FR2782091A1 - DETERGENT TABLET - Google Patents

Abstract

The invention provides a multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a shaped body having at least one mold therein; and b) a second phase in the form of a compressed body adhesively contained within said mold, wherein the tablet composition comprises one or more detergent active substances which are predominantly concentrated in the second phase, and wherein the second phase further comprises a binder. Multi-phase tablets provide improved dissolving and cleaning characteristics along with excellent tablet integrity and strength.

Description

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 The present invention relates to multi-phase detergent tablets.

 Detergent compositions in tablet form are known in the art. It is understood that the detergent compositions in the form of tablets have several advantages compared to the detergent compositions in particulate form, such as the ease of dosing, handling, transport and storage.

 The detergent tablets are most commonly prepared by premixing components of a detergent composition and putting the premixed detergent components into the form of a tablet using any suitable equipment, preferably a tablet press. The tablets are typically formed by compression of the components of the detergent composition, so that the tablets produced are robust enough to be able to withstand handling and transport without being damaged. In addition to being robust, the tablets must also dissolve fast enough for the detergent components to be released into the wash water as quickly as possible at the start of the wash cycle.

 However, there is a dichotomy in that when the compressive force increases, the dissolution rate of the tablets is lower.

Consequently, the present invention aims to find a balance between the robustness of the tablets and the dissolution of the tablets.

 Solutions to this problem, presented in the prior art, include compressing the tablets under low compression pressure. However, tablets produced in this way, although they have a relatively high dissolution rate, tend to fall apart, becoming damaged and unacceptable to the consumer. Other solutions include the preparation of tablets using a high relative compression pressure, in order to reach the required level of robustness, and use a dissolving aid such as an effervescent agent.

 The multi-phase detergent tablets described in the prior art are prepared by compressing a first composition in a tablet press to form a first substantially planar layer. Then deliver another detergent composition to the tablet press above

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 of the first layer. This second composition is then compressed to form another practically flat second layer. Thus, the first layer is generally subjected to more than one compression since it is also compressed during the compression of the second composition. Typically, the first and second compressive forces have the same order of magnitude. The Applicant has found that when this is the case, since the compression force must be sufficient to bind the first and second compositions together, the force used in both the first and in the second compression stages must be within the range from '' about 4,000 to about 20,000 kg (assuming a shelf section of about 10 cm2). A consequence of this is a lower dissolution rate of the tablet. Other multi-phase tablets with differential dissolution are prepared so that the second layer is compressed under less force than for the first layer. However, although the dissolution rate of the second layer is improved, the second layer is soft compared to the first layer and is therefore vulnerable to damage caused by handling and transportation.

 Document EP-B-0 055 100 describes a block of W-C formed by the combination of a shaped body with slow dissolution and a shelf. The W-C block is designed to be placed in the flush tank of a W-C and dissolves over several days, preferably several weeks. As a means of decreasing the rate of dissolution of the block of W-C, the document teaches the addition by mixing of one or more solubility regulating agents. Examples of such solubility regulators are paradichlorobenzene, waxes, fatty acids and long chain alcohols and their esters, and (fatty alkyl) amides. The detergent tablets to be used in the automatic washing of. the dishes or the laundry must dissolve substantially in a single cycle of the washing machine or the dishes, that is to say in the space of 15 to 120 minutes.

SUMMARY OF THE INVENTION
According to a first aspect of the invention, there is provided a multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a shaped body having at least

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 a mold therein; and b) a second phase in the form of a compressed body adhesively contained inside said mold, the tablet composition comprising one or more detergent active substances which are predominantly concentrated in the second phase, and the second phase further comprising a binder.

 Preferably the second phase is in the form of a particulate solid compressed inside said mold.

 In preferred embodiments, the first phase is a compressed shaped body prepared under an applied compression pressure of at least about 40 kg / cm2, preferably at least about 250 kg / cm2, more preferably at least approximately 350 kg / cm2 (3.43 kN / cm2), more particularly from approximately 400 to approximately 2000 kg / cm2, and especially from approximately 600 to approximately 1200 kg / cm2 (the compression pressure here is the force applied divided by the transverse surface of the tablet in a plane perpendicular to the applied force; in fact, the transverse surface of the die of the rotary press). It is also preferred that the particulate solid of the second phase (this terminology being intended to encompass the possibility of multiple "second" phases, sometimes called here "optional subsequent phases") is compressed in said mold under an applied compression pressure lower than that applied to the first phase and preferably under a compression pressure of less than about 350 kg / cm2, preferably in the range of from about 40 kg / cm2 to about 300 kg / cm2 and more preferably about 70 at around 270 kg / cm2, these tablets being preferred here from the point of view of obtaining optimal integrity and resistance of the tablets (measured for example by the Child Bite Strength test (bite force of a child , [CBS])) and optimal dissolution characteristics of the product. The tablets of the invention preferably have a CBS value of at least approximately 6 kg, in particular greater than approximately 8 kg, better still greater than approximately 10 kg, more particularly greater than approximately 12 kg, and very especially greater than approximately 14 kg, the CBS value being measured by the test specification of the US Consumer Product Safety Commission Test Specification. Also, the compression pressures

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 applied to the first and second phases will generally have a ratio of at least about 1.2 / 1, preferably at least about 2/1, more preferably at least about 4/1.

Thus, according to another aspect of the invention, there is provided a multi-phase detergent tablet for use in a washing machine, the tablet comprising: a) a first phase in the form of a compressed shaped body having at at least one mold therein, the shaped body being prepared under a compression pressure of at least about
350 kg / cm2; and b) a second phase in the form of a compressed solid contained adhesively inside said mold, in which the tablet composition comprises one or more detergent active substances which are predominantly concentrated in the second phase, and wherein the second phase further comprises a binder.

 The second phase is in the form of a compressed body contained in an adhesive manner, for example by physical or chemical adhesion, inside the mold at least one of the first body. It is also preferred that the first and second phases have a relatively high mutual weight ratio, for example of at least about 6/1, preferably at least about 10/1; the tablet composition contains one or more detergent active substances (for example enzymes, bleaching agents, bleaching activators, bleaching catalysts, surfactants, chelating agents, etc.) which are predominantly concentrated in the second phase, for example that at least about 50%, preferably at least about 60%, in particular at least about 80% by weight of active substance (relative to the total weight of active substance in the tablet) are in the second tablet phase. Also, these compositions are optimal for the strength, dissolution, cleaning and pH regulation characteristics of the tablet, giving, for example, tablet compositions capable of dissolving in the wash liquor so as to deliver at least 50%, preferably at least 60%, and more preferably at least 80% by weight of detergent active substance in the washing liquor in space

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 10, 5, 4 or even 3 minutes from the start of the washing process.

 An additional advantage of the invention is the ability to achieve differential dissolution of the phases, so that one phase of the tablet will dissolve significantly before another phase, and may even dissolve almost completely before the other phase has dissolved. This is particularly interesting for the differential delivery of detergent active substances.

 Suitably, the detergent active substance or substances are chosen from enzymes, bleaching agents, bleaching activators, bleaching catalysts, surfactants, chelating agents, crystal growth inhibitors and their mixtures, active substances enzymatic being particularly preferred to reinforce the cleaning performances during the very initial stage with cold water of the washing or cleaning operation. Therefore, it is especially preferred to use here detergent-active enzymatic substances and in particular enzymes and mixtures of enzymes comprising one or more enzymes having enhanced or optimal activity in the temperature range from 25 ° C. to 55 ° C. and at a pH value in the range from 8 to 10 (e.g. Natalase).

DETAILED DESCRIPTION OF THE INVENTION
An object of the present invention is to provide a detergent tablet not only which is robust enough to withstand handling and transport, but also of which a significant part dissolves quickly in the washing water, achieving rapid delivery of substance. active detergent. It is preferred that at least one phase of the tablet dissolves in the washing water within the first ten minutes, preferably the first five minutes, better still the first four minutes of the washing cycle of an automatic washing machine. dishes or washing clothes. Preferably, the washing machine is an automatic dishwashing machine or washing machine. The time in which the multi-phase tablet or a phase thereof or an active detergent component dissolves is determined according to DIN 44990, using a dishwasher available from Bosch on the normal washing program at 65 C with water having a hardness of 18 H, using a minimum of six repetitions or a sufficient number to

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 ensure reproducibility.

 The multi-phase detergent tablet of the present invention comprises a first phase, a second phase and possibly 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. Preferred detergent components include builders, bleaches, enzymes and surfactants. The components of the detergent composition are mixed together, for example by mixing the dry components or spraying the liquid components. The components are then put into the form of a first phase using any suitable equipment, but preferably by compression, for example in a tablet press. Alternatively, the first phase can be prepared by extrusion, casting, etc. The first phase can take various geometric shapes such as spheres, cubes, etc., but preferred embodiments have a generally axial and symmetrical shape with a generally round, square or rectangular cross section.

 The first phase is prepared so that it includes at least one mold in the surface of the shaped body. The mold or molds can also have variable sizes and shapes and a variable location, orientation and topology with respect to the first phase. For example, the mold or molds may have a generally circular, square or oval section; they may form a closed cavity or recess therein in the surface of the shaped body, or they may extend between unconnected regions of the body surface (e.g., axially opposite facing surfaces) to form a or several topological "holes" in the shaped body; and they can be arranged axially or otherwise symmetrical with respect to the first phase or they can be arranged asymmetrically. In a preferred embodiment, the mold is created by using a specially designed tablet press in which the surface of the matrix which comes into contact with the detergent composition has a shape such as when it comes into contact with the composition detergent and press, it presses a mold, or multiple molds, in the first phase of the multi-phase detergent tablet. Preferably, the mold will have a concave surface towards

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 the interior or generally concave so as to allow better adhesion to the second phase. Alternatively, the mold can be created by compressing a preformed body of detergent composition disposed annularly around a central die, thereby forming a shaped body having a mold in the form of an axially extending cavity opposite surfaces of the body.

 The tablets of the invention also comprise one or more additional phases prepared from a composition or from several compositions which comprise one or more detergent components as described below. At least one phase (here called "second phase") preferably takes the form of a particulate solid (this term including powders, granules, agglomerates, and other particulate solids, including their mixtures with liquid binders , fusible solids, pulverized products, etc.) compressed into or inside the mold (s) of the first phase of the detergent tablet, so that the second phase itself takes the form of 'a shaped body. Other optional phases include one or more compositions in the form of a layer or separate layers. Preferred detergent components include adjuvants, colorants, binders, surfactants, disruptants and enzymes, particularly enzymes of the amylase and protease types. In another preferred aspect of the present invention, the second phase and the possible subsequent phases comprise a disrupting agent which can be chosen from a disintegrating agent or an effervescent agent. Suitable disintegrants include agents which swell on contact with water or facilitate the entry and / or exit of water by forming channels in the detergent tablet. We consider here the use of any known disintegrating or effervescent agent usable in laundry or dishwashing applications. Suitable disintegrants include starches (such as natural, modified and pregelatinized starches, for example those derived from corn and rice and potato starch), starch derivatives such as U-Sperse (registered trademark ), Primojel (registered trademark) and Explotab (registered trademark), celluloses, microcrystalline celluloses and cellulose derivatives such as Arbocel (registered trademark) and Vivapur (registered trademark), both available from Rettenmaier, Nymcel (trademark

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 registered) available from Metsa-serla, Avicel (registered trademark), Lattice NT (registered trademark) and Hanfloc (registered trademark), alginates, acetate trihydrates, burkeite, carbonate monohydrates of formula Na2CO3 # H2O, STPP hydrate having a phase I content of at least about 40%, carboxymethylcellulose (CMC), polymers based on CMC, sodium acetate, aluminum oxide. Suitable effervescent agents are those which produce a gas on contact with water. Suitable effervescent agents can be species releasing oxygen, nitrogen dioxide or carbon dioxide. Examples of preferred effervescent agents can be chosen from the group consisting of perborates, percarbonates, carbonates and bicarbonates in combination with carboxylic acids or other acids such as citric, sulfamic, maleic or maleic acid. .

 The components of the detergent composition are mixed together, for example, by mixing the dry components and mixing or spraying the liquid components. The components of the second phase and of any subsequent phases are then introduced into the mold produced by the first phase and kept therein.

 The preferred embodiment of the present invention comprises two phases: a first phase and a second phase. The first phase will normally comprise a single mold and the second phase will normally consist of a single detergent active composition.

However, it is contemplated that the first phase may include more than one mold and that the second phase may be prepared from more than one active detergent composition. Furthermore, it is also envisaged that the second phase may comprise more than one active detergent composition contained inside a single mold. It is also envisaged that several active detergent compositions are contained in separate molds. In this way, potentially chemically sensitive detergent components can be separated in order to avoid any loss of performance due to components that react together and which become potentially inactive or exhausted.

 A binder component to be used in the invention is chosen from the group consisting of organic polymers, for example polyethylene glycols and / or polypropylene glycols, in particular those having

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 a molecular weight of 4,000.6,000 or 9,000, paraffins, polyvinylpyrrolidone (PVP), in particular a PVP having a molecular weight of 90,000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, for example hydroxypropylmethylcellulose (HPMC) and carboxymethylcellulose (CMC); and mineral polymers, such as hexametaphosphates. The binder is useful both for the integrity of the tablet and to facilitate obtaining a differential dissolution of the first and second phases, as described below.

 In a preferred aspect of the present invention, the first phase weighs more than about 3 g, preferably more than about 4 g, more preferably more than about 5 g. More preferably, the first phase weighs from about 10 g to about 30 g, more particularly from about 15 g to about 25 g and especially from about 18 g to about 24 g. The second phase and any subsequent phases weigh less than 4 g. More preferably, the second phase and / or any subsequent phases weigh from about 0.1 g to about 3.5 g, preferably from about 1 g to about 3.5 g, most preferably from about 1.3 g about 2.5 g.

 In another embodiment of the present invention, a barrier layer comprising a barrier layer composition is located between the first and second phases and / or any subsequent phases or, if not, between the second phase and any subsequent phases. The barrier layer composition comprises at least one binder chosen from the group described above. The advantage of the presence of a barrier layer is to prevent or reduce the migration of components from one phase to another phase, for example from the first phase in the second phase and / or any subsequent phases, and reciprocally.

 The components of the second phase and any subsequent phases are preferably compressed under a very low compression force compared to the compression force normally used to prepare tablets. Thus, an advantage of the present invention is that since a low compression force is used, the detergent components sensitive to forces or to chemicals can be incorporated into the detergent tablet without supporting the consequent loss of performance.

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 that is usually encountered when incorporating such components into tablets. Alternatively, the second phase (s) can be compressed with a compressive force equal to or greater than that of the first phase in order to achieve differential dissolution of the phases, as described below.

 Another advantage of the present invention is the improved protection of the second phase against damage caused, for example, by handling and transport. As described above, multi-phase detergent tablets were prepared in which the second layer was compressed under a compressive force lower than that of the first layer. However, although its dissolution rate is improved, the second layer of these tablets becomes vulnerable to damage, and tends to fall apart or crumble on contact.

However, the slightly compressed phase or phases of the detergent tablets of the present invention are protected inside the mold produced by the first phase of the detergent tablet.

 Yet another advantage of the present invention is the ability to prepare a multi-phase detergent tablet in which one phase can be designed to dissolve, preferably significantly before another phase. In the present invention, it is preferred that the second phase and the possible subsequent phase or phases dissolve before the first phase. Depending on the preferred weight ranges described above, it is preferred that the first phase dissolve in 5 to 20 minutes, better still in 10 to 15 minutes, and that the second phase and / or any subsequent phases dissolve in less than 5 minutes, better still in less than 4.5 minutes, especially in less than 4 minutes. As a variant, the second phase can dissolve after the first phase or other phases, for example when it is desired to provide cleaning or rinsing advantages towards the end of the washing operation. The moments at which the first phase, the second phase and / or any subsequent phases dissolve are independent of each other. Thus, in a particularly preferred aspect of the present invention, differential phase dissolution is obtained. A particular advantage of the ability to effect differential dissolution of the multi-phase detergent tablet is that a component which is chemically inactivated by the presence of another

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 component can be separated in a different phase. In this case, the component which is inactivated is preferably located in the second phase and in the possible subsequent phases.

 Yet another advantage of the present invention is the improved adhesion between phases of the multi-phase tablet. The improved adhesion is believed to be achieved by reducing the exposure of the second phase compared to multi-phase tablets known in the art, as a result of which the tablets of the present invention are less likely to fracture along the contact line between the phases.

Process
Multi-phase detergent tablets are prepared using any suitable tablet-forming equipment, for example a Courtoy R253 device. Preferably, the 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, following the procedure described below. The die (s) of this tablet press are modified so that the surface of the matrix which comes into contact with the detergent composition has a convex surface.

 A first detergent composition is introduced into the die of the tablet press and the matrix is lowered so that it comes into contact with the detergent composition and then compresses it to form a first phase. The first detergent composition is compressed using an applied pressure generally of at least about 250 kg / cm2, preferably about 350 to about 2000 kg / cm2, more preferably about 500 to about 1500 kg / cm2, most preferably from around 600 to around 1200 kg / cm2. Then the matrix is raised, which exposes the first phase containing a mold. Then a second detergent composition and any subsequent detergent compositions are introduced into the mold. The specially designed tablet press die is then lowered a second time so as to slightly compress the second detergent composition and any subsequent detergent compositions to form the second phase and the phases

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 possible later. 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, practically similar to the second compression step described above. The second detergent composition and any subsequent detergent compositions are compressed under a pressure preferably less than about 350 kg / cm2, more preferably from about 40 to about 300 kg / cm2, most preferably from about 70 to about 270 kg / cm2 .

After compression of the second detergent composition, the matrix is raised a second time and the multi-phase detergent tablet is ejected from the tablet press.

Detergent components
The first phase, the second phase and / or any subsequent phases of the multi-phase detergent tablet described here are prepared by compression of one or more compositions comprising active detergent components. Suitably, the compositions used in any of these phases may include various different detergent components, including adjuvants, surfactants, enzymes, bleaches, alkalinity sources, colorants, fragrances , lime soap dispersants, organic polymeric compounds, including polymeric agents inhibiting the transfer of dyes, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, stabilizers enzyme, corrosion inhibitors, anti-foaming agents, solvents, fabric softeners, optical brighteners and hydrotropes.

 Highly preferred detergent components of the first phase include an adjuvant, a surfactant, an enzyme and a bleach. Highly preferred detergent components of the second phase include an adjuvant, enzymes, crystal growth inhibitors and disruptants and / or binders.

Adjuvant compound
The tablets of the present invention preferably contain an adjuvant compound, typically present in an amount of 1% to 80% by weight, preferably 10% to 70% by weight, most preferably 20% to

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 60% by weight relative to the composition of active detergent components.

Water soluble adjuvant compound
Suitable water-soluble builder components include water-soluble monomeric polycarboxylates, or their acid forms, homopolymeric or copolymeric polycarboxylic acids, or their salts, in which the polycarboxylic acid comprises at least two separate carboxylic groups. one of the other by at most two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures thereof.

 The carboxylate or polycarboxylate builder can be of the monomer or oligomer type, although polycarboxylate monomers 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 their ether derivatives. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, acid tartronic and fumaric acid, as well as ethercarboxylates and sulfinylcarboxylates. The polycarboxylates containing three carboxy groups include, in particular, the water-soluble citrates, aconitrates and citraconates as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British patent N 1 379 241, the lactoxysuccinates described in British patent N 1 389,732, and the aminosuccinates described in the Dutch application 7205873, and the oxypolycarboxylate materials such as the 2-oxa-1,1,3,3-propanetricarboxylates described in the British patent N 1 387 447.

 Polycarboxylates containing four carboxy groups include the oxidisuccinates described in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propanetetracarboxylates and 1,1,2,3- propanetetracarboxylates. The polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000.

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 Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienylpentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyvalent alcohols such as sorbitol, mannitol and xylitol. The aromatic polycarboxylates include the derivatives of mellitic acid, pyromellitic acid and phthalic acid described in British Patent No. 1,425,343.

 Among the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

 The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or their mixtures with their salts, for example citric acid or citrate / citric acid mixtures, are also envisaged as useful adjuvant components.

 Borate builders, as well as builders containing borate-forming materials which can produce borate under washing or detergent storage conditions are also usable but are not preferred for washing conditions below 50 C, in particular below at 40 C.

 Examples of carbonate adjuvants are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and their mixtures with ultrafine calcium carbonate, as described in German patent application N 2 321 001 , published November 15, 1973.

 Adjuvant compounds that are particularly preferred for use in the present invention are water-soluble phosphate builders. Specific examples of water soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates , sodium polymetaphosphate in which the degree of polymerization ranges from 6 to 21, and the salts of phytic acid.

Partially soluble or insoluble adjuvant compound

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The tablet of the present invention may contain a partially soluble or insoluble adjuvant compound. The partially soluble and insoluble adjuvant compounds are particularly useful in tablets prepared for use in laundry cleaning processes. Examples of partially water-soluble adjuvants include crystalline lamellar silicates as described, for example, in EP-A-0 164 514, DE-A-3 417 649 and DE-A-3 742 043. We. preferred the crystalline lamellar sodium silicates of general formula: NaMSixO2 + 1 # yH2O in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. The silicates of Sodium crystalline lamellars of this type preferably have a two-dimensional "sheet" structure, such as the so-called lamellar structure 8, as described in documents EP 0 164 514 and EP 0 293 640. Processes for the preparation of crystalline lamellar silicates of this type are described in documents DE-A-3,417,649 and DE-A-3,742,043. For the purpose of the present invention, x in the general formula above is worth 2.3 or 4 and preferably 2.

 The especially preferred crystalline lamellar sodium silicate compound corresponds to the formula # -Na2Si2O5, and is known under the name NaSKS-6 (registered trademark), available from Hoechst AG.

 The crystalline lamellar sodium silicate material is preferably present in the granular detergent compositions in particulate form in intimate mixture with a solid, ionizable and water-soluble material, as described in PCT patent application No. WO92 / 18594. The ionizable solid material soluble in water is chosen from organic acids, salts of organic and mineral acids and their mixtures; citric acid is preferred.

 Examples of adjuvants largely insoluble in water include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having the unit cell formula Naz [(AlO2) z (SiO2) y] # xH2O, wherein z and y are at least 6; the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline,

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 containing from 10 to 28% and better still from 18 to 22% of water in bound form.

 The aluminosilicate zeolites can be natural materials, but are preferably synthetic. Synthetic ion exchange materials of the crystalline aluminosilicate type are available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and their mixtures.

 A preferred method for synthesizing aluminosilicate zeolites is that described by Schoeman et al. (published in Zeolite (1994) 14 (2), 110-116), in which the author describes a process for preparing colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles are larger than 1 m in diameter and not more than 5% of the particles are smaller than 0.05 m in diameter. Preferably, the aluminosilicate zeolite particles have an average particle size of 0.01 m to 1 m, better still from 0.05 m to 0.9 m, especially from 0.1 m to 0.6 m.

 Zeolite A corresponds to the formula: Na12 [(AlO2) 12 (SiO2) 12] # xH2O in which x is from 20 to 30, in particular 27. Zeolite X corresponds to the formula Na86 [(AlO2) 86 (SiO2) 106] # 276H2O. Zeolite MAP, as described in document EP-B-384,070, is an adjuvant of the zeolite type which is preferred to use here.

 The preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. When used as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloidal zeolite A, provide better adjuvant performance in terms of achieving better soil removal.

There are also improved adjuvant performance in terms of reducing tissue overlay and improving the maintenance of tissue whiteness, problems believed to be associated with detergent compositions of poor build quality as an adjuvant. .

 A surprising discovery is that the detergent compositions containing mixed aluminosilicate zeolites, comprising colloidal zeolite A and colloidal zeolite Y, achieve an equal calcium ion sequestration performance compared to an equal weight of zeolite A

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 commercially available. Another surprising discovery is that the detergent compositions containing mixed aluminosilicate zeolites, described above, provide an improved sequestration performance of magnesium ions relative to an equal weight of commercially available zeolite A.

Surfactant
Surfactants are preferred detergent active components of the compositions described herein. Suitable surfactants are chosen from anionic, cationic, nonionic, ampholyte and zwitterionic surfactants, and mixtures thereof. Products for automatic dishwashers should have a low foaming character and therefore the foaming power of the surfactant system to be used in dishwashing processes should be eliminated or, better still, be a low foaming power, typically of a non-ionic character. . Foaming due to surfactant systems used in laundry cleaning processes does not need to be suppressed to the same extent as that required for washing dishes. Typically, the surfactant is present in an amount of 0.2 to 30% by weight, more preferably 0.5 to 10% by weight, especially 1 to 5% by weight relative to the composition of detergent components. assets.

 A characteristic list of the anionic, nonionic, ampholyte and zwitterionic classes, as well as the species of these surfactants, is given in US Patent No. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. A list of suitable cationic surfactants is given in U.S. Patent No. 4,259,217 issued to Murphy on March 31, 1981.

A list of surfactants typically incorporated in detergent compositions for automatic dishwashing is given, for example, in document EP-A-0 414 549 and PCT applications N WO 93/08876 and WO 93/08874.

Nonionic surfactant
Almost any nonionic surfactant useful for detergent purposes can be incorporated into the detergent tablet. Preferred non-limiting classes of useful nonionic surfactants are shown below.

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Non-ionic surfactant of ethoxylated alcohol type
The condensation products of alkyl ethoxylate and aliphatic alcohols having from 1 to 25 moles of ethylene oxide can be used here. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

Surfactant alkyl alkoxylate capped at the end
Alkyl alkoxylate surfactants of suitable end-capped types are the epoxy-capped polyoxyalkylenated alcohols represented by the formula:
R1O [CH2CH (CH3) O] x [CH2CH2O] y [CH2CH (CH) R2] (I) wherein RI is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20.

 Preferably, the surfactant of formula 1 has at least 10 carbon atoms in the terminal epoxy unit [CH2CH (OH) R2]. Suitable surfactants of formula I according to the present invention are the nonionic surfactants POLY-TERGENT SLF-18B from Olin Corporation, as described, for example, in document WO 94/22800, published on October 13, 1994 by Olin Corporation.

Ether-capped polyoxyalkylenated alcohols
The surfactants which are preferred to use here include the ether-capped polyoxyalkylenated alcohols of formula:
R1O [CH2CH (R3) O] x [CH2] kCH (OH) [CH2] jOR2 in which RI and R2 are saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R2 is H or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer with an average value from 1 to 30, where, when x is 2 or more, the R3 can be the same or different, and k and j are integers with an average value from 1 to 12, and better still from 1 to 5.

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 R1 and R2 are preferably aliphatic or aromatic, saturated or unsaturated, linear or branched, hydrocarbon radicals having from 6 to 22 carbon atoms, and very especially from 8 to 18 carbon atoms. For R3, H is particularly preferred or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms. Preferably, x is an integer having an average value from 1 to 20, better still from 6 to 15.

 As described above, when, in the preferred embodiments, x is greater than 2, the R3s may be the same or different. Namely, R3 can vary among any of the alkylene oxy units described above. For example, if x is 3, R3 can be chosen to form ethylene oxy (EO) or propylene oxy (PO) and the order can vary among (EO) (PO) (EO), (EO) (EO) ) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). Of course, we only chose the integer three by way of example only and the variations can be much greater with a higher integer value for x, and they include, for example, multiple (EO) patterns with a much smaller number of patterns (PO).

 Particularly preferred surfactants as described above include those with a low cloud point below 20 C. These low cloud surfactants can then be used in conjunction with a high cloud point surfactant, as described in detail below, bringing superior fat cleaning benefits.

Especially preferred ether-capped polyoxyalkylenated alcohol surfactants are those in which k is 1 and j is 1, so that the surfactants have the formula:
R1O [CH2CH (R3) O] xCH2CH (OH) CH2OR2 in which R ', R2 and R3 are as defined above and x is an integer having an average value from 1 to 30, preferably from 1 to 20, and better still from 6 to 18. Very particularly preferred are the surfactants in which R1 and R2 range from 9 to 14, R3 is H forming an ethylene-oxy radical and x ranges from 6 to 15.

 Ether-capped polyoxyalkylenated alcohol type surfactants comprise three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether-end capping. The

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 The styling at the end of the alkyl ether and the alcohol serve as the oil-soluble hydrophobic part of the molecule, while the alkylene oxide group forms the water-soluble hydrophilic part of the molecule.

 These surfactants exhibit significant improvements in staining and filming and grease removal characteristics when used in conjunction with high cloud point surfactants compared to conventional surfactants.

 Generally, the ether-capped polyoxyalkylenated 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 epoxy. The second epoxide is then reacted with an alkoxylated alcohol to form the new compounds of the present invention. Examples of processes for preparing ether-capped polyoxyalkylenated alcohol surfactants are described below.

Preparation of C 12/14 alkyl glycidyl ether
100.0 g (0.515 mol) of C12 / 14 fatty alcohol and 0.58 g (2.23 mmol) of tin (IV chloride from Aldrich) are combined in a round-bottomed bottle with three necks 500 ml bottle fitted with a condenser, an argon inlet, an addition funnel, a magnetic stirrer and an internal temperature probe. The mixture is heated to 60 C. 47.70 g (0.515 mol) of epichlorohydrin (available from Aldrich) are added dropwise so as to maintain the temperature between 60 and 65 C. After stirring for an additional hour, 60 C, the mixture is brought to room temperature.

The mixture is treated with a 50% solution of 61.80 g (0.773 mol, 50%) of sodium hydroxide while agitating it mechanically. Once the addition is complete, the mixture is heated to 90 ° C. for 1.5 hours, cooled, and filtered with ethanol. The filtrate is separated and the organic phase is washed with 100 ml of water, dried over MgSO4, filtered and concentrated. Distillation of the oil at 100-120 ° C. under 0.1 mm Hg gives the glycidyl ether in the form of an oil.

Preparation of C9 / 11 ether-capped alcohol surfactant of C12 / 14 alkyl
20.60 g (0.0393 mol) of Neodol 91-8 (ethoxylated alcohol, available from Shell Chemical Co.) and 0.58 g (2.23 mmol) are combined.

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 of tin (IV) chloride a 250 ml three-necked round-bottom flask fitted with a condenser, an argon inlet, an addition funnel, a magnetic stirrer and a internal temperature probe. The mixture is heated to 60 ° C., at which point 11.00 g (0.0393 mol) of C 12/14 alkyl glycidyl ether are added dropwise over 15 minutes. After 18 hours of stirring at 60 ° C., the mixture is brought to ambient temperature and dissolved in an equal portion of dichloromethane. The solution is passed over a 2.54 cm (1 inch) pad of silica gel while eluting with dichloromethane. The filtrate is concentrated by evaporation on a rotary evaporator and then it is extracted in an oven of the Kugelrohr ball tube type at 100 ° C. at 0.5 mm Hg to obtain the surfactant in the form of an oil.

Non-ionic surfactant of ethoxylated / propoxylated fatty alcohol type
The ethoxylated C6 to C18 fatty alcohols and the C6 to C18 ethoxylated / propoxylated mixed fatty alcohols are surfactants which can be used here, in particular when they are soluble in water. Preferably, the ethoxylated fatty alcohols are ethoxylated C10 to C18 fatty alcohols having a degree of ethoxylation from 3 to 50; especially, they are C1 to C18 ethoxylated fatty alcohols having a degree of ethoxylation from 3 to 40. Preferably, the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length having from 10 to 18 carbon atoms, a degree of ethoxylation from 3 to 30 and a degree of propoxylation from 1 to 10.

Propylene glycol OE / OP nonionic condensation products
The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol can be used here. The hydrophobic part of these compounds preferably has a molecular weight of 1500 to 1800 and exhibits insolubility in water. Examples of such compounds include some of the commercially available Pluronic # surfactants marketed by BASF.

Nonionic Condensation Products OE of Propylene Oxide / Ethylenediamine Adducts
The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine can be used here. The hydrophobic fragment of these products consists of

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 product of the reaction of ethylenediamine and an excess of propylene oxide, and generally has a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic compounds by BASF.

Mixed nonionic surfactant system
In a preferred embodiment of the present invention, the detergent tablet comprises a mixed nonionic surfactant system comprising at least one nonionic surfactant with low cloud point and at least one nonionic surfactant with high cloud point.

 The "cloud point", as used herein, is a well-known property of nonionic surfactants, which is a result of the fact that the surfactant becomes less soluble as the temperature increases, the temperature at which the appearance of a second phase is observable being called "trouble point" (see Kirk Othmer, Encyclopedia of Chemical Technology, 3rd edition, volume 22, pages 360 to 379).

 As used herein, a "low cloud point" surfactant is defined as a nonionic surfactant system ingredient having a cloud point below 30 C, preferably below 20 C, and most preferably below 10 C Typical low cloud nonionic surfactants include alkoxylated nonionic surfactants, especially ethoxylation products derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers . Thus, these non-ionic surfactants with a low cloud point include, for example, ethoxylated / propoxylated alcohols (for example Poly-tergent SLF 18 from Olin Corporation), polyoxyalkylenated alcohols with epoxy capping (for example the series of nonionics Poly-Tergent SLF18B from Olin Corporation, described for example in document WO 94/22800, published on October 13, 1994 by Olin Corporation), and surfactants of ether-capped polyoxyalkylenated alcohol type.

 The nonionic surfactants can also optionally contain propylene oxide in an amount up to 15% by weight.

Other preferred nonionic surfactants can be prepared by the methods described in US Patent 4,223,163, issued September 16, 1980 to Builloty and incorporated herein by reference.

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 The low cloud nonionic surfactants further comprise a polyoxyethylene / polyoxypropylene block polymer compound.

The polyoxyethylene / polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine serving as initiator compound containing active hydrogen. Some of the block polymeric surfactant compounds called PLURONIC, REVERSED PLURONIC, and TETRONIC, of BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. Preferred examples include REVERSED PLURONIC 25R2 and TETRONIC 702. These surfactants are typically useful here as non-ionic low cloud surfactants.

 As used herein, a "high cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point greater than 40 C, preferably greater than 50 C, and more preferably greater at 60 C. Preferably, the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxylated alcohol or of an alkylphenol containing from 8 to 20 carbon atoms with from 6 to 15 moles of oxide of ethylene per mole of alcohol or alkylphenol, on average. These high cloud point nonionic surfactants include, for example, Tergitol 15S9 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhône Poulenc), and Neodol 91-8 (sold by Shell).

 For the purpose of the present invention, it is also preferred that the non-ionic surfactant with a high cloud point also has a hydro-lipophilic equilibrium value ("HLB"; see Kirk Othmer, above) situated in the range ranging from 9 to 15, preferably from 11 to 15. These materials include, for example, Tergitol 15S9 (sold by Union Carbide), Rhodasurf TMD 8.5 (sold by Rhône Poulenc), and Neodol 91-8 (sold by Shell ).

 Another preferred non-ionic surfactant with a high cloud point is derived from a fatty alcohol with a straight chain or preferably branched, or secondary, containing from 6 to 20 carbon atoms (C6 to C20 alcohol), including secondary alcohols and branched chain primary alcohols.

Preferably, the high cloud point nonionic surfactants are

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 ethoxylation products of branched or secondary alcohols, better still ethoxylation products of branched alcohols, C9 to C11 or C11 to Ci 5, condensed with on average 6 to 15 moles, preferably 6 to 12 moles, and especially 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactants thus derived have a narrow distribution of the oxyethyl radicals relative to the average.

Anionic surfactant
Almost any anionic surfactant useful for detergent purposes is suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and tri-ethanolamine salts) of anionic surfactants of the type sulfate, sulfonate, carboxylate and sarcosinate. Anionic sulfate surfactants are preferred.

 Other anionic surfactants include isethionates such as acylisethionates, N-acyltaurates, methyltauride fatty acid amides, alkylsuccinates and sulfosuccinates, sulfosuccinate monoesters (in particular C12 to Ci g saturated monoesters) , sulfosuccinate diesters (in particular C6 to C14 saturated and unsaturated diesters), N-acylsarcosinates. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in tallow or derived therefrom.

Anionic sulfate surfactant
The anionic sulfate surfactants usable here include alkyl sulfates, ethoxylated alkyl sulfates, (fatty oleyl) glycerolsulfates, ethoxylated, linear and branched, alkylphenol ethersulfates, primary and secondary, sulfates of (C5 to C17 acyl) -N- (CI alkyl to C4) - and-N- (C1 to C2 hydroxyalkyl) glucamine, and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the nonionic non-sulfated compounds being described here).

 The alkyl sulfate surfactants are preferably chosen from linear and branched C10 to Cis primary alkyl sulfates, better still branched chain C11 to C15 alkyl sulfates and straight chain C12 to C14 alkyl sulfates.

 The ethoxylated alkyl sulphate surfactants are preferably chosen

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 overall consisting of C10 to C18 alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the ethoxylated alkyl sulfate surfactant is a C11 to C18, especially C11 to C15, alkyl sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.

 A particularly preferred aspect of the invention employs mixtures of the preferred ethoxylated alkyl sulfate and alkyl sulfate surfactants.

These mixtures are described in PCT patent application N WO 93/18124.

Anionic sulfonate surfactant
Anionic sulfonate surfactants usable here include (C5 to C20 linear alkyl) -benzenesulfonates and estersulfonates salts, C6 to C22 primary or secondary alkanesulfonates, C6 to C24 olefinesulfonates, sulfonated polycarboxylic acids, alkylglycerolsulfonates (fatty acyl) glycerolsulfonates, (fatty oleyl) glycerolsulfonates, and any of their mixtures.

Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include ethoxylated alkylcarboxylates, polyethoxylated alkylpolycarboxylate surfactants and soaps ("alkylcarboxyls"), in particular certain secondary soaps described herein.

 Suitable ethoxylated alkylcarboxylates include those of the formula RO (CH2CH2O) xCH2COO-M + in which R is a C1-6 alkyl group, x ranges from 0 to 10, and the distribution of ethoxylates is such that, on a weight basis amount of material where x is 0 is less than 20%, and M is a cation. Suitable polyethoxylated alkylpolycarboxylate surfactants include those of formula RO- (CHRI- CHR2-0) -R3 in which R is a C6 to C18 alkyl group, x is from 1 to 25, RI and R2 are chosen from the group consisting of hydrogen, a methyl acid radical, a succinic acid radical, a hydroxysuccinic acid radical, and their mixtures, and R3 is chosen from the group consisting of hydrogen, substituted and unsubstituted hydrocarbons having from 1 to 8 atoms carbon, and mixtures thereof.

 Suitable soap surfactants include secondary soap surfactants which contain a carboxyl unit connected to an atom

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 secondary carbon. Secondary soap surfactants which are preferred to be used here are water-soluble elements chosen from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, of 2-ethyl acid -l-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. It is also possible to incorporate certain soaps intended to serve as anti-foaming agents.

Surfactant alkali metal sarcosinate
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R ') CH2COOM, in which R is a C5 to C17 alkyl or alkenyl group, linear or branched, R1 is a C1 to C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Amphoteric surfactant
Amphoteric surfactants usable here include amine oxide surfactants and alkylamphocarboxylic acids.

 Suitable amine oxides include the compounds of formula R3 (OR4) xN0 (R5) 2 wherein R3 is selected from alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl groups, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a poly (ethylene oxide) group containing from 1 to 3 ethylene oxide groups. The oxides of (C10 to C18 alkyl) dimethylamine and the oxides of (acylamidoalkyl C10 to C18) dimethylamine are preferred.

 A suitable example of an alkylamphodicarboxylic acid is Miranol C2M concentrate, manufactured by Miranol Inc., Dayton, NJ.

Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent compositions. These surfactants can be roughly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are

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 examples of zwitterionic surfactants to be used here.

 Suitable betaines are the compounds of formula R (R ') 2N + R2COO- in which R is a C6 to C18 hydrocarbyl group, each R1 is typically a C1 to C3 alkyl group, and R2 is a C1 to hydrocarbyl group C5. The preferred betaines are dimethyl C 12 -C 1 ammoniohexanoates and (C 10 -C 18 acyl) amidopropane (or ethane) dimethyl (or diethyl) betaines.

 Complex betaine surfactants can also be used here.

Cationic surfactants
The cationic ester surfactants used in this invention are preferably water dispersible compounds having surfactant properties, comprising at least one ester bond (i.e., COO-) and at least one cationically charged group. Other suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat. Nos. 4,228,042.4 239,660 and 4,260,529.

 Suitable cationic surfactants include surfactants of the quaternary ammonium type chosen from surfactants of the mono-N- (alkyl or C6 to C16, preferably C6 to C10) ammonium type in which the remaining N positions are substituted by methyl groups , hydroxyethyl or hydroxypropyl.

Enzymes
Enzymes are preferred detergent components of the first phase and more particularly of the second phase and / or any subsequent phases. When present, said enzymes are chosen from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases , keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, P-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or their mixtures .

 Preferred enzymes include proteases, amylases, lipases, peroxidases, cutinases and / or cellulases together with one or more enzymes that degrade the cell wall of plants.

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 The cellulases which can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and an activity exceeding 50 CEVU (cellulose viscosity units). Suitable cellulases are described in US Patent No. 4,435,307 to Barbesgoard et al. and documents J61078384 and WO96 / 02653 which describe fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from new Bacillus species. Suitable cellulases are also described in GB-A-2,075,028, GB-A-2,095,275, DE-OS-2,247,832 and WO95 / 26398.

 Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. Thermoidea), in particular the strain Humicola DSM1800. Other suitable cellulases are cellulases from Humicola insolens having a molecular weight of 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; and an endoglucanase of about 43 kD, derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component to the amino acid sequence described in PCT patent application N WO 91/17243. Suitable cells are also the EGIII cellulases originating from Trichoderma longibrachiatum, described in document WO94 / 21801, Genencor, published on September 29, 1994. Particularly suitable cellulases are the cellulases having advantages in color care. Examples of such cellulases are the cellulases described in European patent application N 91202879. 2, filed on November 6, 1991 (Novo). The enzymes Carezyme and Celluzyme (Novo Nordisk A / S) are particularly useful.

See also documents W096 / 34092, W096 / 17994 and W095 / 24471 for other cellulases suitable for tissue care and / or cleaning properties.

 Said cellulases are normally incorporated into the detergent composition in amounts of 0.0001 to 2% of active enzyme relative to the weight of the detergent composition.

 Peroxidase enzymes are used in combination with oxygen sources, for example percarbonates, perborates,

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 persulfates, hydrogen peroxide, etc. They are used for "bleaching in solution", that is to say to prevent the transfer of dyes or pigments, removed from the substrates during the washing operations, on other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidases such as chloroperoxidase and bromoperoxidase. Detergent compositions containing a peroxidase are described for example in international PCT applications WO 89/099813 and W089 / 09813 and in European patent applications EP N 91202882. 6 filed on November 6, 1991 and EP N 96870013. 8 filed on February 20 1996. Also suitable for the enzyme laccase.

 Preferred enhancers are phenothiazine or substituted phenoxazine: 10-phenothiazinepropionic (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in the document WO 94/12621), as well as the substituted syringates ((C 3 -C 5 alkyl) syringates) and the phenols. As the source of hydrogen peroxide, sodium percarbonate or perborate is preferred.

 Said cellulases and / or peroxidases are normally incorporated into the detergent composition in amounts of 0.0001 to 2% of active enzyme relative to the weight of the detergent composition.

 Other preferred enzymes which can be incorporated into the detergent compositions of the present invention include lipases.

Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, for example Pseudomonas stutzeri ATCC 19,154, as described in GB N 1372 034. Suitable lipases include those which exhibit an immunological cross-reaction positive with the lipase antibody, produced by the fluorescent micro-organism Pseudomonas IAM 1057. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trademark Lipase P "Amano", ci -after called "Amano-P". Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB

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 3673 of Toyo Jozo Co., Tagata, Japan; lipases from Chromobacter viscosum marketed by U.S. Biochemical Corp., USA, and Disoynth Co., The Netherlands, as well as lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as Ml Lipase and Lipomax (Gist-Brocades), and Lipolase # and Lipolase Ultra @ (Novo), which have been found to be very effective when used in combination with compositions of the present invention. Also suitable are the lipolytic enzymes described in documents EP 258 068, WO 92/05249 and WO 95/22615 from Novo Nordisk and in documents WO 94/03578, WO 95/35381 and WO 96/00292 from Unilever.

 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 activation at the interface. The addition of cutinases to detergent compositions has been described for example in documents WO-A-88/09367 (Genencor), WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever) .

 The lipases and / or cutinases are normally incorporated into the detergent composition in amounts ranging from 0.0001 to 2% of active enzyme relative to the weight of the detergent composition.

 Suitable proteases are subtilisins, which 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, the maximum activity of which corresponds to the pH range of 8 to 12, developed and marketed by Novo Industries A / S in Denmark, hereinafter called " Novo ", under the name SPERASE #.

The preparation of this enzyme and analogous enzymes is described in GB Patent No. 1,243,784 to Novo. Other suitable proteases include the enzymes KANNASE, ALCALASE, DURAZYM and SAVINASE from Novo and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (protein genetically produced from Maxacal) from Gist-Brocades. The proteolytic enzymes also include the modified bacterial serine proteases, such as those described in the European patent application bearing the serial number 87 303761. 8, filed on April 28, 1987 (in particular pages 17, 24 and 98), and which are called here

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 "Protease B", and in European patent application 199 404, Venegas, published on October 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, called here "Protease A". Useful is that called here "Protease C", which is a variant of an alkaline serine protease from Bacillus, in which lysine replaces with arginine in position 27, tyrosine replaces with valine in position 104 , the serine replaced by asparagine in position 123, and the alanine replaced by threonine in position 274. Protease C is described in document EP 90915958. 4, corresponding to WO 91/06637, published on May 16, 1991. Genetically modified variants, in particular of Protease C, are also envisaged here.

 A preferred protease, called "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by replacement of a plurality of residues d amino acids by a different amino acid in one position, in said carbonyl hydrolase, equivalent to position +76, preferably also in combination with one or more positions of amino acid residues equivalent to those chosen 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 numbering of the subtilisin of Bacillus amyloliquefaciens, as described in documents W095 / 10591 and the request from C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes" with serial number US N 08/322 677, filed October 13, 1994.

 Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/06637, the BLAP protease described in document WO91 / 02792, and their variants described in document WO 95/23221.

 See also a high pH protease from Bacillus sp. NCIMB 40338 described in document WO 93/8140 A from Novo. WO 92/03529 A from Novo describes enzymatic detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor. If desired, a protease with lower adsorption and higher hydrolysis is available, as described in WO

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 95/07791 by Procter & Gamble. WO 94/25583 from Novo describes a recombinant trypsin-type protease for detergents suitable here.

Other suitable proteases are described in document EP 516,200 from Unilever.

 Other preferred protease enzymes include protease enzymes which are variants of carbonyl hydrolase having an amino acid sequence not found in nature, which are derived by replacement from a plurality of amino acid residues d a precursor carbonylhydrolase with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme correspond 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, where the numbered positions correspond to the natural subtilisin of Bacillus amyloliquefaciens or the equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as the subtilisin of Bacillus lentus). Preferred enzymes of this type include those carrying changes at positions +210, +76, +103, +104, +156, and +166.

 The proteolytic enzymes are incorporated into the detergent composition of the present invention in amounts ranging from 0.0001 to 2%, preferably from 0.001 to 0.2% and more preferably from 0.005 to 0.1% of pure enzyme relative to the weight of the composition.

 Amylases (a or ss) can be incorporated to remove stains based on carbohydrates. WO / 94/02597 of Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions which incorporate amylase mutants. See also document W095 / 10603 of Novo Nordisk A / S, published on April 20, 1995. Other amylases known to be used in cleaning compositions include a- and (3-amylases. A-amylases are known in the art. technical and include those described in US Patents N 5,003,257, EP N 252,666, WO / 91/00353, FR N 2,676,456, EP N 285,123, EP N 525,610, EP N 368,341, and the application for British Patent No. 1,296,839 (Novo) Other suitable amylases are the amylases with enhanced stability, described in documents WO 94/18314, published on August 18

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 1994, and WO96 / 05295 from Genencor, published February 22, 1996, and amylase variants carrying an additional modification in the immediate parent strain, available from Novo Nordisk A / S and described in document WO 95/10603, published in April 1995. The amylases described in documents EP 277 716, W095 / 26397 and W096 / 23873 (all from Novo Nordisk) are also suitable.

 Examples of commercially produced α-amylases are Purafect Ox Am # from Genencor and Termamyl, Ban #, Fungamyl and Duramyl, Natalase, all available from Novo Nordisk A / S, Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% greater than the specific activity of Termamyl in the temperature range from 25 C to 55 C and in the pH range from 8 to 10, as measured by the Phadebas α-amylase activity assay. The variants of the above enzymes, described in document WO96 / 23873 (Novo Nordisk) are suitable. Other amylolytic enzymes having improved properties regarding the activity level and the combination of thermal stability and a higher activity level are described in WO95 / 35382.

 Preferred amylase enzymes include those described in WO95 / 26397 and in the pending application PCT / DK96 / 00056 from Novo Nordisk.

 The amylolytic enzymes are incorporated into the detergent composition of the present invention in amounts ranging from 0.0001 to 2%, preferably from 0.00018 to 0.06% and more preferably from 0.00024 to 0.048% of pure enzyme relative to the weight of the composition.

 In a particularly preferred embodiment, the detergent tablets of the present invention comprise amylase enzymes, in particular those described in document WO95 / 26397 and in the simultaneously pending application PCT / DK96 / 00056 from Novo Nordisk, in combination with an amylase complementary.

 By "complementary" is meant the addition of one or more amylases suitable for detergency purposes. Examples of complementary amylases (a and / or P) are described below. W094 / 02597 and W095 / 10603 from Novo Nordisk A / S describe

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 cleaning compositions which incorporate amylase mutants. Other amylases known to be used in cleaning compositions include a- and (3-amylases. A-amylases are known in the art and include those described in US Pat. Nos. 5,003,257, EP No. 252,666, WO / 91/00353, FR N 2 676 456, EP N 285 123, EP N 525 610, EP N 368 341, and British patent application N 1 296 839 (Novo). Other suitable amylases are the stable amylases. enhanced, described in documents WO 94/18314 and W096 / 05295 from Genencor, and amylase variants carrying an additional modification in the immediate parent strain, available from Novo Nordisk A / S and described in document WO 95/10603 Also suitable are the amylases described in document EP 277 716 (Novo Nordisk). Examples of commercially produced α-amylases are Purafect Ox Am # from Genencor and Termamyl, Ban #, Fungamyl and Duramyl, all available from Novo. Nordisk A / S, Denmark, document W095 / 26397 crit of other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% greater than the specific activity of Termamyl in the temperature range from 25 C to 55 C and in the pH range from 8 to 10, as measured by the Phadebas # α-amylase activity assay. The variants of the above enzymes, described in document WO96 / 23873 (Novo Nordisk) are suitable. Other amylolytic enzymes having improved properties regarding the activity level and the combination of thermal stability and a higher activity level are described in WO95 / 35382. Preferred complementary amylases in the present invention are the amylases sold under the trade names Purafect Ox Am #. described in documents WO 94/18314 and W096 / 05295, sold by Genencor; Termamyl #, Fungamyl, Ban #, Natalase and Duramyl, all available from Novo Nordisk A / S, and Maxamyl from Gist- Brocades.

 Said complementary amylase is generally incorporated in the detergent compositions of the present invention in an amount of 0.0001 to 2%, preferably from 0.00018 to 0.06%, more preferably from 0.00024 to 0.048% of pure enzyme relative to the weight of the composition. Preferably, the weight ratio of pure enzyme of the specific amylase to

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 the complementary amylase is between 9/1 and 1/9, better still between 4/1 and 1/4, and especially between 2/1 and 1/2.

 The enzymes mentioned above may have any suitable origin, for example a plant, animal, bacterial or fungal origin, or may also come from a yeast. Their origin can also be mesophilic or extremophilic (psychrophile, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halogenophilic, etc.). Purified or unpurified forms of these enzymes can be used. This definition also includes mutants of native enzymes. The mutants can be obtained for example by protein and / or genetic, chemical and / or physical engineering modifications of native enzymes. It is also common practice to express the enzyme by host organisms into which the genetic material responsible for producing the enzyme has been cloned.

 Said enzymes are normally incorporated into the detergent composition in amounts ranging from 0.0001 to 2% of active enzyme relative to the weight of the detergent composition. Enzymes can be added as separate single ingredients (nuggets, aggregates, stabilized liquids, etc., containing an enzyme), or as mixtures of two or more enzymes (e.g. co-aggregates).

 Other suitable detergent ingredients which can be added are enzyme oxidation fixers which are described in the simultaneously pending European patent application 92870018.6 filed January 31, 1992. Examples of such enzyme oxidation fixers are ethoxylated tetraethylene polyamines .

 Various enzymatic materials and means for their incorporation in synthetic detergent compositions are also described in documents WO 9307263 A and WO 9307260 A of Genencor International, WO 8908694 A of Novo, and US N 3,553,139 of January 5, 1971 of McCarty et al . Enzymes are further described in US Pat. Nos. 4,101,457, Place et al., Of July 18, 1978 and US Pat. No. 4,507,219, Hughes, of March 26, 1985. Enzymatic materials useful for liquid detergent formulations, and their incorporation in these formulations, are described in US Pat. No. 4,261,868, Hora et al., of April 14, 1981. Enzymes for use in detergents can be stabilized by various

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 techniques. Enzyme stabilization techniques are described and exemplified in US Pat. Nos. 3,600,319 of August 17, 1971, Gedge et al., EP N 199,405 and EP 200,586 of October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US Patent 3,519,570. A useful Bacillus, sp. AC 13, giving proteases, xylanases and cellulases, is described in document WO 9401532A from Novo.

Bleaching agent
A particularly preferred component of the composition of detergent components is a bleach. Suitable bleaching agents include chlorine-releasing and oxygen-releasing bleaches.

 In a preferred aspect, the oxygen-releasing bleach contains a source of hydrogen peroxide and a precursor compound of organic peroxyacid bleach. The production of the organic peroxyacid takes place by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include mineral bleaches.

In another preferred aspect, a preformed organic peroxyacid is incorporated directly into the composition. Compositions are also contemplated containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Perhydrated mineral bleaches
The detergent component compositions preferably include a source of hydrogen peroxide, serving as a bleaching agent releasing oxygen. Suitable sources of hydrogen peroxide include inorganic perhydrated salts.

 The mineral perhydrated salts are normally incorporated in the form of the sodium salt, in an amount of 1 to 40% by weight, better still from 2 to 30% by weight and especially from 5 to 25% by weight relative to the compositions.

 Examples of inorganic perhydrated salts include the perborate, percarbonate, perphosphate, persulfate and persilicate salts. Inorganic perhydrated salts are normally alkali metal salts. The

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 mineral perhydrated salt can be incorporated in crystalline solid form without additional protection. However, for certain perhydrated salts, the preferred embodiments of these granular compositions use a coated form of the material, which offers better storage stability of the perhydrated salt in the granular product.

 The sodium perborate can be in the monohydrate form, of nominal formula NaB02H202, or tetrahydrate, NaB02H202.3H20.

 The alkali metal percarbonates, in particular sodium percarbonate, are the preferred perhydrated compounds for incorporation in the compositions according to the invention. Sodium percarbonate is an addition compound having the formula corresponding to 2Na2CO3; 3H202, and it is commercially available as a crystalline solid. Sodium percarbonate, which is a hydrogen peroxide addition compound, tends, upon dissolution, to rapidly release hydrogen peroxide, which can increase the tendency for high localized concentrations to appear. bleaching agent. Most preferably, the percarbonate is incorporated into these compositions in a coated form which provides stability in the product.

 A suitable coating providing stability in the product comprises a mixed salt of water-soluble alkali metal sulfate and carbonate. These coatings, as well as the coating methods, have been described previously in the document GB-1 466 799, assigned to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to percarbonate is situated in the range ranging from 1/200 to 1/4, better still from 1/99 to 1/9, and especially from 1/49 to 1/19. Preferably, the mixed salt consists of sodium sulfate and sodium carbonate and corresponds to the general formula Na2SO4 # nNa2CO3 in which n is from 0.1 to 3, preferably from 0.3 to 1.0 and very especially from 0.2 to 0.5.

 Another suitable coating material providing stability in the product comprises sodium silicate having an SiO2 / Na20 ratio of 1.8 / 1 to 3.0 / 1, preferably 1.8 / 1 to 2.4 / 1, and or sodium metasilicate, preferably applied in an amount of 2 to 10% (normally 3 to 5%) of SiO2 relative to the weight of the mineral perhydrated salt.

The coating may also include magnesium silicate. Also suitable for coatings which contain silicate and borate salts or

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 boric acids or other mineral compounds.

 In the present invention, it is also advantageous to use other coatings which contain waxes, oils or fatty soaps.

 Another mineral perhydrate salt useful in the compositions presented here is potassium peroxymonopersulfate.

où L est un groupe partant et X est pratiquement n'importe quelle fonctionnalité, de telle sorte que, lors de la perhydrolyse, la structure du peroxyacide produit est la suivante :

Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. In general, the peroxyacid bleach precursors can be represented in the following way:

where L is a leaving group and X is practically any functionality, so that, during perhydrolysis, the structure of the peroxyacid produced is as follows:

The peroxyacid bleach precursor compounds are preferably incorporated in an amount of 0.5 to 20% by weight, better still from 1 to 10% by weight, especially from 1.5 to 5% by weight relative to the compositions.

 Typically, suitable peroxyacid bleach precursor compounds contain one or more N- or O-acyl groups, these precursors being able to be chosen from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acyl derivatives of imidazoles and oximes. Examples of useful materials falling into these classes are described in GB-A-1,586,789. Suitable esters are described in GB-A-836,988,864,798.1 147,871.2 143,231 and EP-A- 0 170 386.

Leaving groups
The leaving group, hereinafter called group L, must be sufficiently reactive for the perhydrolysis reaction to take place within an interval of

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 optimal time (for example a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

et leurs mélanges, où R' est un groupe alkyle, aryle ou alcaryle contenant de 1 à 14 atomes de carbone, R3est une chaîne alkyle contenant de 1 à 8 atomes de carbone, R4 est H ou R3, R5 est une chaîne alcényle contenant de 1 à 8 atomes de carbone et Y est H ou un groupe solubilisant. L'un quelconque de R', R3 et R4 peut être substitué par pratiquement n'importe quel groupe fonctionnel, y compris, par exemple, les groupes alkyle, hydroxy, alcoxy, halogéno, amino, nitrosyle, amido et ammonium ou alkylammonium. Preferred L groups are chosen from the group consisting of:

and mixtures thereof, where R '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 R ', R3 and R4 can be substituted by virtually any functional group, including, for example, alkyl, hydroxy, alkoxy, halo, amino, nitrosyl, amido and ammonium or alkylammonium.

 The preferred solubilizing groups are -S03-M +, -CO2-M +, -SO4-M +, -N + (R3) 4X- and 0 <-N (R3) 3, and especially -SO3-M + and -CO2-M + where R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation

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 which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium being very particularly preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor
Perbenzoic acid precursor compounds generate perbenzoic acid during perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, including, for example, benzoyloxybenzenesulfonate:

Ac = COCH3 ; Bz = benzoyle
Les composés précurseurs d'acide perbenzoïque du type imide comprennent le N-benzoylsuccinimide, la tétrabenzoyléthylènediamine et les urées à substitution N-benzoyle. Des précurseurs d'acide perbenzoïque de type imidazole convenables comprennent le N-benzoylimidazole et le N- benzoylbenzimidazole, et d'autres précurseurs d'acide perbenzoïque contenant un groupe N-acyle utiles comprennent la N-benzoylpyrrolidone, la dibenzoyltaurine et l'acide benzoylpyroglutamique. Also suitable are benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including, for example:

Ac = COCH3; Bz = benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid .

 Other perbenzoic acid precursors include benzoyl diacylperoxides, benzoyl tetraacylperoxides, and the compound of formula:

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Phthalic anhydride is another precursor compound of perbenzoic acid suitable here:

dans laquelle n vaut de 0 à 8, de préférence de 0 à 2, et R6 est un groupe benzoyle. Suitable perbenzoic acid precursors of the N-acylated lactam type correspond to the formula:

in which n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.

Perbenzoic acid derivatives precursors
Precursors of perbenzoic acid derivatives provide substituted perbenzoic acids during perhydrolysis.

 Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic precursors described herein in which the benzoyl group is substituted by virtually any non-positively charged (i.e. non-cationic) functional group y including, for example, alkyl, hydroxy, alkoxy, halo, amino, nitrosyl and amido.

A preferred class of precursor compounds of substituted perbenzoic acid comprises the amide-substituted compounds corresponding to one of the general formulas:

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 wherein R 'is an aryl or aralkyl group having from 1 to 14 carbon atoms; R2 is an arylene or alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aiyl or alkaryl group containing from 1 to 10 carbon atoms, and L can be virtually any leaving group. R 'preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R 'may be an aryl, substituted aryl or alkylaryl group containing branches, substitutions or both, and may be from synthetic or natural sources, including, for example, tallow. Similar structural variations are allowed for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical organic compounds or substituent groups. Preferably, R5 is H or the methyl group, R 'and R5 should not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in document EP-A-0 170 386.

Cationic peroxyacid precursors
The cationic peroxyacid precursor compounds produce cationic peroxyacids during perhydrolysis.

 Typically, cationic peroxyacid precursors are formed by replacing 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 methyl-ammonium group. . The cationic peroxyacid precursors are typically present in the compositions in the form of a salt with a suitable anion, such as, for example, a halide ion or a methyl sulfate ion.

 The peroxyacid precursor compound to have such a cationic substitution can be a precursor compound of a perbenzoic acid, or of a substituted derivative of such an acid, as described above. Alternatively, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide substituted alkylperoxyacid precursor as described below.

 Cationic peroxyacid precursors are described in US Patents 4,904,406.4 751,015.4 988,451.4 397,757.5 269,962, 5,127,852.5,093,022.5 106,528, GB 1,382,594, EP 475 512, 458 396 and 284 292,

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 and JP 87-318 332.

 Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium substituted alkyl or benzoyl oxybenzenesulfonates, N-acylated caprolactams, and monobenzoyltetraacetylglucosebenzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzenesulfonate is the 4- (trimethylammonium) methyl derivative of benzoyl oxybenzenesulfonate:

A preferred cationically substituted alkyl oxybenzenesulfonate has the formula:

Preferred cationic peroxyacid precursors from the class of N-acylated caprolactams include trialkylammonium-methylene-benzoylcaprolactams, in particular trimethylammonium-methylene-benzoylcaprolactam:

Other preferred cationic peroxyacid precursors from the class of N-acylated caprolactams include trialkylammonium-methylene-alkylcaprolactams:

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dans laquelle n vaut de 0 à 12, en particulier de 1 à 5.

in which n is from 0 to 12, in particular from 1 to 5.

 Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) ethyl sodium carbonate-4-sulfophenyl chloride.

Alkylpercarboxylic acid bleach precursors
The alkylpercarboxylic acid bleach precursors form percarboxylic acids during perhydrolysis. Preferred precursors of this type provide peracetic acid during perhydrolysis.

 Preferred alkylpercarboxylic acid compounds of the imide type include N, N, N1, N1-tetraacetylalkylenediamines in which the alkylene group contains 1 to 6 carbon atoms, in particular compounds in which the alkylene group contains 1, 2 or 6 carbon atoms. Particularly preferred is tetraacetylethylenediamine (TAED).

 Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

dans lesquelles R est un groupe alkyle ayant de 1 à 14 atomes de carbone ; R2est un groupe alkylène contenant de 1 à 14 atomes de carbone, et R5 est H ou un groupe alkyle contenant de 1 à 10 atomes de carbone, et L peut être pratiquement n'importe quel groupe partant. R' contient de préférence de 6 à 12 atomes de carbone. R2 contient de préférence de 4 à 8 atomes de carbone. R' peut être un groupe alkyle à chaîne droite ou ramifiée contenant Amide substituted alkylperoxyacid precursors
Amide-substituted alkylperoxyacid precursor compounds are also suitable, including those of the following general formulas:

wherein R is an alkyl group having 1 to 14 carbon atoms; R2 is an alkylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing from 1 to 10 carbon atoms, and L can be virtually any leaving group. R 'preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R 'can be a straight or branched chain alkyl group containing

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 offshoots, substitutions, or both, and can come from synthetic or natural sources, including, for example, tallow. Similar structural variations are allowed for R2. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical organic compounds or substituent groups. Preferably, R5 is H or the methyl group, R 'and R5 should not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in document EP-A-0 170 386.

y compris les benzoxazines substituées de type :

où RI est H ou un groupe alkyle, alcaryle, aryle, arylalkyle, et où R2, R3, R4 et R5 peuvent être des substituants identiques ou différents choisis parmi H, les halogènes et les fonctions alkyle, alcényle, aryle, hydroxyle, alcoxyle, amino, alkylamino, COOR6 (où R6 est H ou un groupe alkyle) et carbonyle. Benzoxazine-type organic peroxyacid precursors
Also suitable are the precursor compounds of the benzoxazine type, as described for example in documents EP-A-332,294 and EP-A-482,807, in particular those of formula:

including substituted benzoxazines of type:

where R1 is H or an alkyl, alkaryl, aryl, arylalkyl group, and where R2, R3, R4 and R5 may be identical or different substituents chosen from H, halogens and the alkyl, alkenyl, aryl, hydroxyl, alkoxyl functions, amino, alkylamino, COOR6 (where R6 is H or an alkyl group) and carbonyl.

A particularly preferred benzoxazine type precursor is the following:

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Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to or in place of an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, usually in an amount of 0.5 to 25% by weight, more preferably from 1 to 10% by weight relative to the composition.

dans lesquelles R1 est un groupe alkyle, aryle ou aralkyle ayant de 1 à 14 atomes de carbone ; R2 est un groupe alkylène, arylène ou alcarylène contenant de 1 à 14 atomes de carbone, et R5 est H ou un groupe alkyle, aryle ou alcaryle contenant de 1 à 10 atomes de carbone. R1 contient de préférence de 6 à 12 atomes de carbone. R2 contient de préférence de 4 à 8 atomes de carbone. R1 peut être un groupe alkyle à chaîne droite ouy ramifiée, aryle substitué ou alkylaryle, contenant des ramifications, des substitutions ou les deux, et peut provenir de sources synthétiques ou de sources naturelles, y compris, par exemple, le suif. Des variations de structure analogues sont autorisées pour R2. La substitution peut comprendre des groupes alkyle, aryle, halogène, azote, soufre et d'autres composés organiques ou groupes substituants typiques. De préférence, R5 est H ou le groupe méthyle, R' et R5 ne devraient pas contenir plus de 18 atomes de carbone au total. Des peroxyacides organiques à substitution amide de ce type sont décrits dans le document EP-A-0 170 386. A preferred class of organic peroxyacid compounds includes the amide substituted compounds of the following general formulas:

wherein R1 is an alkyl, aryl or aralkyl group having from 1 to 14 carbon atoms; R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl group 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 a straight or branched chain alkyl, substituted aryl or alkylaryl group, containing branches, substitutions, or both, and may be from synthetic or natural sources, including, for example, tallow. Similar structural variations are allowed for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical organic compounds or substituent groups. Preferably, R5 is H or the methyl group, R 'and R5 should not contain more than 18 carbon atoms in total. Amide-substituted organic peroxyacids of this type are described in document EP-A-0 170 386.

 Other organic peroxyacids include the diacyl- and tetraacyl-peroxides, in particular diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. As the organic peroxyacid, dibenzoyl peroxide is preferred here.

Also suitable here are mono- or di-perazelaic acid, mono- or di-perbrassylic acid and N-phthaloylaminoperoxycaproic acid.

Controlled speed release means
Means can be provided to control the rate of release of bleaching agent, in particular oxygenated bleaching agent, into the washing solution.

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 The means for controlling the rate of release of the bleaching agent may allow the controlled release of peroxide species in the washing solution. These means could, for example, include controlling the release of any inorganic perhydrated salt, acting as a source of hydrogen peroxide, in the washing solution.

 Another mechanism for controlling the rate of release of bleach may be to coat the bleach with a coating designed to allow controlled release. The coating may therefore comprise, for example, a material poorly soluble in water, or be a coating having a thickness sufficient for the kinetics of dissolution of the thick coating to control the rate of release.

 The coating material can be applied using various methods. Any coating material is typically present in a weight ratio of the coating material to the bleaching agent from 1/99 to 1/2, preferably from 1/49 to 1/9.

 Suitable coating materials include triglycerides such as vegetable oil, soybean oil, hydrogenated cottonseed oil (for example partially), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any of their mixtures.

 Other suitable coating materials may include alkali or alkaline earth metal sulfates, silicates and carbonates, including calcium carbonate and silicas.

 A preferred coating material, in particular for a source of mineral perhydrated salt bleach, comprises sodium silicate with an SiO 2 / Na 2 O ratio of 1.8 / 1 to 3.0 / 1, preferably of 1.8 / 1 to 2.4 / 1, and / or sodium metasilicate, preferably applied in an amount of 2 to 10% (normally 3 to 5%) of SiO2 relative to the weight of the mineral perhydrate salt. The coating may also include magnesium silicate.

 Any coating material based on mineral salt can be combined with organic binder materials to make composite coatings mineral salt / organic binder. Suitable binders

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 include the ethoxylation products of C10 to C20 alcohols containing 5 to 100 moles of ethylene oxide per mole of alcohol and, better still, the ethoxylation products of primary C15 to C20 alcohols containing 20 to 100 moles of ethylene oxide per mole of alcohol.

 Other preferred binders include certain polymeric materials.

As examples of such polymeric materials, mention may be made of polyvinylpyrrolidones having an average molecular weight of 12,000 to 700,000 and polyethylene glycols (PEG) having an average molecular weight of 600 to 5 x 10 6, preferably 1,000 to 400,000, especially from 1,000 to 10,000.

 Other examples of polymeric materials useful as binding agents include copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride constituting at least 20 % in moles of the polymer. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the ethoxylation products of C10 to C20 alcohols mentioned above containing from 5 to 100 moles of ethylene oxide per mole. Other examples of binders include C10 to C20 monoglycerol and diglycerol ethers and also C10 to C20 fatty acids.

 Other examples of binders which can be used here include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, as well as polycarboxylic acids, homolymers or copolymers or their salts.

 A method of applying the coating material involves agglomeration. Preferred agglomeration methods include the use of any of the organic binder materials described above. Any conventional agglomerator / mixer can be used, including, but not limited to, the bin, rotary drum and vertical mixer types. The molten coating compositions can also be applied either by being poured onto a movable bed of bleaching agent, or by being sprayed on it by spraying.

 Other means for achieving the required controlled release include mechanical means for altering the physical characteristics of the bleaching agent in order to control its solubility and speed of release. Suitable protocols could include

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 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 depends both on the composition of the particulate component and on the desire to meet the desired kinetics of controlled release, it is desirable that the particle size is greater than 500 micrometers and preferably that the average particle size is from 800 to 1200 micrometers.

 Additional protocols for providing the means for controlled release include the suitable choice of any other components of the detergent composition matrix so that when the composition is introduced into the washing solution, the ionic strength environment provided therein allows obtaining the required kinetics of controlled release.

Metal-containing bleaching catalyst
The compositions described herein, which contain a bleach as a detergent component, may further include, as a preferred component, a metal-containing bleach catalyst. Preferably, the bleaching catalyst containing a metal is a bleaching catalyst containing a transition metal, more preferably a bleaching catalyst containing manganese or cobalt.

 A suitable type of bleaching catalyst is one comprising a heavy metal cation having a defined bleaching catalytic activity, such as copper or iron cations, an auxiliary metal cation having little or no bleaching catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the cations of catalytic and auxiliary metals, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid), and their water-soluble salts. These catalysts are described in US Pat. No. 4,430,243.

 Preferred types of bleaching catalysts include the manganese-based complexes described in US Patent No. 5,246,621 and US Patent No. 5,244,594. As preferred examples of these catalysts, mention may be made of MnIV2 (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF6) 2, MnIII2 (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-

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triazacyclononane)a(CIOa)2, le MnIIIMnIV4(u-0) (u-OAc )2( 1,4, 7-triméthyl- 1,4,7-triazacyclononane)2(ClO4)3, et leurs mélanges. D'autres tels composés sont décrits dans la demande publiée de brevet européen N 549 272. triazacyclononane) 2 (CI04) 2, MnIV4 (uO) 6 (1,4,7-

triazacyclononane) a (CIOa) 2, MnIIIMnIV4 (u-0) (u-OAc) 2 (1,4, 7-trimethyl-1,4,7-triazacyclononane) 2 (ClO4) 3, and mixtures thereof. Other such compounds are described in the published European patent application N 549 272.

Other ligands which can be used here 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 their mixtures.,
The bleaching catalysts useful in the compositions presented herein can also be selected as required for the present invention. For examples of suitable bleaching catalysts, see US Patent No. 4,246,612 and US Patent No. 5,227,084. Also see US Patent No. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn ( 1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH3) 3- (PF6).

* Yet another type of bleaching catalyst, as described in US Pat. No. 5,114,606, is a water-soluble complex of manganese (III) and / or (IV) with a ligand which is a non-polyhydroxy compound carboxylate having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

dans laquelle chacun de R1, R2, R3 et R4 peut être choisi parmi H et les groupes alkyle et aryle substitués, de façon que R1-N=C-R2 et R3-C=N-R4 forment un cycle à cinq ou six chaînons. Ledit cycle peut en outre être substitué. B est un groupe pontant choisi parmi 0, S, CR5R6, NR7 et C=O, où chacun de R5, R6et R7 peut être H ou un groupe alkyle ou aryle, y compris un groupe substitué ou non substitué. Des ligands préférés comprennent les cycles pyridine, pyridazine, pyrimidine, pyrazine, US Patent No. 5,114,611 teaches a bleaching catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu, with a non (macro) cyclic ligand. The ligands correspond to the formula:

wherein each of R1, R2, R3 and R4 may be selected from H and substituted alkyl and aryl groups, such that R1-N = C-R2 and R3-C = N-R4 form a five or six membered ring . Said cycle can also be substituted. B is a bridging group selected from 0, S, CR5R6, NR7 and C = O, where each of R5, R6 and R7 may be H or an alkyl or aryl group, including a substituted or unsubstituted group. Preferred ligands include the pyridine, pyridazine, pyrimidine, pyrazine rings,

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 imidazole, pyrazole and triazole. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleaching catalysts include the complexes of Co, Cu, Mn, Fe and bispyridylmethane or bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl2, di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) 202CI04, bis (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate, and mixtures thereof.

 Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII (u-O) 2MnIV (N4) + and [bipy2MnIII (u-O) 2MnIVbipy2] - (ClO4) 3.

 Although the structures of the manganese bleaching catalyst complexes of the present invention have not been elucidated, it can be assumed that they include chelates or other hydrated coordination complexes which result from the interaction of carboxyl groups and nitrogen atoms of the ligand with the manganese cation. Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and it may be the valence state (+11), (+111), (+ IV) or (+ V). Because of the six possible points of attachment of the ligands to the manganese cation, it can be reasonably assumed that structures of the polynuclear and / or "cage" type may exist in aqueous bleaching media. Whatever form of the active Mn-ligand species that actually exists, it works in an apparently catalytic manner to provide improved bleaching performance on stubborn stains such as tea, ketchup, coffee stains, of wine, juice and the like.

 Other bleaching catalysts are described, for example, in the published European patent application N 408 131 (complex cobalt catalysts), the published European patent applications N 384 503 and 306 089 (metalloporphyrin catalysts), the patent US N 4 728 455 (manganese catalyst / multidentate ligand), US patent N 4 711 748 and the published European patent application N 224 952 (manganese catalyst absorbed by an aluminosilicate), US patent N 4 601 845 (support

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 aluminosilicate with a manganese salt and zinc or magnesium), US patent N 4,626,373 (manganese / ligand catalyst), US patent N 4,119,557 (ferric complex catalyst), German patent application N 2 054 019 (cobalt chelating catalyst), Canadian patent N 866 191 (salts containing transition metals), US patent N 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations), and US patent N 4,728,455 (manganese gluconate catalysts).

Other preferred examples include the cobalt (III) catalysts of formula:
Co [(NH3) nM'mB'bT'tQqPp] Yy in which the cobalt is in the +3 oxidation state; is an integer from 0 to 5 (preferably 4 or 5, especially 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; especially 1); represents a bidentate ligand; is an integer from 0 to 2; T 'represents a ttidentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; is a pentadentate ligand; p is 0 or 1; n + m + 2b + 3t + 4q + 5p = 6; is one or more suitably selected counter anions, present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; especially 2 when Y is a charged anion-1), to obtain a salt with balanced charge, and preferably Y is chosen from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate ions and combinations thereof; and in which, in addition, at least one of the coordination sites attached to the cobalt is labile under conditions of use in automatic dishwashing and the remaining coordination sites stabilize the cobalt under conditions of automatic washing of the dishes, such that the reduction potential of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volt (preferably less than 0.2 volt) compared to a hydrogen electrode normal.

 Preferred cobalt catalysts of this type have the formula: [Co (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5; especially 5); M 'is a fragment of labile coordination, chosen from

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 preferably in the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) their combinations; m is an integer from 1 to 3 (preferably 1 or 2; especially 1); m + n = 6; and Y is an appropriately selected counter anion, present in a number y, which is an integer of 1 to 3 (preferably 2 to 3; especially 2 when Y is a charged anion-1), to obtain a balanced load salt.

 The preferred cobalt catalysts of this type useful here are the cobalt-pentamine chloride salts of the formula [Co (NH3) 5Cl] Yy, and in particular [Co (NH3) 5Cl] Cl2.

 More preferred are the compositions of the present invention which use cobalt (III) bleaching catalysts of the formula: [Co (NH3) n (M) m (B) b] Ty in which the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated with cobalt by a single 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 suitably selected counter anions present in a number y where y is an integer so as to obtain a salt with balanced charge (preferably y is from 1 to 3; especially 2 when T is an anion loaded -1); and wherein, in addition, said catalyst has a base hydrolysis rate constant of less than 0.23 M-1s-1 (at 25 C).

 The preferred T radicals are chosen from the group consisting of chloride, iodide, 13-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6-, BF4 ', B (Ph) 4 ions. -, phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T can be protonated if there is more than one anionic group in T, for example HPO42-, HCO3-, H2PO4-, etc. In addition, T can be chosen from the group consisting of non-traditional mineral anions such as anionic surfactants (for example linear alkylbenzenesulfonates (LAS), alkylsulfates (AS), ethoxylated alkylsulfonates (AES), etc.), and / or the anionic polymers (for example polyacrylates, polymethacrylates, etc.).

 Fragments M include, but are not limited to, for example, F-, solo, NCS-, SCN-, S2O32-, NH3, PO43-, and carboxylates (which preferably are monocarboxylates, but more than one carboxylate can be

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present in the fragment as long as cobalt is only bound by one carboxylate per fragment, in which case the other carboxylate in fragment M may be protonated or be in its salt form). Optionally, M can be protonated if there is more than one anionic group in M (for example HPO42-, HC03-, H2P04 ', HOC (0) CH2C (0) 0-, etc). The preferred fragments M are the substituted and unsubstituted CI to C30 carboxylic acids of formula:
RC (O) O- in which R is preferably chosen from the group consisting of hydrogen and unsubstituted and substituted C1 to C30 (preferably C1 to C18) alkyl radicals, C6 to C30 aryl (of preferably C6 to C18) unsubstituted and substituted, and heteroaryl C3 to C30 (preferably C5 to C18) unsubstituted and substituted, where the substituents are chosen from the group consisting of -NR'3, -NR'4 \ -C (O) OR ', -OR', -C (O) NR'2, where R 'is chosen from the group consisting of hydrogen and fragments from CI to C6. Consequently, these substituted R radicals include the fragments - (CH2) nOH and - (CH2) nNR'4 +, where n is an integer from 1 to 16, preferably from 2 to 10, and especially from 2 to 5.

 Very particularly preferred fragments M are carboxylic acids corresponding to the above formula in which R is chosen from the group consisting of hydrogen and methyl or ethyl, linear or branched C4 to C12 alkyl radicals, and benzyl. The most especially preferred fragment R is the methyl radical. Preferred M carboxylic acid moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, and acids stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and in particular acetic acid.

 Fragments B include the carbonate, dicarboxylate and higher carboxylate radicals (for example oxalate, malonate, malic, succinate, maleate), picolinic acid, and the a- and P-amino acids (for example glycine, alanine, (3- alanine, phenylalanine).

 The cobalt bleaching catalysts useful here are known and are described, for example, in conjunction with their hydrolysis rates of

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 bases, in M.L. Tobe, "Base Hydrolysis of Transition-Métal Complexes", Adv. Inorg. Bioinorg. Mech. (1983), 2, pages 1 to 94. For example, Table 1 on page 17 indicates the rates of hydrolysis of bases (here called kOH) for cobalt-pentamine catalysts complexed with an oxalate (kOH = 2.5 x 10-4 M-1s-1 (at 25 C)), NCS- (kOH = 5.0 x 10-4 M-1s-1 (at 25 C)), a formate (kOH = 5.8 x 10 -4 M-1s-1 (at 25 C)) and an acetate (koH = 9.6 x 10-4 M-1s-1 (at 25 C)). The especially preferred cobalt catalysts useful herein are the cobalt-pentamine acetate salts of the formula [Co (NH3) 50Ac] Ty in which OAc represents an acetate moiety, and in particular the cobalt-pentamine acetate chloride [Co ( NH3) 5OAc] Cl2; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 50Ac] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2 (here called "PAC").

 These cobalt catalysts are easily prepared by known procedures, such as those taught for example in the article by Tobe above and the references cited therein, in US Pat. No. 4,810,410 to Diakun et al., issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-1045; The Synthesis and Characterization of Inorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pages 461 to 463; Inorg.

Chem. 18, 1497-1502 (1979); Inorg. Chem. 21.2881-2885 (1982); Inorg.

Chem. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry 56, 22-25 (1952); as well as the synthesis examples presented below.

 Cobalt catalysts suitable 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, the descriptions of which are incorporated herein reference.

 These catalysts can be treated together with additive materials so as to reduce the impact on colors, if desired, for the aesthetics of the product, or so as to incorporate them into particles containing enzymes, as indicated in example. below, or alternatively, the compositions can be made so that they contain catalyst "spots".

Organic polymer compound

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According to the invention, organic polymeric compounds can be added as preferred components of the detergent tablets. By "organic polymeric compound" is meant virtually any organic polymeric compound commonly found in detergent compositions, having dispersing, anti-redeposition, soil removal or other detergent properties.

 The organic polymer compound is typically incorporated in the detergent compositions of the invention in an amount of 0.1 to 30%, preferably 0.5 to 15%, especially 1 to 10% by weight relative to the compositions.

 Examples of organic polymeric compounds include water-soluble organic homopolymeric or copolymeric polycarboxylic acids, modified polycarboxylates or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated by at most two carbon atoms. The polymers of the latter type are described in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 2,000 to 10,000 and their copolymers with any other suitable monomer units, including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acids or their salts, maleic anhydride, acrylamide, alkylene, vinyl methyl ether, styrene and any of their mixtures. 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 of less than 15,000 include those sold under the trademark Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the registered trademark Acusol 45N, 480N, 460N by Rohm and Haas.

 The 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 a salt thereof and b) 10 to 90%, preferably 20 to 80% by weight of a substituted acrylic monomer or of a salt thereof, of general formula - [CR2-CRI (CO- O-R3)] - in which at least 1 '' one of the substituents Ri, R2 and R3, of

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 preferably R1 or R2, is an alkyl or hydroxyalkyl group having from 1 to 4 carbon atoms, RI or R2 can be hydrogen and R3 can be hydrogen or an alkali metal salt. Most preferred is a substituted acrylic monomer wherein R1 is the methyl radical and R2 is hydrogen (i.e., a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3,500 and contains 60 to 80% by weight of acrylic acid and 40 to 20% by weight of methacrylic acid.

 Polyamines and modified polyamine compounds are useful here, including those derived from aspartic acid such as those described in documents EP-A-305,282, EP-A-305,283 and EP-A-351,629.

 Other optional polymers can be poly (vinyl alcohols) and acetates, modified or unmodified, celluloses and modified celluloses, polyoxyethylenes, polyoxypropylenes, and their copolymers, modified or unmodified, ethylene glycol terephthalate esters or propylene glycol, or mixtures thereof with polyoxyalkylene units.

 Suitable examples are described in US Pat. Nos. 5,591,703.5,597,789 and 4,490,271.

Soil removal agents
Suitable polymeric soil-removing agents include soil-removing agents having: (a) one or more nonionic hydrophilic components consisting primarily of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization from 2 to 10, in which said hydrophilic segment does not include any oxypropylene unit unless it is linked to fragments adjacent to each end by ether 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% of oxyethylene units and better still, in particular for components having from 20 to 30 oxypropylene units, at least 50% of 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,

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 the ratio of the oxyethylene terephthalate / oxyalkylene terephthalate units at C3 is 2/1 or less, (ii) C4 to C6 alkylene or C4 to C6 oxyalkylene segments, or mixtures thereof, (iii) poly segments (vinyl ester), preferably poly (vinyl acetate), having a degree of polymerization of at least 2, or (iv) substituents C1-C4 alkyl ether or C4 hydroxyalkyl ether, or mixtures thereof, in which said substituents are present in the form of cellulosic derivatives of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether, 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 degrees can be used, preferably 3 to 150, more preferably 6 to 100. Hydrophobic oxyalkylene segments suitable C4 to C6 include, but are not limited to, end styling of polymeric soil removal agents such as MO3S (CH2) nOCH2CH2O-, where M is sodium and n is an integer from 4 to 6 , as described in US Patent No. 4,721,580 issued January 26, 1988 to Gosselink.

 Polymeric soil removal agents useful herein also include cellulose derivatives such as cellulosic polymers of hydroxyether, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyoxyethylene or polyoxypropylene terephthalate, and the like. These agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). Cellulose removal agents for use herein also include those selected from the group consisting of (C1-C4 alkyl) - and (C4 hydroxyalkyl) -celluloses; see US Patent N 4,000,093 issued December 28, 1976 to Nicol et al.

 Soil removal agents characterized by poly (vinyl ester) hydrophobic segments include graft copolymers of poly (vinyl ester), for example poly (alkylene oxide) frameworks, such as poly (vinyl oxide framework) (ethylene), onto which are grafted C1 to C6 vinyl esters, preferably poly (vinyl acetate).

See European patent application 0 219 048 by Kud et al., Published on April 22, 1987.

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 Another suitable soil removal agent is a copolymer having random blocks of ethylene terephthalate and poly (ethylene oxide) terephthalate (PEO). The molecular weight of this polymeric soil removal agent is in the range of 25,000 to 55,000. See US Patent No. 3,959,230 to Hays, issued May 25, 1976, and US Patent No. 3,893,929 de Basadur, issued July 8, 1975.

 Another suitable polymeric soil-removing agent is a polyester with ethylene terephthalate repeating units, which contains 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol having a molecular weight of 300 to 5,000.

 Another suitable polymeric soil removal agent is a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric ester framework of terephthaloyl and oxyalkylene oxy repeating units and terminal moieties covalently attached to the framework. These soil removal agents are fully described in US Patent No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E. P. Gosselink. Other suitable polymeric soil-removing agents include the polyesters terephthalates of US Patent No. 4,711,730, issued December 8, 1987 to Gosselink et al., The anionic end-capped oligomeric esters of US Patent No. 4,721,580, issued January 26, 1988 to Gosselink, and the polyester oligomeric compounds sequenced from US Patent No. 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric soil-removing agents also include the soil-removing agents of US Patent No. 4,877,896, issued October 31, 1989 to Maldonado et al., Which describes anionic end capped terephthalate esters, in particular particular sulfoaroyl.

 Another soil-removing agent is an oligomer with repeating units terephthaloyl, sulfoisoterephthaloyl, oxyethylene-oxy and oxy-1,2-propylene. The repeating patterns form the framework of the oligomer and are preferably terminated by stylings at the modified isethionate end.

A particularly preferred soil-removing agent of this type comprises 1 sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethylene-oxy and oxy-1,2-propylene-oxy units in a ratio of 1.7 to 1.8, and 2 styling patterns at the end 2- (2-hydroxyethoxy) ethanesulfonate sodium.

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Heavy metal ion sequestrant
The tablets of the invention preferably contain, as an optional component, a sequestering agent of heavy metal ions. By "heavy metal ion sequestrant" is meant herein components which act to sequester (chelate) heavy metal ions. These components can also have a chelating power of calcium and magnesium, but preferably have a selectivity of fixing to ions of heavy metals such as iron, manganese and copper.

 The heavy metal ion sequestrants are generally present in an amount of 0.005 to 20%, preferably from 0.1 to 10%, better still from 0.25 to 7.5% and especially from 0.5 to 5% by weight relative to the compositions.

 The sequestrants of heavy metal ions, which are acidic in nature, for example having phosphonic acid or carboxylic acid functionalities, can be present either in their acid form or in the form of a complex / salt with a suitable counter cation. such as an alkali ion, an alkali metal ion, or a substituted ammonium ion, or any of their mixtures. Preferably, all the salts / complexes are soluble in water. The molar ratio of said counter-cation to the sequestrant of heavy metal ions is preferably at least 1/1.

 The heavy metal ion sequestrants which can be used here include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), (alkali metal) -ethane-1-hydroxy-diphosphonates and nitrilotrimethylenephosphonates. Among the above compounds, diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate are preferred.

 Other heavy metal ion sequestrants usable here include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-

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 hydroxypropylenediaminedisuccinique or any of their salts.

 Particular preference is given to ethylenediamine-N, N'-disuccinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or their mixtures. The preferred EDDS compounds are in free acid form or in the form of the sodium or magnesium salt or one of their complexes.

Crystal growth inhibitor component
The detergent tablets preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, preferably incorporated in an amount of 0.01 to 5%, more preferably 0, 1 to 2% by weight relative to the compositions.

 By "organodiphosphonic acid" is meant here an organodiphosphonic acid which does not contain nitrogen which is part of its chemical structure. Consequently, this definition excludes organoaminophosphonates, which however can be incorporated into the compositions of the invention as sequestering components of heavy metal ions.

 The organodiphosphonic acid is preferably a C1 to C4 diphosphonic acid, better still a C2 diphosphonic acid, such as ethylenediphosphonic acid, or very especially ethane-1-hydroxy-1,1-diphosphonic acid (HEDP) , and it can be present in partially or fully ionized form, in particular in the form of a salt or a complex.

Water soluble sulfate salt
The detergent tablet optionally contains a water-soluble sulfate salt. When it is present, the water-soluble sulphate salt is in an amount of 0.1 to 40%, better still from 1 to 30%, especially from 5% to 25% by weight relative to the compositions.

 The water-soluble sulfate salt can be virtually any sulfate salt with any counter cation. The preferred salts are chosen from alkali and alkaline earth metal sulfates, and in particular it is sodium sulfate.

Alkali metal silicate
An alkali metal silicate is a preferred component of the tablet of the present invention. A preferred alkali metal silicate is a silicate of

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 sodium having an SiO 2 / Na 2 O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, especially 2.0. The sodium silicate is preferably present in an amount of less than 20%, preferably from 1 to 15%, especially from 3 to 12% by weight of SiO2. The alkali metal silicate can be in the form of the anhydrous salt or a hydrated salt.

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

 The alkalinity system also preferably contains sodium metasilicate, present in an amount of at least 0.4% by weight of SiO2. Sodium metasilicate has a nominal SiO2 / Na20 ratio of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured in SiO 2, is preferably from 50/1 to 5/4, better still from 15/1 to 2/1, especially from 10/1 to 5/2.

Dye
The term "dye" as used herein means any substance which absorbs specific wavelengths of light in the spectrum of visible light. These dyes, when added to a detergent composition, have the effect of changing the visible color and therefore the appearance of the detergent composition. The dyes can be, for example pigments or dyes. Preferably, the dyes are stable in the composition in which they are to be incorporated. Thus, in a composition at high pH, the dye is preferably stable to alkalis, and in a composition at low pH, the dye is preferably stable to acids.

 The first phase and / or the second phase and / or any subsequent phases may contain a dye, a mixture of dyes, colored particles or a mixture of colored particles so that the various phases have different visual aspects. Preferably, one or the other of the first and second phases comprises a dye. When both the first and second phases and / or the subsequent phases comprise a dye, it is preferred that the dyes have a different visual appearance.

 Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes,

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 quinoline dyes, and monoazo, disazo and polyazo dyes. More preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-HRL 180% (registered trademark), SANDOLAN MILLING BLUE (registered trademark), TURQUOISE ACID BLUE (registered trademark) and SANDOLAN BRILLIANT GREEN (registered trademark), all available from Clariant GB, HEXACOL QUINOLINE YELLOW ( trademark) and HEXACOL BRILLIANT BLUE (trademark), both available from Pointings, UK, ULTRA MARINE BLUE (trademark) available from Holliday or LEVAFIX TURQUOISE BLUE EBA (trademark), available from Bayer, USA.

 The dye can be incorporated into the phases by any suitable method. Suitable methods include mixing all of the detergent components or selected detergent components with a dye in a drum, or spraying all of the detergent components or selected detergent components with the dye in a rotary drum.

 The dye, when present as a component of the first phase, is present in an amount of 0.001 to 1.5%, preferably 0.01 to 1.0%, most preferably 0.1 to 0, 3%. When it is present as a component of the second phase and / or any subsequent phases, the dye is generally present in an amount from 0.001 to 0.1%, better still from 0.005 to 0.05%, especially from 0.007 at 0.02%.

Corrosion inhibitor compound
The tablets of the present invention which can be used in dishwashing methods may contain corrosion inhibitors, preferably chosen from organic silver coating agents, in particular paraffin, nitrogen corrosion inhibitor compounds and compounds of Mn (II), in particular the Mn (II) salts of organic ligands.

 Organic silver coating agents are described in published PCT application N WO94 / 16047 and the simultaneously pending European application N EP-A-690 122. Nitrogen corrosion inhibiting compounds are described in the simultaneously pending European application N EP- A-634 478. Mn (II) compounds to be used for

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 the inhibition of corrosion are described in the European application simultaneously pending N EP-A-672 749.

 The organic silver coating agent can be incorporated in an amount of 0.05 to 10%, preferably 0.1 to 5% by weight based on the total composition.

 The functional role of the silver coating agent is to form a protective coating layer "in use" on all the silverware components of the washing load to which the compositions of the invention are applied. The silver coating agent should therefore have a strong affinity for attachment to massive silver surfaces, especially when it is present as a component of an aqueous washing and bleaching solution in which massive silver surfaces are treated.

 Suitable organic silver coating agents herein include fatty esters of monovalent or polyvalent alcohols having from 1 to 40 carbon atoms in the carbon chain.

 The fatty acid part of the fatty ester can be obtained from monocarboxylic or polycarboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, l butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and ss, ss'-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include n-butylmalonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

 The fatty alcohol radical in the fatty ester can be represented by monovalent or polyvalent alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include: behenyl, arachidyl, coconut, oleyl and lauryl alcohols, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaeyythritol, sorbitol or sorbitan.

 Preferably, the fatty acid and / or fatty alcohol group of the fatty ester addition material has from 1 to 24 carbon atoms in the alkyl chain.

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 Preferred fatty esters here are the sorbitan and ethylene glycol or glycerol esters in which the fatty acid part of the ester normally comprises a compound chosen from behenic acid, stearic acid, oleic acid, palmitic acid and myristic acid.

 Glycerol esters are also particularly preferred. These are monoesters, diesters or triesters of glycerol and the fatty acids defined above.

 Specific examples of fatty alcohol esters to be used here include: stearyl acetate, palmityl dilactate, coconut isobutyrate, oleyl maleate, oleyl dimaleate, and propionate follow it. The fatty acid esters useful here include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan distearate , sorbitan dioleate, and also monoesters and mixed diets of tallow and sorbitan.

 The glycerol esters which are preferred here are glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate.

 Suitable organic silver coating agents include triglycerides, monoglycerides or diglycerides, and their partially or fully hydrogenated derivatives, as well as any of their mixtures. 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, grape seed oil, palm oil and corn oil.

 Waxes, including microcrystalline waxes, are suitable organic silver coating agents herein. Preferred waxes have a melting point in the range of 35 C to 110 C and generally include 12 to 70 carbon atoms. We prefer petroleum waxes

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 paraffin type and microcrystalline type which are composed of long chain saturated hydrocarbon compounds.

 Alginates and gelatin are suitable organic silver coatings here.

 Also suitable are dialkylamine oxides such as C12 to C20 methylamine oxide, and quaternary dialkyl ammonium compounds and salts and salts such as C12 to C20 methylammonium halides.

 Other suitable organic silver coatings include certain polymeric materials. As examples of such polymeric materials, mention may be made of polyvinylpyrrolidones having an average molecular weight of 12,000 to 700,000, polyethylene glycols (PEG) having an average molecular weight of 600 to 10,000, poly (N- amine oxide), copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.

 Certain scented materials, particularly those with high substantivity for metallic surfaces, are also useful here as organic silver coatings.

 As organic silver coating agent, polymeric soil removal agents can also be used.

 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; preferred paraffin oil is chosen from predominantly branched C25 to C45 species, having a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons of 1/10 to 2/1, preferably 1/5 to 1/1. A paraffin oil with these characteristics, having a cyclic to non-cyclic hydrocarbon ratio of 32/68, is sold by Wintershall, Salzbergen, Germany, under the registered trademark WINOG 70.

Nitrogen corrosion inhibitor compounds
Suitable nitrogen corrosion inhibitor compounds include imidazole and its derivatives such as benzimidazole, 2-heptadecylimidazole and imidazole derivatives described in the patent

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 Czech N 139,279 and British Patent GB-A-1,137,741, which also describes a process for preparing imidazole compounds.

 As nitrogen corrosion inhibitor compounds, the pyrazole compounds and their derivatives are also suitable, in particular those in which the pyrazole is substituted in any one of the 1,3, 4 or 5 positions by substituents R1, R3, R4 and R5 where R1 is any of H, CH20H, CONH3 and COCH3, R3 and R5 are any of a C1 to C20 alkyl radical and a hydroxyl radical, and R4 is any of H, NH2 and N02.

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

 Also suitable are nitrogen compounds such as amines, in particular distearylamine, and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrogen citrate.

Mn (II) corrosion inhibitor compounds
Detergent tablets may contain a corrosion inhibiting Mn (II) compound. The compound of Mn (II) is preferably incorporated in an amount of 0.005 to 5% by weight, better still from 0.01 to 1%, especially from 0.02 to 0.4% by weight relative to the compositions. Preferably, the Mn (II) compound is incorporated in an amount providing from 0.1 to 250 ppm, better still from 0.5 to 50 ppm, especially from 1 to 20 ppm by weight of Mn (II) ions. in any bleaching solution.

 The Mn (II) compound can be a mineral salt in anhydrous form or in any hydrated form. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The Mn (II) compound can be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.

 The compound of Mn (II) can be a salt or complex of a ligand

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 organic. In a preferred aspect, the organic ligand is a sequestrant of heavy metal ions. In another preferred aspect, the organic ligand is an inhibitor of crystal growth.

Other corrosion inhibiting compounds
Other suitable additional corrosion inhibiting compounds include mercaptans and diols, in particular mercaptans having 4 to 20 carbon atoms, including laurylmercaptan, thiophenol, thionaphthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated C10 to C20 fatty acids, or their salts, in particular aluminum tristearate. C12 to C20 hydroxylated fatty acids, or their salts, are also suitable. Also suitable are phosphonated octadecane and other antioxidants such as P-hydroxytoluene (BHT).

 The copolymers of butadiene and maleic acid, in particular those sold under the reference number N 07787 by Polysciences Inc., prove to be particularly useful as corrosion-inhibiting compounds.

Hydrocarbon oils
Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain aliphatic hydrocarbon, having a number of carbon atoms in the range of 20 to 50; the preferred hydrocarbons are saturated and / or branched; the preferred hydrocarbon oils are chosen from predominantly branched C25 to C45 species having a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons of 1/10 to 2/1, preferably 1/5 to 1/1. A preferred hydrocarbon oil is paraffin. A paraffin oil having the characteristics indicated above, having a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons of 32/68, is sold by Wintershall, Salzbergen, Germany, under the registered trademark WINOG 70.

Composed of water soluble bismuth
The detergent tablets of the present invention for use in dishwashing methods may contain a water-soluble bismuth compound, preferably present in an amount of 0.005 to 20%, more preferably 0.01 to 5%, all especially from 0.1 to 1% by weight relative to the compositions.

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 The water-soluble bismuth compound can be virtually any salt or complex of bismuth with virtually any mineral or organic counter anion. The preferred bismuth mineral salts are chosen from bismuth trihalides, bismuth nitrate and bismuth phosphate. The salts with a preferred organic counter anion are acetate and bismuth citrate.

Stabilizing enzyme system
The compositions containing enzymes preferred herein may comprise from 0.001 to 10%, preferably from 0.005 to 8%, most preferably from 0.01 to 6% by weight of an enzyme stabilizer system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. These stabilizing systems can include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acid, chlorine bleach fixatives and mixtures thereof. These stabilizing systems may also include reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime soap dispersant compound
The tablets of the present invention may contain a lime soap dispersing compound, preferably present in an amount of 0.1 to 40% by weight, more preferably 1 to 20% by weight, especially 2 to 10% by weight. weight relative to the compositions.

 A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts and fatty acids by calcium or magnesium ions. The preferred dispersants of lime soap are described in PCT application N WO93 / 08877.

Anti-foaming system
The detergent tablets of the present invention, when formulated for use in machine wash compositions, preferably include an anti-foaming system present in an amount of 0.01 to 15%, preferably 0.05 to 10%, especially from 0.1 to 5% by weight relative to the composition.

 Anti-foaming systems usable herein can include virtually any known anti-foaming compound, including, for example,

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 for example, silicone anti-foaming compounds, 2-alkylated anti-foaming compounds and based on alkanol. Preferred anti-foaming systems and anti-foaming compounds are described in PCT application No. WO93 / 08876 and document EP-A-705,324.

Polymeric agents inhibiting the transfer of dyes
The detergent tablets presented here can also comprise from 0.01 to 10%, preferably from 0.05 to 0.5% by weight of polymeric agents inhibiting the transfer of dyes.

 The polymeric agents inhibiting the transfer of dyes are preferably chosen from poly (N-amine oxide) polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polymers of polyvinylpynolidone, and combinations thereof.

Optical brightener
The detergent tablets that can be used in laundry washing processes as described here also optionally contain from 0.005 to 5% by weight of certain types of hydrophilic optical brighteners.

dans laquelle R1 est choisi parmi les groupes anilino, N-2-bis-hydroxyéthyle et NH-2-hydroxyéthyle ; R2 est choisi parmi les groupes N-2-bis- hydroxyéthyle, N-2-hydroxyéthyl-N-méthylamino, morpholino, chloro et amino ; et M est un cation formant un sel tel que le sodium ou le potassium. The hydrophilic optical brighteners useful here include those of structural formula:

in which R1 is chosen from the anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl groups; R2 is selected from the groups N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

 When, in the above formula, R1 is the anilino group, R2 is the N-2-bis-hydroxyethyl group and M is a cation such as sodium, the brightener is 4,4'-bis acid [ (4-anilino-6- (N-2-bishydroxyethyl) -s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic acid or its disodium salt. This particular type of brightener is sold commercially under the trademark Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the invention.

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 When, in the above formula, R1 is the anilino group, R2 is the N-2-hydroxyethyl-N-2-methylamino group and M is a cation such as sodium, the brightener is the disodium salt of the 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular type of brightener is sold commercially under the registered trademark Tinopal 5BM-GX by Ciba-Geigy Corporation.

 When, in the above formula, R1 is the anilino group, R2 is the morpholino group and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis acid (( 4-anilino-6-morpholino-s-triazine-2-yl) amino] -2,2'-stilbenedisulfonic. This particular type of brightener is sold commercially under the trademark Tinopal AMS-GX by Ciba Geigy Corporation.

Clay softener system
Detergent tablets for use in laundry cleaning processes may contain a clay softener system comprising a clay mineral compound and optionally a clay flocculating agent.

 The clay mineral compound is preferably a compound of smectite clay type. Smectite clays are described in US Patents N 3,862,058.3 948,790.3 954,632 and 4,062,647. European Patents N EP-A-299,575 and EP-A-313,146 in the name of Procter & Gamble Company describe suitable organic polymeric clay flocculants.

Softening agents for cationic tissues
Cationic fabric softeners can also be incorporated into compositions according to the present invention which are useful in laundry washing processes. Suitable cationic tissue softeners include water-insoluble tertiary amines or di (long chain) amide materials described in GB-A-1514 276 and EP-B-0 0 11 340.

 The cationic fabric softeners are typically incorporated in total amounts of 0.5 to 15% by weight, normally 1 to 5% by weight.

Other optional ingredients
Other optional ingredients which may be incorporated into

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compositions of the invention include perfumes and fillers in the form of salts, sodium sulfate being a preferred salt filler. pH of the compositions
The detergent tablets of the present invention are preferably not formulated so as to have an unduly high pH, and preferably have a pH, measured in 1% solution in distilled water, of 8.0 to 12.5 , better still from 9.0 to 11.8, especially from 9.5 to 11.5.

Dish washing machine
Any suitable method for washing or machine washing soiled dishes is contemplated.

 A preferred method of washing dishes in a machine includes treating soiled items, selected from plates, glasses, silverware, metalware, cutlery and their mixtures, with an aqueous liquid in which is dispersed or dissolved an effective amount of a detergent tablet according to the invention. By "effective amount of the detergent tablet" is meant 8 to 60 g of product dissolved or dispersed in a washing solution having a volume of 3 to 10 liters, which represents doses of product and volumes of washing solution typical commonly used in conventional machine dishwashing processes. Preferably, the detergent tablets have a weight of 15 to 40 g, better still a weight of 20 to 35 g.

Washing method
The machine washing methods used herein typically include treating soiled laundry with an aqueous washing solution in a washing machine in which an effective amount of a detergent tablet composition is dispersed or dissolved. machine washing according to the invention. By "effective amount of the detergent tablet composition" is meant from 40 to 300 g of product dissolved or dispersed in a volume of 5 to 65 liters of washing solution, which represents characteristic doses of product and volumes of solution commonly used in conventional machine washing processes.

 In a preferred aspect of use, a dispensing device is employed in the washing process. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the

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 washing machine drum before the start of the wash cycle.

Its volume capacity should be such that it can contain a sufficient quantity of detergent corresponding to that which would normally be used in the washing process.

 Once the washing machine has been loaded with the laundry, the dispensing device containing the detergent product is placed inside the drum.

At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the dispensing device should be such that it allows the confinement of the dry detergent product but then allows the release of this product during the washing cycle in response to its agitation when the drum is rotating, and also as a result of its contact with wash water.

 To allow release of the detergent product during washing, the device may have a number of openings through which the product can pass. In another way, the device can be made of a material which is permeable to liquids but impermeable to solid products, which will allow the release of the dissolved product. Preferably, the detergent product will be released quickly at the start of the washing cycle, so as to provide transient localized high concentrations of product in the drum of the washing machine at this stage of the washing cycle.

 Preferred dispensing devices are reusable and are designed so that the integrity of the container is maintained both in the dry state and during the wash cycle.

 Alternatively, the dispensing device can be a flexible container, such as a bag or pocket. The bag may have a fibrous construction coated with a waterproof protective material so as to preserve the content, as described in the published European patent application No. 0188 678. Alternatively, it may be formed of '' a water-insoluble synthetic polymer material provided with a seal or a peripheral closure designed to rupture in an aqueous medium, as described in the published European patent applications N 0011 500, 0 011 501,0 011 502 and 0 011 968. A convenient form of water-breakable closure includes a water-soluble adhesive disposed along an edge of a sachet formed from an impermeable polymer film

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 with water such as polyethylene or polypropylene, and closing this edge.

Examples Abbreviations used in the examples
In detergent compositions, the abbreviated identifications of components have the following meanings.

STPP Sodium tripolyphosphate Bicarbonate Sodium hydrogencarbonate Citric acid. Anhydrous citric acid Carbonate Anhydrous sodium carbonate Silicate Amorphous sodium silicate (Si02 / Na20 ratio = 2.0) SKS-6 Lamellar crystalline silicate of formula # -Na2Si2O5 PB1 Anhydrous sodium perborate monohydrate Non-ionic C13 to C15 ethoxylated fatty alcohol / mixed propoxylate with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the registered trademark Plurafac by BASF GmbH TAED Tetraacetylethylenediamine HEDP Ethane acid - 1 - Hydroxy - 1, 1 - diphosphonic PAAC Salt pentamine-cobalt (III) acetate Paraffin Paraffin oil sold under the trademark
Winog 70 by Wintershall Protease Proteolytic enzyme Amylase Amylolytic enzyme BTA Benzotriazole Sulfate Anhydrous sodium sulfate PEG 3000 Polyethylene glycol with a molecular weight of approximately 3000, available from Hoechst PEG 6000 Polyethylene glycol with a molecular weight of approximately 6000, available from Hoechst pH Measured in 1% solution in distilled water at 20 C
In the examples which follow, all the quantities are given in parts by weight.

Example 1 to IV
The following illustrates examples of detergent tablets of the present invention for use in a dishwasher.

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I II III IV V VI Phase 1 STPP 9.62 9.62 10.45 9.57 9.57 11.47 Silicate 0.50 0.67 1.60 1.00 1.00 2.40 SKS-6 1 5.5 1.50 2.30 2.25 Carbonate 2.33 2.74 3.5 3.59 4.10 5.25 HEDP 0.18 0.18 0.18 0.28 0.28 0.28 PB1 2.45 2.45 2.45 3.68 3.68 3.68 PAAC 0.002 0.002 0.002 0.003 0.004 0.004 Amylase 0.148 0.110 0.110 0.252 0.163 0.163 Protease 0.06 0.06 0.06 0.09 0.09 0, 09 Non-ionic 0.40 0.80 0.80 1.20 1.20 1.20 PEG 6000 0.4 0.26 0.26 0.38 0.39 0.39 BTA 0.04 0.04 0 0.04 0.06 0.06 Paraffin 0.10 0.10 0.10 0.15 0.15 0.15 Perfume 0.02 0.02 0.02 0.013 0.013 0.013 Sulfate 0.502 0.05 2.843
Total 17.75 g 18.55 g 19.57 g 23.0 g 23.0 g 23.0 g 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 1.09 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 3000 0.06 0.06 0.06 0.06 0.06 0.06
Total 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g
The multi-phase tablet compositions are prepared as follows. The active detergent composition of phase 1 is prepared by mixing the granular and liquid components which are then passed through the die of a conventional rotary press. The press includes a die of suitable shape to form the mold. The cross section of the die is approximately 30 x 38 mm. Then we submit

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 the composition at a compression force of 940 kg / cm2 and the matrix is then raised, exposing the first phase of the tablet containing the mold in its upper surface. The active detergent composition of phase 2 is prepared in a similar manner and it is passed through the die. Then the particulate active composition is subjected to a compressive force of 170 kg / cm 2, the matrix is raised, and the multi-phase tablet is ejected from the tablet press. The resulting tablet dissolves or disintegrates in a washing machine as described above in the space of 12 minutes, phase 2 of the tablets dissolves in the space of 5 minutes. The tablets offer excellent dissolution and cleaning characteristics together with good tablet integrity and good resistance.

 Of course, the invention is not limited to the embodiments described above and shown, from which we can provide other modes and other embodiments, without departing from the scope of the invention .

Claims (8)

1. Multi-phase detergent tablet for use in a washing machine, characterized in that it comprises: a) a first phase in the form of a shaped body having at least one mold therein; and b) a second phase in the form of a compressed body adhesively contained inside said mold, the tablet composition comprising one or more detergent active substances which are predominantly concentrated in the second phase, and the second phase further comprising a binder.  2. Multi-phase detergent tablet for use in a washing machine, characterized in that it comprises: a) a first phase in the form of a compressed shaped body having at least one mold in it, the shaped body being prepared under a compression pressure of at least about 350 kg / cm2; and b) a second phase in the form of a compressed body adhesively contained inside said mold, the tablet composition comprising one or more detergent active substances which are predominantly concentrated in the second phase, and the second phase further comprising a binder.  3. Multi-phase detergent tablet according to any one of the preceding claims, characterized in that the detergent active substance or substances are chosen from enzymes, bleaching agents, bleaching activators, bleaching catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof.  4. Multi-phase detergent tablet according to any one of the preceding claims, characterized in that the binder is chosen from the group consisting of sugar and sugar derivatives, starch and starch derivatives, and mineral and organic polymers.  5. Multi-phase detergent tablet according to any one of the preceding claims, characterized in that it further comprises a barrier phase between the first and the second phases. <Desc / Clms Page number 78>  6. Multi-phase detergent tablet according to claim 5, characterized in that the barrier layer comprises a binder applied in liquid form.  7. Washing method in a washing machine, characterized in that it comprises the loading into a washing machine of one or more detergent tablets with multiple phases according to any one of the preceding claims.  8. Method according to claim 7, characterized in that the multi-phase detergent tablet dissolves or disintegrates in less than 15 minutes in a dishwasher, in accordance with the dissolution test method described here.