ring may be further substituted. B is a bridging group selected from O, S, CR5R6, NR7 and C = O, 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, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. The ligand which is particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleach catalysts include complexes of Co-, Cu-, Mn-, Fe-bispyridylmethane and -bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) CI2, di (isothiocyanato) bispyridyl-cobalt (II), trisdipyridylamine-cobalt perchlorate (II), Co (2.2 ' bispyridine) 2? 2CI? 4, bis- (2,2'-bispyridylamine) copper (ll) perchlorate, tris (di-2-pyridylamine) perchlorate (II), and mixtures of the same. Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including N4Mnl "(u-O) 2MnlvN4) + and [Bipy2Mn" l (u-0) 2Mnlvbipy2] - (CIO4) 3. Although the structures of the manganese complexes bleach catalysts 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 the manganese cation. Similarly, the oxidation state of the manganese cation is unknown during the catalytic process with certainty, and may be the valence state (+ II), (+ III), (+ IV) or (+ V). Due to the six possible points of adhesion of the ligand to the manganese cation, it can reasonably be speculated that there could be multi-nuclear species and / or "cage" structures in the aqueous bleach medium. Whichever way the active Mn ligand species may actually exist, they function in a seemingly catalytic way to provide improved bleaching performance on difficult stains such as tea, ketchup, coffee, wine, juice, and the like. Other bleach catalysts are described, for example, in EP-A-0408131 (cobalt complex catalysts), EP-A-0384503 and EP-A-0306089 (metalloporphyrin catalysts), US-A-4,728,455 (manganese catalyst / multidentate ligand), US-A-4,711, 748 and EP-A-0224952 (manganese catalyst absorbed on aluminosilicate), US-A-4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), US- A- 4,626,373 (manganese / ligand catalyst), US-A-4,119,557 (ferric complex catalyst), DE-A- 2,054,019 (cobalt co-builder catalyst), CA-A-866,191 (salts containing metal transition), US-A- 4,430,243 (co-builders with manganese cations and non-catalytic metal cations) and US-A- 4,728,455 (manganese gluconate catalysts). Other preferred examples include cobalt catalysts (III) having the formula: Co [(NH3) nM'mB'bT'tQqPp] Yy in which the cobalt is in the oxidation state +3, n is an integer from 0 to 5 (preferably 4 or 5; more preferred 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, most preferred 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more selected counterions 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 charge, preferred Y's are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and in which additionally at least one of the coordination sites adhered to the cobalt is labile under the conditions of use of automatic dishwashing and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions so that the reduction potential of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) against a normal hydrogen electrode. Preferred cobalt catalysts of this type have the formula: [Co (NH3) n (M ') 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 y, which is an integer 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) 5CI] CI2.

More preferred are the compositions of the present invention which use cobalt bleach catalysts (III) having the formula: [Co (NH3) n (M) m (B) b] Ty in which the cobalt is in the state of oxidation +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more selected counterions suitably present in a number and, where y is an integer to obtain a salt with balanced charge (preferably and is 1 to 3, most preferred 2 when T is an anion with charge -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, l3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF4", B (Ph) 4", phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T may be protonated if there is more than one anionic group in T, for example, HPO42", HCO3", H2PO4", etc. Additionally, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants ( for example linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl ethoxy sulphonates (AES), etc.) and / or anionic polymers (for example polyacrylates, polymethacrylates, etc.).

The M-portions include, but are not limited to, for example, F \ SO4"2, NCS", SCN ", S2O3" 2, NH3, PO3", and carboxylates (which are preferably monocarboxylates, but may be more of a carboxylate in the portion as long as the binding to cobalt is only by one carboxylate per portion, in which case the other carboxylate in the M portion may be protonated or in the form of its salt.) Optionally, M may be protonated if there is more than one anionic group in M (e.g., HPO42", HCO3", H2PO4", HOC (O) CH2C (O) O-, etc.). Preferred M-portions are substituted and unsubstituted C 1 -C 30 carboxylic acids having the formulas: RC (O) 0-in which R is preferably selected from the group consisting of hydrogen and C?-C 30 alkyl (preferably C? -C18) substituted and unsubstituted, substituted and unsubstituted C6-C3_ (preferably Cß-Ciß) aryl and C3-C3_ (preferably C5-C d) substituted and unsubstituted heteroaryl, in which the substituents are selected from the group consisting of -NR'3) -NR'4 +, -C (O) OR \ -OR ', -C (O) NR'2, wherein R' is selected from the group consisting of hydrogen and portions of C? -C6. Said substituted R thus includes the portions - (CH2) nOH and - (CH2) nNR'4 +, in which n is an integer from 1 to 6, preferably from 2 to 10, and more preferred from 2 to 5. The most preferred M are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 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, italic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric acid , acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid. Portions B include carbonate, dicarboxylates and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha- and beta-amino acids (eg, glycine, alanine, beta-alanine, phenylalanine). The 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 rates of hydrolysis in basic medium (designated therein as k0H) for pentaaminobalt catalysts complexed with oxalate (k0H = 2.5 x 10"4 M" 1 s "1 (25). ° C)), NCS- (kOH = 5.0 x lo-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 s "1 (25 ° C).) The most preferred cobalt catalysts useful in the present invention are cobalt pentaaminoacetate salts having the formula [Co (NH3) 5OAc ] Ty, in which OAc represents an acetate portion, and especially cobalt pentaaminoacetate chloride, [Co (NH3) 5OAc] CI2; as well as [Co (NH3) 5OAc] (OAc) 2); [Co (NH3) 5? Ac] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2 ("PAC" in the present invention).

These cobalt catalysts are easily prepared by known methods, such as those taught for example in the Tobe article above and the references cited therein, in the U.S. patent. 4,810,410, for Diakun et al, issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem. 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); v Journal of Phvsical Chemistrv. 56, 22-25 (1952); as well as the synthesis examples provided hereinafter. 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 US Pat. Nos. 5,559,261, 5,581, 005 and 5,597,936. 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. 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, itaconic, aconitic, mesaconic, citraconic and methylenemalonic modified or their salts, maleic anhydride, acrylamide , alkylene, vi nyl methyl ether, styrene and any of mixtures thereof. Copolymers of acrylic acid and maleic 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 Haas.

Preferred acrylic acid-containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight of acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of substituted acrylic monomer or its salts having the general formula - [CR2-CR? (CO-0-R3)] - in which at least one of the substituents Ri, R2 or R3, preferably R1 or R2 is an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms, R1 or R2 may be a hydrogen and R3 may 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 methacrylic acid. The polyamine and modified polyamine type compounds are useful in the present invention including those obtained from aspartic acid such as those described in EP-A-0305282, EP-A-0305283 and EP-A-0351269. Other optional polymers may 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 Release Agents Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 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, at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, in which, if said hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate units to oxyalkylene terephthalate of C3 is 2: 1 or less, (ii) C -C6 alkylene segments or C4-C6 oxyalkylene, or mixtures thereof, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) substituents of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether, or mixtures thereof, wherein said substituents are present in the form of C-alkyl ether cellulose derivatives C4 or hydroxyalkyl ether of C4, or mixtures thereof, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of 200, although higher levels, preferably from 3 to 150, more preferred from 6 to 100 may be used. The hydrophobic oxyalkylene segments of C4- C6 include, but are not limited to, polymeric soil release agents, such as M? 3S (CH2) pOCH2CH2? -, in which M is sodium and n is an integer of 4-6, as described in US-A-4,721, 580. The polymeric soil release agents useful herein also include cellulose derivatives such as cellulose hydroxy ether polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene terephthalate oxide, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulosic soil release agents for use in the present invention also include those that are selected from the group consisting of C 1 -C 4 alkyl cellulose and C 4 hydroxyalkyl cellulose; see US-A-4,000,093. Soil release agents characterized by hydrophobic poly (vinyl ester) segments include grafted copolymers of poly (vinyl ester), for example C 1 -C 6 vinyl esters, preferably poly (vinyl acetate) grafted to base structures of poiyalkylene, such as the polyethylene oxide base structures. See EP-A-0 219 048. Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene terephthalate oxide (PEO). The molecular weight of this polymeric soil release agent is in the range of 25,000 to 55,000. See U.S. Patent No. 3,959,230 and U.S. Patent No. 3,893,929. Another suitable polymeric soil release agent is a polyester with repeated units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, obtained at 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 repeating terephthaloyl and oxyalkylenoxy units and terminal portions linked by covalent bonds to the base structure. These soil release agents are fully described in US Patent No. 4., 968,451. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent No. 4,711,730, the blocked end anionic oligomeric esters of U.S. Patent No. 4,721, 580, and the block polyester oligomeric compounds. U.S. Patent No. 4,702,857. Other polymeric soil release agents also include the soil release agents of U.S. Patent No. 4,877,896, which discloses anionic, especially sulfoaroyl, blocked end esters of terephthalate.

Another soil release agent is an oligomer with repeated units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy units and oxy-1,2-propylene. The repeating units form the base structure of the oligomer and preferably are terminated with modified isethionate end blockers. A particularly preferred soiling agent of this type comprises a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8 and two end blockers of 2- (2-hydroxyethoxy). sodium acetate sulfonate.

Heavy metal ion sequestrant The tablets of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant is meant in the present invention compounds that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably they show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants, which are acidic in nature, having for example functional groups of phosphonic acid or carboxylic acid, may be present in their acid form or as a complex / salt with an appropriate countercation such as an ion of alkali or alkali metal, ammonium or substituted ammonium or any of the mixtures thereof. Preferably any of the salts / complexes are soluble in water. The molar ratio of said countercation to the heavy metal ion sequestrant is preferably at least 1: 1. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkullenpoly (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), ethylenediaminetri- (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate. Other heavy metal ion sequestrants suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediaminedisuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamindisuccinic acid or any of the salts thereof. Especially preferred is ethylenediamine-N.N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.

Crystal Growth Inhibiting 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%, preferably 0.1% to 2% by 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, preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or even more preferred, ethan-1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or completely ionized form, particularly as a salt or complex.

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

Alkali metal silicate A preferred alkali metal silicate is sodium silicate having an SiO: Na2O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, preferably 2.0. The sodium silicate is preferably present at a level of less than 20%, preferably from 1% to 15%, preferably from 3% to 12% by weight of Si? 2. The alkali metal silicate can be in the form of either anhydrous salt or a hydrated salt. The compositions herein may also contain sodium metasilicate, present at a level of at least 0.4% SiO2 by weight. Sodium metasilicate has a nominal Si02: Na20 ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO 2, is preferably from 50: 1 to 5: 4, preferably from 15: 1 to 2: 1, preferably 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 visible light spectrum. Said colorants when added to a detergent composition have the effect of changing the visible color and hence the appearance of the detergent composition. The dyes can be, for example, inks or pigments. Preferably, the dyes are stable in the composition in which they are to be incorporated. Thus, in a composition with high pH, the dye is preferably stable in an alkaline medium and in a composition with low pH, the dye is preferably stable in an acidic medium. Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline dyes, monoazo, disazo and polyazo 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 RU, 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 by any suitable method. Suitable methods include mixing all active or selected detergent components with a colorant in a drum or spraying all detergent components active or selected with the colorant into a rotating drum.

The dye is typically added at a level of 0.001% to 1.5%, preferably from 0.01% to 1.0%, preferably from 0.1% to 0.3% of the composition.

Corrosion inhibiting compound The compositions of the present invention, especially for use in dishwashing, may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing corrosion inhibiting compounds and Mn compounds. (ll), particularly salts of Mn (ll) of organic ligands. Organic silver coating agents are described in WO-A-94/16047 and EP-A-690122. Nitrogen-containing corrosion inhibiting compounds are described in EP-A-634,478. The compounds of Mn (ll) which are used to inhibit corrosion are described in EP-A-672 749. The functional role of the silver coating agent is to form a protective coating layer "in use" over any of the components of silver articles 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 pol-carboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and ß, ß acid. '-dihydroxy-isobutyric acid. Examples of suitable polycarboxylic acids include n-butyl malonic acid, citric acid, citric acid, maleic acid, malic acid and succinic acid. The fatty acid alcohol radical in the fatty acid ester may 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, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol 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 normally comprises a selected species of behenic acid, stearic acid, oleic 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: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, giicerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomiristate, sorbitan monobehenate, sorbitan monoleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mono- and di-esters of tallowalkylsorbitan. Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate 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, palm oil and oil. of corn. Waxes, including microcrystalline waxes are suitable organic silver coating agents in the present invention. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise from 12 to 70 carbon atoms. Preferred are paraffin waxes and microcrystalline waxes which are composed of saturated long chain hydrocarbon compounds. Alginates and gelatin are suitable organic silver coating agents in the present invention. Also suitable are dialkylamine oxides such as C12-C20 methylamine oxides, and the quaternary dialkylammonium compounds and salts, such as the C12-C20 mephilamonium halides. Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, polymers of N-oxide polyamine, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and derivatives of Cellulose such as mephilecellulose, carboxymethylcellulose and hydroxymethylcellulose are examples of said polymeric materials. Certain perfume materials, particularly those that demonstrate a high substantivity towards metallic surfaces, are also useful as organic silver coating agents in the present invention. The polymeric soil release agents can also be used as an organic silver coating agent. A preferred organic silver coating agent is a paraffin oil, typically a predominantly 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 having these characteristics, which has a cyclic to non-cyclic hydrocarbon ratio of 32:68 is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Nitrogen corrosion inhibiting compounds Suitable nitrogenous corrosion inhibiting compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecylimidazole, and those imidazole derivatives described in Czechoslovakia Patent No. 139,279 and 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 the pyrazole is substituted in 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 NO2. Other suitable nitrogenous corrosion inhibiting compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1, 2,3,4-tetrazole, tionalide, morpholine, melamine, distearylamine, stearoyltearamide, cyanuric acid, aminotriazole, aminotetrazole 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 citrate.

Mn corrosion inhibitors (ll) Preferably, the Mn compound (ll) is incorporated at a level that provides 0.1 ppm to 250 ppm, preferably 0.5 ppm to 50 ppm, more preferably 1 ppm to 20 ppm. ppm by weight of Mn ions (ll) in 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 Mn (II) compound can be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate. The compound Mn (ll) can be a salt or complex of an organic ligand. In a preferred aspect, the organic ligand is a heavy metal ion sequestrant. In another preferred aspect the organic ligand is a crystal growth inhibitor.

Other Corrosion Inhibiting Compounds Other suitable corrosion inhibiting compounds include mercaptans and diols, especially mercaptans having 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionephthol, tionalide and thioanthranol.

Also suitable are saturated or unsaturated C 10 -C 20 fatty acids, or their salts, especially aluminum tristearate. Also suitable are the C2-C2o hydroxy fatty acids > or its salts. Phosphonated octadecane and other antioxidants such as betahydroxytoluene (BHT) are also suitable. It has been found that butadiene and maleic acid copolymers, particularly those supplied under the trademark No. 07787 by Polysciences Inc., are of particular utility as corrosion inhibiting compounds.

Water-soluble Bismuth Compound The compositions herein, especially for use in dishwashing, may contain a water-soluble bismuth compound, preferably present at a level of 0.005% to 20%, preferably 0.01% to 5%, preferably from 0.1% to 1% by weight of the composition. The water-soluble bismuth compound can be essentially any bismuth salt or 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 stabilizer system Preferred enzyme containing compositions in the present invention may comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferred from 0.01% to 6% by weight of an enzyme stabilizer system. The enzyme stabilizing system can be any stabilizing system that is compatible with the detersive enzyme. Said stabilizing systems may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boric acid, chlorine bleach scrubbers and mixtures thereof. Said stabilizing systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime Soap Dispersant Compound The compositions of the present invention may contain a lime soap dispersing compound, preferably present at a level of from 0.1% to 40% by weight, preferably from 1% to 20% by weight, preferably from 2% to 10% by weight of the composition. A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or fatty acid amine salts caused by calcium or magnesium. Preferred lime soap dispersant compounds are described in WO-A-93/08877.

Foam suppression system The compositions of the present invention preferably comprise a foam suppression system present at a level from 0.01% to 15%, preferably from 0.05% to 10%, preferably from 0.1% to 5% by weight of the composition. Foam suppression systems suitable for use in the present invention may comprise essentially any known antifoam compound, including, for example, silicone anti-foaming compounds and 2-alkyl and alkanol antifoaming compounds. Preferred foam suppression systems and antifoam compounds are described in WO-A-93/08876 and EP-A-705324.

Polymeric Agents Dye Transfer Inhibitors The compositions of the present invention can also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. The polymeric agents, dye transfer inhibitors are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

Optical brightener The compositions may also 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 Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, 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-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6- (N- 2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular kind of brightener is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. 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 such as sodium, the brightener is the disodium salt of acid 4.4, -b1s [(4 -an-lino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular kind of brightener is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula R < | is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin-2-yl) amino acid] 2,2'-stybenedisulfonic. This particular kind of brightener is marketed under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Clay Softening System The compositions herein may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are described in US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. EP-A-299,575 and EP-A-313,146 describe suitable organic polymeric clay flocculating agents.

Cationic fabric softening agents Cationic fabric softening agents suitable include water-insoluble tertiary amines or long double-chain amide materials such as those described in GB-A-1 514 276 and EP-BO 011 340. Cationic fabric softeners are typically incorporated at total levels of 0.5% to 15% by weight, typically 1% to 5% by weight.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent tablet for use in a washing machine, the tablet having one or more phases, at least one of which is in the form of a compressed particulate solid characterized in that it comprises: a) a polymeric disintegrant having a size distribution of particle so that at least 90% by weight thereof has a particle size of less than about 0.3 mm and at least 30% by weight thereof has a particle size of less than about 0.2 mm; and b) a hydrosoluble hydrated salt having a solubility in distilled water of at least about 25 g / 1 OOg at 25 ° C.

2. The detergent tablet according to claim 1, further characterized in that the polymeric disintegrant has a particle size distribution so that at least 90% by weight thereof has a particle size of less than about 0.25 mm and therefore less 50% by weight thereof has a particle size of less than about 0.2 mm.

3. The detergent tablet according to any of claims 1 or 2, further characterized in that the polymeric disintegrant has a particle size distribution so that at least 90% by weight thereof has a particle size greater than about 0.05 mm, preferably greater than about 0.75 mm.

4. A detergent tablet for use in a washing machine, the tablet having one or more phases, at least one of which is in the form of a compressed particulate solid characterized in that it comprises: a) a polymeric disintegrant; b) a hydrosoluble hydrated salt having a solubility in distilled water of at least about 25 g / 1 OOg at 25 ° C; and optionally c) an effervescent agent.

5. The detergent tablet according to any of claims 1 to 4, further characterized in that the polymeric disintegrant I is selected from starch, cellulose and derivatives thereof, alginates, sugars, polyvinylpyrrolidones, expandable clays and mixtures thereof.

6. The detergent tablet according to any of claims 1 to 5, further characterized in that the hydrosoluble hydrated salt is selected from hydrates of sodium acetate, sodium metaborate, sodium orthophosphate, sodium diacid phosphate, disodium hydrogen phosphate, Sodium potassium tartrate, potassium aluminum sulfate, calcium bromide, calcium nitrate, sodium citrate, potassium citrate and mixtures thereof.

7. The detergent tablet according to any of claims 1 to 6, further characterized in that the hydrosoluble hydrated salt is selected from water-soluble mono-, di-tri- and tetrahydrate salts and mixtures thereof.

8. The detergent tablet according to any of claims 1 to 7, further characterized in that the hydrosoluble hydrated salt has a melting point in the range from about 30 ° C to about 95 ° C.

9. The detergent tablet according to any of claims 1 to 8, further characterized in that the hydrosoluble hydrated salt has a melting point in the range from about 30 ° C to about 75 ° C.

10. The detergent tablet according to any of claims 1 to 9 containing from about 0.5% to about 10% by weight of the polymeric disintegrant and hydrosoluble hydrated salt. 11- The detergent tablet according to any of claims 1 to 10, which has a resistance to a child bite (CBS) of at least about 6 kg, preferably greater than about 14 kg. 12. The detergent tablet according to any of claims 1 to 11, further characterized in that the particulate solid is compressed at a pressure of at least about 40 kg / cm2, preferably at least about 250 kg / cm2, preferably at least about 350 kg / cm2. 13. The detergent tablet according to any of claims 1 to 12, further characterized in that it comprises: a) a first phase in the form of a body configured having at least one mold in it; and b) a second phase which is in the form of a particulate solid compressed within said mold. 14. The detergent tablet according to claim 13, further characterized in that the second phase is compressed at a pressure less than about 350 kg / cm2. 15. The detergent tablet according to claim 12 or 14, further characterized in that the first phase is compressed at a pressure of at least about 350 kg / cm2.