ITMI991569A1 - COMPRESSED DETERGENT - Google Patents

Abstract

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

Description

Description of the patent for industrial invention entitled:

"Cleansing tablet"

Technical field

The present invention relates to multiphase cleansing tablets.

Background

Detergent compositions in tablet form are known in the art. It is understood that detergent compositions in tablet form have several advantages over detergent compositions in particle form, such as ease of dosage, handling, transport and storage.

The detergent tablets are prepared, according to the most common procedures, by premixing the components of a detergent composition and providing the components with premixed detergents in the form of a tablet using any suitable equipment, preferably a tablet press. The tablets are typically formed by compressing the components of the detergent composition, pressing them in such a way that the tablets produced are strong enough to be able to withstand the stresses to which they are exposed during handling and transport, without undergoing 'In addition to being robust,' the tablets must also dissolve quickly enough so that the detergent components are released into the wash water as soon as possible at the start of the wash cycle.

However, there is a dichotomy in that as the compressive force increases, the dissolution rate of the tablets decreases. The present invention therefore seeks to find a balance between the strength of the tablets and the dissolution rate of the tablets.

The solutions proposed for this problem, as seen in the prior art, have included tableting the tablets with a low pressing pressure. However, tablets made in this way, despite having a relatively rapid dissolution rate, tend to crumble, becoming damaged and presenting themselves as unacceptable to the consumer. Other solutions have provided for preparing tablets using a relatively high pressing pressure, in order to achieve the required level of strength, and with the inclusion of a dissolving aid, such as an effervescent agent.

The multiphase detergent tablets disclosed in the prior art are prepared by compressing a first composition in a press to form a substantially planar first layer. Subsequently, a further detergent composition is fed to the tablet press over the first layer. This second composition is subsequently compressed in order to form another second substantially planar layer. Thus, the first layer is generally subject to more than one compression and is also compressed during the compression of the second composition. Typically, the first and second compressive forces are of the same order of magnitude. The Applicant has found that when this is the case, since the compressive force must be sufficient to bind the first and second compositions together, the force used in both the first compression stage and the second compression stage must have a value comprised in the range of from about 4000 to about 20,000 kg (assuming that the tablet has a surface area of the cross section of about 10 cm2). A consequence of this is a reduction in the dissolution rate of the tablet. Other multiphase tablets with differential dissolution rates are prepared by compressing the second layer with a lower compressive force than that used 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 susceptible to damage caused by handling and transport stresses.

EP-B-0.055.100 discloses a toilet block formed by combining a slow dissolving formed body with a tablet. The toilet block is designed to be placed in a toilet flush water tank and dissolves over a period of days, preferably weeks. As a means of reducing the rate of dissolution of the toilet block, the document teaches mix one or more solubility control agents. 'Examples of such solubility control agents are paradichlorobenzene, waxes, long-chain fatty acids and alcohols and their esters and fatty alkylamides. they must be dissolved substantially within a cycle of the washing machine or dishwashing machine, that is, within a time ranging from 15 to 120 minutes.

Summary of the invention.

According to a first aspect of the present invention, a multiphase detergent tablet for use in a washing machine is provided, the tablet comprising:

a) a first step in the form of a formed body having at least one imprint therein; .e

b) a second step in the form of an adhesively compressed body contained within said impression, wherein the tablet composition comprises one or more detergent activity species which are predominantly concentrated in the second step, and wherein the second step additionally comprises a binder .

Preferably, the second phase is in the form of a solid particle compressed within said footprint.

In preferred embodiments, the first step is a compressed formed body prepared at an applied compression pressure of at least about 40 kg / cm <2>, preferably at least about 150 kg / cm <2>, more preferably at least about 350 kg / cm <2> (3.43 kN / cm <2>), even more preferably in the range between about 400 and about 2000, and especially between about 600 and about 1200 kg / cm <2> (the "pressure of compression "herein is the applied force divided by the cross-sectional area of the tablet in a plane perpendicular to the direction of the applied force - in effect, the cross-sectional surface area of the rotary press mold). It is also preferred that the particulate coin of the second phase (with which terminology is intended to include the possibility of a plurality of "second" phases, sometimes referred to herein as "optionally present subsequent phases") is compressed within said imprint to a applied compression pressure lower than that applied to the first phase and preferably at a compression stress lower than about 350 kg / cm <2>, preferably in the range of from about 40 kg / cm <2> to about 300 kg / cm <2>, and more preferably from about 70 to about 270 kg / cm <2>, such tablets being preferred herein from the point of view of achieving optimum levels of integrity and strength of the tablets [characteristics measured, for example, for means of the test for the determination of the Child Bite Strength (CBS)] and the dissolution characteristics of the product. The tablets of the present invention preferably have a CBS of at least about 6 kg, preferably greater than about 8 kg more preferably greater than about 10 kg, especially greater than about 12 kg, and even more especially greater than about 14 kg, the CBS being measured in accordance with the procedure specified in the US Consumer Product Safety Commission Test Specification. Further, the compression pressures applied to the first and second stages will generally be in a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1.

Thus, according to a further aspect of the present invention, a multiphase detergent tablet is provided for use in a washing machine, the tablet comprising.

a) a first step in the form of a compressed formed body having at least one imprint therein, the formed body being prepared for a compression pressure of at least about 350 kg / cm 2; And

b) a second phase in the form of an adhesively compressed body contained within said impression, wherein the tablet composition comprises one or more species endowed with detergent activity which are predominantly concentrated in the second - phase, and wherein the second phase additionally comprises a binder.

The second step is in the form of a compressed body adhesively contained, for example, by physical or chemical adhesion, within at least one mold of the first body. It is also preferred that the first phase and the second phase are in a relatively high weight ratio to each other, for example at least about 6: 1, preferably at least 10: 1; and further that the tablet composition contains one or more species endowed with detergent activity (for example, enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, and so on), which are predominantly concentrated in the second phase, for example, to such an extent that at least about 50%, preferably at least about 60%, especially at least about 80% by weight of the active species (with reference to the total weight of the active species in the tablet) is in the second phase of the tablet. Again, these compositions are optimal as regards the values of the strength of the tablet, of the dissolution of the complex, of the detergent power of the tablet and of the pH regulation characteristics providing, for example, compositions of tablets capable of dissolving in the washing liquid. so as to deliver at least 50%, preferably at least 60% and more preferably at least 80% by weight of the species endowed with detergent activity to the washing bath within 10, 5, 4 or even within 3 minutes from the start of the washing process wash.

An additional benefit of the invention is the ability to achieve differential phase dissolution, whereby one phase of the tablet will dissolve significantly before another phase and may even dissolve to an essentially complete extent before the other phase has dissolved. This is particularly useful for the differential dispensing of species endowed with detergent activity.

Suitably, the one or more species endowed with detergent activity are selected from the group consisting of enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and their mixtures, the active species having an enzyme character being particularly preferred for enhancing the cleaning performance during the very first stage of the washing or cleaning operation, carried out in cold water. Highly preferred for use herein, therefore, are species endowed with enzymatic detergent activity, and especially enzymes and enzyme mixtures comprising one or more enzymes having enhanced or optimal activity in the temperature range of 25 ° C to 55 ° C. ° C and a pH value in the range of 8 to 10 (for example, Natalase).

Detailed Description of the Invention An object of the present invention is to provide a cleaning tablet which is not only strong enough to withstand handling and transport, but is also such that at least a significant portion of it dissolves rapidly in the wash water providing the · Rapid supply of the species with detergent activity. It is preferred that at least one phase of the tablet dissolve in the wash water within 1. first 10 minutes, preferably within the first 5 minutes, more preferably within the first 4 minutes of the washing cycle of an automatic dishwashing or laundry washing machine. Preferably, the washing machine is an automatic dishwasher or washing machine. The time during which the multiphase tablet or a phase of it or a component with detergent activity dissolves is determined according to the standardized procedure DIN 44990 using a dishwasher machine available from the Bosch company set on the normal washing program at 65 ° C with water hardness equal to 18 ° H using a minimum of 6 replicate tests, or a sufficient number of replicate tests to ensure reproducibility.

The multiphase detergent tablet of the present invention comprises a first phase, a second phase and optionally subsequent phases. The first step is in the form of a body formed of detergent composition comprising one or more detergent components as described below. Preferred detergent components include adjuvant, bleach, enzymes and surfactant. The components of the detergent composition are mixed together, for example, by adding to each other and mixing the dry components, or by applying liquid components by spraying. A first step is then formed from the components using any suitable equipment, however, preferably, by compression, for example, by pressing in a tablet press. Alternatively, the first step can be prepared by extrusion, casting, and so on. The first step may take a variety of geometric shapes - such as spheres, cubes, and so on, however preferred embodiments generally have an axially symmetrical shape with a generally round, square or rectangular cross section.

The first step is prepared in such a way that it comprises at least one mold in the surface of the formed body. The one or more footprints can also have variable size and shape, as well as they can vary as regards their position, their orientation, and their topology relative to the first phase. For example, the one or more impressions could generally be with a circular, square or oval cross section; they can form a cavity, or hollow, closed internally in the surface of the formed body, or they can extend between unconnected regions of the body surface (for example, on axially opposite facing surfaces) in order to form one or more "holes" topological in the formed body; and furthermore they can be arranged with axial symmetry or of another type with respect to the first phase, or they can be arranged asymmetrically. In a preferred embodiment, the impression is created using a specially designed tablet press, in which the surface of the punch intended to come into contact with the detergent composition has a shape such that when it contacts and compresses the detergent composition, produces, by compression, a cavity, or impression, or a plurality of cavities, or impressions, for molding in the first phase of the multiphase detergent tablet. Preferably, the impression will have an inwardly concave or generally concave surface in order to provide improved adhesion to the second phase. Alternatively, the imprint can be created by compressing a preformed body of detergent composition disposed in annular configuration around a central punch, thereby forming a formed body having an imprint in the form of an axially extending cavity between opposite surfaces of the body.

The tablets of the present invention also comprise one or more additional phases prepared starting from one or more compositions which comprise one or more detergent components, as described below. At least one phase (referred to in the present "second phase") preferably takes the form of a particulate solid (which term includes powders, granules, agglomerates and other particulate solids, including their mixtures with liquid binders, meltable solids, components, spray applied , and so on) compressed into / within the one or more impressions of the detergent tablet phase, so that the second phase in turn will take the form of a formed body. Further optional steps comprise one or more compositions in the form of one or more separate layers. Components of preferred detergents include adjuvants, color conferring agents, binders, surfactants, disintegrating agents and enzymes, in particular enzymes having an amylase and protease character. In another preferred aspect of the present invention, the second and optionally present subsequent steps comprise a disintegrating agent which can be selected from a disintegrating agent or an effervescent agent. Suitable disintegrating agents include agents which swell upon contact with water or facilitate the entry and / or exit of water by forming channels in the detergent tablet. It is contemplated that any known disintegrating or effervescent agent suitable for use in applications in fabric washing or dishwashing may be used here. Suitable disintegrating agents include starches (such as natural, modified and pregelatinized starches, for example, those derived from corn starch, rice starch and potato starch), starch derivatives, such as U-Sperse products (trade name), Primojel (trade name), and Explotab (trade name), cellulose, microcrystalline cellulose and cellulose derivatives, such as Arbocel (trade name), and Vivapur (trade name), both available from Rettenmaier, Nymcel (trade name), available from Metsa -serla, Avicel (trade name), Lattice NT (trade name), and Hanfloc (trade name), alginates, acetate trihydrate, burkeite, carbonate monohydrate having the formula Na2CO3.H2O, STPP hydrate with 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 upon contact with water. Suitable effervescent agents can be species which develop oxygen, nitrogen dioxide or carbon dioxide. Examples of preferred effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with carboxylic acids or other acids, such as citric acid, sulfamic acid, malic acid or maleic acid.

The components of the detergent composition are mixed together, for example, by mixing the dry components and adding and mixing or applying by spraying the liquid components. The components of the second phase and of the subsequent phases optionally present are subsequently fed into and retained inside the impression provided by the first phase.

The preferred embodiment of the present invention comprises two steps; a first and a second phase. The first step will normally comprise an impression and the second step will normally consist of a single composition having a detergent activity. However, it is envisaged that the first phase may comprise more than one impression and the second phase may be prepared starting from more than one composition having a cleaning activity. Furthermore, it is also envisaged that the second step may comprise more than one composition having a detergent activity contained within a mold. It is also envisaged that various compositions endowed with detergent activity are contained in separate impressions. In this manner, potentially chemically sensitive detergent components can be kept separate in order to avoid any loss of performance caused by the fact that some components may react together and potentially become deactivated or exhausted.

A suitable binder component is selected from the group consisting of organic polymers, for example, polyethylene glycols and / or polypropylene glycols, especially those having molecular weight 4000, 6000 and 9000, paraffins, polyvinylpyrrolidone (PVP), especially PVP with molecular weight 90,000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, for example, hydroxy-propylmethylcellulose (HPMC) and carboxymethylcellulose (CMC); and inorganic polymers, such as hexametaphosphate. The binder is useful both for the integrity of the tablet and for helping to achieve the differential dissolution of the first and second phases, as will be described later.

In a preferred aspect of the present invention, the first phase weighs more than about 3 grams, preferably more than about 4 grams, more preferably more than about 5 grams. More preferably, the first phase weighs from about 10 grams to about 30 grams, even more preferably from about 15 grams to about 50 grams, and most preferably from about 18 grams to about -24 grams. The second phase and the optionally present subsequent phases weigh less than 4 grams. More preferably, the optionally present second and / or subsequent phases weigh between about 0.1 grams and about 3.5 grams, preferably between about 1 gram and about 3.5 grams, most preferably between about 1.3 grams. and about 2.5 grams.

In another practical embodiment of the present invention, a barrier layer comprising a constituent composition of the barrier layer is arranged between the first and second phase and / or the optionally present subsequent phases, or also between the second phase and possible phases later optionally present. The constitutive composition of the barrier layer comprises at least one binder selected from the group as described above. The advantage of the presence of a barrier layer is that in this way the migration of components from one phase to another phase is prevented or reduced, for example, from the first phase to the second and / or subsequent optional phases, and vice versa. .

The optionally present second and subsequent step components are preferably compressed with a very low compressive force, compared to the compressive force normally used to produce tablets. Thus, an advantage of the present invention stems from the fact that since a low compressive force is used, heat, force or chemically sensitive detergent components can be incorporated into the detergent tablet without suffering the consequent loss of performance encountered. usually when incorporating components of this type in tablets. Alternatively, the second phase or phases may be compressed at the same compressive force or at a higher compressive force, than the force used for the compression of the first phase, in order to achieve differential dissolution of the phases, as described in following.

A further advantage of the present invention is the improved protection of the second phase from damage caused, for example, by handling and transport. As described above, multiphase cleaning tablets have been prepared in which the second layer is compressed to a compression force less than the compressive force of the first layer. However, although this improves the dissolution rate, the second layer of these tablets becomes vulnerable to damage., Tending to crumble or chip upon contact, the one or more lightly compressed phases of the detergent tablets of the present invention are nevertheless protected inside the impression provided by the first phase of the cleaning tablet.

Still another advantage of the present invention is the ability to prepare a multiphase cleansing 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 optionally present subsequent phases dissolve before the first phase. According to the preferred weight ranges described above, it is preferable that the first phase dissolves in 5 to 20 minutes, more preferably 10 to 15 minutes, and that the second phase and / or the one or more optionally present subsequent phases occur dissolve in less than 5 minutes, preferably in less than 4.5 minutes, most preferably in less than 4 minutes. Alternatively, the second phase may dissolve after the first or after the other phases, for example, when it is desired to deliver cleansing or rinsing benefits towards the end of the washing operation. The time during which the first phase, the second phase and / or the optionally present subsequent phases dissolve are independent of each other. Thus, in a particularly preferred aspect of the present invention, differential dissolution of the phases is achieved. A particular benefit of being able to achieve differential dissolution of the multiphase detergent tablet is that a component that is chemically deactivated by the presence of another component can be kept separate in a different phase. In this case, the component which is deactivated will preferably be arranged in the second phase and in the one or more subsequent phases optionally present.

Still another advantage of the present invention is the improved inter-phase adhesion of the multiphase tablet. It is believed that the improvement in adhesion is achieved by reducing the exposure of the second phase as compared to the multiphase tablets known in the art, with the result that the tablets of the present invention are less susceptible to fracture along the line of contact between the phases.

Method

Multi-stage cleaning tablets are prepared using any suitable tableting equipment, for example, a Courtoy R253 tablet press. Preferably, the tablets are prepared by compression in a tablet press capable of preparing a tablet comprising an impression. In a particularly preferred embodiment of the present invention, the first step is prepared using a specially designed tablet press following the procedure described below. The one or more punches of this tablet press are modified so that the surface of the punch which comes into contact with the detergent composition has a convex surface.

A first detergent composition is fed into the die of the tablet press and the punch is lowered until it comes into contact with, and subsequently compresses the detergent composition for the purpose of forming the first phase. The first detergent composition is compressed using an applied pressure generally of at least about 250 kg / cm <2>, preferably in the range from about 250 to about 2000 kg / cm <2>, more preferably in the range from about 500 to about 1500 kg / cm <2>, most preferably in the range between about 600 and about 1200 kg / cm <2>. The punch is then raised, exposing the first step with the impression. Subsequently, a second detergent composition and, optionally, one or more subsequent optional detergent compositions are fed into the impression. The specially designed tablet press punch is subsequently lowered a second time in order to slightly compress the second detergent composition and the one or more additional detergent compositions optionally present in order to form the second and, optionally, the one or more subsequent steps . In another embodiment of the present invention in which a subsequent step is optionally present, the optionally present next step is prepared in an optional subsequent compression step similar to the second compression step described above. The second and one or more optionally present successive detergent compositions are compressed to a pressure preferably less than about 350 kg / cm <2>, more preferably about 40 to about 300 kg / cm <2>, most preferably. of about 70 to about 270 kg / cm <2>. After compression of the second detergent composition, the punch is raised a second time and the multiphase detergent tablet is then expelled from the tablet press.

Detergent components - The first and second and / or one or more optionally present phases of the multiphase detergent tablet described herein are prepared by compressing one or more compositions comprising active components of the detergents. Suitably, the compositions used in any of these steps may comprise a variety of different detergent components including adjuvant compounds, surfactants, enzymes, bleaching agents, alkalinity sources, color imparting agents, perfume, calcium soap dispersants, organic polymeric compounds comprising polymer dye transfer inhibitors, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilizers, corrosion inhibitors, foaming suppressants, solvents, fabric softening agents, optical and hydrotropic brighteners.

Highly preferred first step detergent components include an adjuvant compound, a surfactant, an enzyme and a bleaching agent. Highly preferred second step detergent components include adjuvants, enzymes, crystal growth inhibitors and disintegrating and / or binding agents.

Adjuvant compound

The tablets of the present invention preferably contain an adjuvant compound, typically present at a level in the range of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight, with reference to the weight of the composition of active components of the detergents.

Water-soluble adjuvant compound

Suitable water-soluble adjuvant compounds include the water-soluble monomeric polycarboxylates, or their acid forms, homopolymer or copolymer polycarboxylic acids or their salts, wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by no more than 2 carbon atoms , carbonates, bicarbonates, borates, phosphates and mixtures of any of the above.

The carboxylate or polycarboxylate adjuvant can be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing a carboxyl group include the water-soluble salts of lactic acid, glycolic acid, and their ether derivatives. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, mayionic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and acid fumaric, as well as heterecarboxylates and inylcarboxylates alone. Polycarboxylates containing 3 carboxyl groups include, in particular, water-soluble citrates, aconitates and citraconates, as well as derivatives of succinate, such as the carboxymethyloxysuccinates described in the British Patent No. 1,379,241, the lactoxysuccinates described in the British Patent No. 1,389,732, and the aminosuccinates. described in the Netherlands patent application 7205873, and the oxypolycarboxylate materials, such as the 2-oxo-1,3-propantricarboxylates, described in the British patent No. 1,387,447.

The polycarboxylates containing the 4 carboxylic groups include the oxidisucciriates described in British Patent No. 1,261,829, the 1,1,2,2-ethantetracarboxylates, the 1,1,3,3-propantetracarboxylates and the 1,1,2,3 -propantetracarboxylates. Polycarboxylates containing sulfur substituents include the sulfosuccinate derivatives disclosed in British Pat. Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolyzed citrates disclosed in British Patent No. 1,439,000.

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

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxyl groups per molecule, more particularly citrates.

Parent acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g., citric acid, or mixtures of citrates / citric acid are also contemplated as useful adjuvant components.

Adjuvants of borate character, as well as adjuvants containing borate-forming materials that can produce borate in the storage conditions of detergents or in washing conditions can also be used, however they are not preferred when washing conditions at temperatures below 50 ° C, especially below 40 ° C.

Examples of adjuvants with carbonate character are alkaline earth metal carbonates and alkali metal carbonates, including sodium carbonate and sesquicarbonate and their mixtures with ultrafine calcium carbonate, as described in German patent application No. 2,321,001 , published November 15, 1973.

Highly preferred adjuvant compounds for use in the present invention are water-soluble phosphate adjuvants. Specific examples of hydrosoluble phosphate adjuvants are alkali metal tripolyphostates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, potassium sodium orthophosphate, sodium polymetaphosphate, in which the degree of polymerization is in the range of from 6 to 21, and salts of phytic acid.

Specific examples of adjuvants with water-soluble phosphate character are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate in which the degree of. polymerization is in the range of 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Adjuvant Compound The tablets of the present invention may contain a partially soluble or insoluble adjuvant compound. Partially soluble and insoluble adjuvant compounds are particularly suitable for use in tablets prepared for use in textile washing methods. Examples of partially water-soluble adjuvants include layered crystalline silicates as described, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Layered crystalline sodium silicates of the general formula are preferred

NaMSixO2 + 1 yH2O

where M is sodium or hydrogen, x is a value number in the range of 1.9 to..4, and y is a value number in the range of 0 to 20. Layered crystalline sodium silicates , of this type preferably have a two-dimensional "sheet" structure, such as the so-called "delta" layer structure, as described in EP 0164514 and EP 01293640. Methods for the preparation of layered crystalline silicates of this type are described in DE -A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula presented above has a value of 2, 3 or 4, and preferably is equal to 2.

The most preferred crystalline layered sodium silicate compound has the formula and is known as "NaSKS-6" (trade name), available from Hoechst AG.

The layered crystalline sodium silicate material is preferably present in the granular detergent compositions in the form of a particulate material in intimate admixture with a solid, water-soluble, ionizable material, as described in the patent application under PCT No. W092 / 18594.

The solid, water-soluble, ionizable material is selected from organic acids, salts of organic and inorganic acids, and mixtures thereof, in which context citric acid is preferred.

Examples of largely water insoluble adjuvants include sodium aluminosilicates. Suitable aluminosilicates include zeolites of the aluminosilicate type having the unit cell formula in which z and y are equal to at least 6; the molar ratio between z and y is in the range of from 1.0 to 0.5 and x is equal to at least 5, preferably in the range of from 7.5 to 276, more preferably from 10 to 264. The materials a aluminosilicates character are in hydrated form and are preferably crystalline, containing from 10% to 28%, most preferably from 18% to 22% of water in bound form.

The aluminosilicate zeolites can be materials present in nature, however they are preferably obtained by synthesis. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations 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 method for preparing colloidal aluminosilicate zeolites. The particles of colloidal aluminosilicate zeolite preferably should be such that no more than 5% of the particles have a size greater than 1 μm in terms of diameter, and no more than 5% of the particles have a size smaller than 0.05 μm in terms of diameter. Preferably, the aluminosilicate zeolite particles have an average particle size, in terms of average diameter, in the range from 0.01 μm to 1 μm, and more preferably between 0.05 μm and 0.9 μm, most preferably between 0.1 μm and 0.6 μm.

Zeolite A has the formula

where x is from 20 to 30, and especially is equal to 27. The zeolite X has the formula

MAP zeolite, as described in EP-B-384.070 is a preferred zeolite-like adjuvant for use herein.

The preferred zeolites having an aluminosilicate character are the zeolites having a colloidal aluminosilicate character. When employed as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloidal zeolyte A, provide improved performance as adjuvants in terms of improved stain removal. An improved performance of the adjuvants is also seen in terms of reducing the deposits deposited on the tissues and improving the conservation of the whiteness of the tissues; problems which are believed to be associated with detergent compositions with compositions which are not optimal in terms of the adjuvants contained.

detergents containing mixed aluminosilicate zeolites, and precisely comprising colloidal zeolite A and colloidal Y zeolite, provide a sequestering performance of calcium ions which is equal to that provided by an equal weight of commercially available zeolite A. Another surprising finding is that the detergent compositions containing mixed aluminosilicate zeolites, described above, provide a magnesium ion sequestration performance that is improved over that provided by an equal weight of commercially available zeolite A.

Surfactant

The surfactants are active components of the preferred detergents of the compositions described herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants, and mixtures thereof. Products for washing dishes in automatic washing machines must have a low foaming character and therefore the foaming caused by the surfactant system for use in dishwashing methods must be suppressed, or more preferably the foaming must occur to a reduced extent, as typically provided by non-ionic types. Foaming caused by surfactant systems used in methods for washing textiles (laundry) should not be suppressed to the same extent as is necessary. for washing dishes. The surfactant is typically present at a level in the range of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight. weight, with reference to the weight of the composition, of active components of detergents.

A typical listing of the classes of anionic, nonionic, ampholytic and zwitterionic surfactants, and species of these surfactants, is provided in U.S. Pat. 3,929,678 issued to Laughlin and Heuring on: December 30, 1975. A list of suitable cationic surfactants is provided in U.S. Pat. 4,259,217 issued to Murphy on March 31, 1981. A list of surfactants typically included in detergent compositions for dishwashing in automatic dishwashing machines is provided, for example, in EP-A-0414 549 and in applications under the PCT Ni. WO 93/08876 and WO 93/08874.

Non ionic surfactant

Essentially any nonionic surfactant useful for cleansing purposes can be included in the cleansing tablet. Preferred, non-limiting, classes of useful non-ionic surfactants are listed below.

Non-ionic surfactant with ethoxylated alcohol character

The alkylethoxylated condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are useful for use herein. The alkyl chain of aliphatic alcohol can be linear or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mol of alcohol.

Alkylalkoxylate surfactant with hooded end

A suitable surfactant having an alkylalkoxylated character with capped chain ends are poly (oxyalkylated) alcohols with capping epoxy groups represented by the formula:

(I) wherein R <3> is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R <2> is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably it is equal to 1; and y is an integer having a value of at least 15, more preferably at least 20.

Preferably, the surfactant of formula I contains at least 10 carbon atoms in the terminal epoxy unit Suitable surfactants of formula I, according to the present invention, are 1 non-ionic surfactants called POLY-TERGENT © SLF-18B of Olin Corpoaration, as described , for example, in WO 94/22800, published October 13, 1994, by Olin Corporation.

Poly (oxyalkylated) alcohols with capping ether groups

Preferred surfactants for use herein include poly (oxyalkylated) alcohols with capping ether groups having the formula:

wherein R <1> and R <2> are linear or branched aliphatic hydrocarbon radicals, saturated or unsaturated, or aromatic, having from 1 to 30 carbon atoms; R <3> is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30, where when x is 2 or more, 1 radicals R <3> can all be the same or different, and k and j are integers having an average value of 1 to 12 , and more preferably 1 to 5.

R <1> and R <2> are preferably linear or branched, saturated or unsaturated, or aromatic aliphatic hydrocarbon radicals, having from 6 to 22 carbon atoms, in which context those with 8 to 18 carbon atoms are most preferred. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms - are the most preferred meanings for R <3>. Preferably, x is an integer having an average value in the range of from 1 to 20, more preferably from 6 to 15.

As described above, when, in the preferred embodiments, X is greater than 2, the radicals R <2> can all be the same, or different. In other words, R <3> can have a variable meaning selected from any of the alkyleneoxy units as described above. For example, if x is 3, R <3> can be chosen so as to form ethyleneoxy (EO) or propyleneoxy (PO) and the order of presentation can be variable, being able to take the forms (EO) (PO) (EO) , (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO) . Of course, the integer "3" was chosen for the purpose of example only, and the variability can be much greater when x takes on a higher integer value and in this case the compounds can comprise, for example, a plurality of units (EO). and a much smaller number of units (POs).

Particularly preferred surfactants as described above include those which have a low fog point, less than 20 ° C. These low fog point surfactants can then be used in association with a high fog point surfactant, as detailed in. followed herein in order to achieve superior fat cleansing benefits.

Surfactants having poly (oxyalkylated) alcohol character with the most preferred capping ether groups are those in which k is 1 and j is 1 for which the surfactants have the formula

wherein R <1>, R <2> and R <3> are defined as above and x is an integer having an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18. Most preferred are surfactants in which R <1> and R <2> are present in a variable number between 9 and 14, R <3> is H, forming ethyleneoxy, and x is in the range between 6 and 15.

Ϊ surfactants with poly (oxyalkylated) alcohol character with capping ether groups comprise 3 general components, namely a linear or branched alcohol, an alkylene oxide and a terminal capping group with an alkyl ether character. The terminal capping group having an alkyl ether character and the alcohol serve as the hydrophobic, oil-soluble portion of the molecule, while the group formed by the alkylene oxide units forms the hydrophilic, water-soluble portion.

These surfactants show significant improvements in the characteristics of streaking, staining and residual patinas on cleansed surfaces and removal of dirty greases, when used in conjunction with high fog point surfactants, compared to conventional surfactants.

Generally speaking, the poly (oxyalkylene) alcohol surfactants with capping ether groups of the present invention can be produced by reacting an aliphatic alcohol with an epoxide in order to form an ether which is subsequently reacted with a base in order to form a second epoxide. The second epoxide can then be reacted with an alkoxylated alcohol in order to form the new compounds of the following invention. Examples of methods of preparation of surfactants having a character of poly (oxyalkylated) alcohols capped with ether groups are described below:

Preparation of C12 / 14 alkylglycidyl ether

A C12 / 14 fatty alcohol (100.00g 0.515 moles) and tin (IV) chloride (0.58g, 2.23mmol, available from Aldrich) are combined in a 500ml 3-necked round bottom flask of capacity, equipped with a coolant, fitting for argon inlet, loading funnel, magnetic stirrer and internal temperature sensor. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 moles, available from Aldrich) is added drop by drop, operating to maintain the temperature between 60 and 65 ° C. After stirring for another hour at a temperature of 60 ° C, the mixture E is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 moles, 50%), while it is simultaneously kept stirred mechanically. After completion of the addition, the mixture is heated to 90 ° C for 1.5 hours, then it is cooled and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO 4, then filtered and concentrated. Distilling the oil at 100-120 ° C (0.1 mmHg) gives the glycidyl ether in the form of an oil.

Preparation of surfactant with character of C9 / 11-ethereal alcohol C12 / 14 alkyl-hooded

Neodol © 91-8 (20.60 g, 0.0393 mol, ethoxylated alcohol available from Shell Chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) are combined in a background flask spherical with 3 necks of 250 ml capacity equipped with a coolant, argon inlet, loading funnel, magnetic stirrer and internal temperature sensor. The mixture is heated to 60 ° C, and at this point C12 / 14 alkylglycidyl ether (11.00 g, 0.0393 moles) is added drop by drop over 15 minutes. After stirring for 18 hours at 60 ° C, the mixture is cooled to room temperature and dissolved in an equal portion of dichloromethane. The solution is passed through a one-inch bed of silica gel, eluting with dichloromethane. The filtrate is concentrated by evaporation on the rotational evaporator and is subsequently stripped in an oven with bubble refrigerant ("Kugelrohr") (100 ° C, 0.5 mmHg), giving the surfactant in the form of an oil.

Non-ionic surfactant with ethoxylated fatty alcohol / propos silate character

The ethoxylated C6-C18 fatty alcohols and mixed ethoxylated / propoxy C6-C18 fatty alcohols are surfactants suitable for use herein, particularly when they are water-soluble. Preferably, the. ethoxylated fatty alcohols are the ethoxylated C10-C18 fatty alcohols with a degree of ethoxylation of from 3 to 50. most preferably they are the ethoxylated C12-C18 fatty alcohols with a degree of ethoxylation of 3 to 40. Preferably, the mixed ethoxylated / propoxyate fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, one degree di.ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

EO / PO condensates with propylene glycol, non-ionic

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight in the range of from 1500 to 1800 and exhibits insolubility in water. Examples of compounds of this type include certain of the surfactants commercially available under the name Pluronic ™, marketed by BASF. Non-ionic condensation products of EQ with addition products of propylene oxide / diethylenediamine

The condensation products of ethylene oxide with the reaction product of propylene oxide and ethylene diamine are suitable for use herein. The hydrophobic grouping of these products consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight in the range of 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available compounds. under the name Tetronic ™ marketed by BASF.

Mixed non-ionic surfactant system

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

The term "fog point", as used herein, is a well known property of non-ionic surfactants, it is the result of the surfactant becoming progressively less soluble with increasing temperature; the temperature at which the appearance of a second phase can be observed is called the "fog temperature" (see Kirk Othmer's Encyclopedia of Chemical Technology, third edition, volume 22, pages 360-379).

As this term is used herein, a "low fog point non-ionic surfactant" is defined as an ingredient of a non-ionic surfactant system having a fog point of less than 30 ° C, preferably less than 20 °. C, and most preferably less than 10 ° C. Typical low fog point nonionic surfactants include nonionic alkoxylated surfactants, especially primary alcohol derived ethoxylates, and inverted block polymers such as polyoxypropylene / polyoxyethylene / polyoxyxypropylene (PO / EO / PO).

In addition, such low-fog non-ionic surfactants include, for example, ethoxylated propoxylated alcohol (e.g., Olin Corporation's Poly-Tergeiit® SLF18B), poly (oxyalkylated) alcohols with capping epoxy groups (e.g., the Poly series -Tergent © SLF18B of non-ionic surfactants of Olin Corporation, as described, for example, in WO 94/22800, published on October 13, 1994, of Olin Corporation), and surfactants having a character of poly (oxyalkylated) alcohols with capping ether groups.

Non-ionic surfactants can proportionally contain propylene oxide in an amount of up to 15%. by weight. Other preferred nonionic surfactants can be prepared by the processes described in U.S. Pat.

4 .223. 163, issued September 16, 1980, Builloty, incorporated herein by reference.

The low fog point nonionic surfactants additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound. Polyoxyethylenepolyoxypropylene block polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as the reactive hydrogen-containing initiator compound. Certain of the block polymeric surfactant compounds called PLURONIC ©, REVERSED PLURONIC®, and TETRONIC ©, marketed by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the present invention. Preferred examples include REVERSED PLURONIC® 25R2, -and TETRONIC © 702. Such surfactants are typically useful herein as low fog point nonionic surfactants.

With the term "high fog point non-ionic surfactant" used herein, such surfactant is defined as an ingredient of non-ionic surfactant systems having a fog point above 40 ° C, preferably above 50 ° C and more preferably higher than 60 ° C. Preferably, the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxylated or alkylphenol alcohol containing 8 to 20 carbon atoms, with 6 to 15 moles of ethyloxide per mole of alcohol or alkylphenol, on a medium basis. Such high fog point non-ionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

It is also preferred, for purposes of the present invention, that the nonionic high fog point surfactant further has a hydrophilic-lipophilic balance ("HLB"; see Kirk Othmer, loco cited) in the range of 9 to 15, preferably 11 to 15. Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).

Another preferred nonionic high fog point surfactant is derived from a straight or preferably branched or secondary chain fatty alcohol containing 6 to 20 carbon atoms (C6-C20 alcohol) / including secondary alcohols. and primary branched-chain alcohols. Preferably, the nonionic high fog point surfactants are ethoxylates of branched or secondary alcohols, more preferably branched alcohol ethoxylates C9-C1 or C11-C15, condensed with an average of from 6 to 15 moles, preferably from .6 to 12 moles, and most preferably 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant thus derived has a narrow distribution of the degree of ethoxylation, relative to the average degree of ethoxylation.

Anionic surfactant

Essentially any anionic surfactant useful for detergency purposes is suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of anionic surfactants having a sulfate, sulphonate, carboxylate and sarcosin character. Anionic sulfate surfactants are preferred.

Other anionic surfactants include isethionates, such as acylisethionates, N-acyltaurates, fatty acid amides of methyltauride, alkyl succinates and sulphosuccinates, sulfosuccinate monoesters (especially C12-C18 saturated and unsaturated monoesters), sulfosuccinate diesters (especially C6-C14 diesters) saturated and unsaturated), N-acylsarcosinates. Also suitable are resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic surfactant with a sulphate character

Sulfate anionic surfactants suitable for use herein include primary and secondary linear and branched alkyl sulfates, alkylethoxy sulphates, (fatty oleoyl) -glycerolosulfates, alkylphenolethylene oxide ether sulfates, C5-C1-acyl-N- (C1-C4-alkyl ) - and -N (C1-C2 hydroxyalkyl) glucaminesulphates and alkyl polysaccharide sulfates, such as sulfates of alchiipoliglucosi.de (the non-ionic, non-sulfated compounds being described herein}.

The surfactants having an alkyl sulfate character are preferably selected from the range of C10-C18 alkyl sulfates with primary linear and branched akyl radicals, more preferably the C11-C15 branched chain alkyl sulphates and the C12-C14 linear chain alkyl sulphates.

The surfactants having an alkylethoxysulfate character are preferably selected from the group consisting of C10-C18 alkylsulfates which have been hydroxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the surfactant having an alkylethoxy sulfate character is a C11-C18, more preferably C11-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 present invention employs mixtures of the surfactants having a preferred alkyl sulfate and alkylethoxysulfate character. Such mixtures have been described in the patent application pursuant to PCT No. WO 93/18124. Sulfonate anionic surfactant

Sulfonate anionic surfactants suitable for use herein include salts of C5-C20 (linear alkyl) benzenesulfonates, alkylesteresulfonates, primary or secondary C6-C22 alkanesulfonates, C16-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol -glycerol sulphonates, (fatty oleyl) glycerol sulphonates, and any mixture thereof.

Carboxylate anionic surfactant Suitable carboxylate anionic surfactants include. alkylethoxycarboxylates, alkylpolyethoxypolycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps, as described herein.

Suitable alkylethoxycarboxylates include those with the formula where R is a C6 to C15 alkyl group, x is in the range of 0 to 10, and the distribution of the degree of ethoxylation is such that, on a weight basis, the amount of material where x is 0 is less than 20%, and M is a cation. Suitable surfactants of alkyl polyethoxy polycarboxylates include those having the formula where R is a C6-C18 alkyl group, x is 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl-acid radical, acid radical succinic, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants which contain a carboxylic unit bonded to a secondary carbon atom. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-acid. nonanoic, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as foaming suppressing agents.

Surfactant with character of alkali metal sarcosinate

Other suitable anionic surfactants are x alkali metal sarcosinates of the formula wherein R is a linear or branched C5-C1 alkyl or alkenyl group, R <1> is a C1-C4 alkyl group and M is an alkali metal ion. Preferred agents are myristyl- and oleoylmethylsarcosinates, in the form of their sodium salts.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include amino oxide surfactants and alkylanphocarboxylic acids.

Suitable aminooxides include those compounds having the formula in which R <3> is selected from an alkyl, hydroxyalkyl, propyl and alkylphenyl acylamide group, or mixtures thereof, containing from 8 to 26 carbon atoms; R <4> is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R <5> is an alkyl or hydroxyalkyl group containing 1 to 3, or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Preferred are C10 “C18 alkyldimethylaminooxide, and C10-18acylamidoalkyldimethylaminooxide.

A suitable example of an alkylanphodicarboxylic acid is Miranol <(> ™ <)> C2M Conc. Manufactured by Mixanol, Inc., Dayton, NJ.

Zwitterionic surfactant

The zwitterionic surfactants can also be incorporated in the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or ternary sulfonium compounds. Betaine and soltaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds which have the formula in which R is a C3-C18 hydrocarbyl group, each R <1> is typically C1-C3 alkyl and R <z> is a C3-C5 hydrocarbyl group. Preferred betaines are C12-C18 di-methyl-ammoniumhexanoate and the CI0-CIB acylammidopropan (or ethane) dimethyl (or diethyl) betaines.

Complex betainic surfactants are also useful for use herein.

Cationic surfactants

The cationic ester surfactants used in the present invention are preferably water dispersible compounds having surfactant properties comprising at least one ester bond (i.e., -C00-), and at least one cationically charged group. Other suitable ester cationic surfactants, including cholinic ester surfactants, have been described, for example, in U.S. Pat. Ni. 4228042, 4239660. And 4260529..

Suitable cationic surfactants include quaternary ammonium surfactants selected from the mono-C6-C16- surfactants, preferably -C6-C1-N-alkyl- or -alkenylammonium, in which the remaining positions on the nitrogen are substituted with groups methyl, hydroxyethyl or hydroxypropyl. Enzymes

Enzymes are preferred detergent components for the first step and more particularly for the second step and / or further optionally present steps. When present, said enzymes are selected from the group consisting of cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenoloxidase, lipoxigenase, ligninase , pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase or their mixtures.

Preferred enzymes include protease, amylase, lipase, peroxidase, cutinase and / σ cellulase in association with one or more plant cell wall degrading enzymes.

Cellulases usable in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimal pH value in the range from 5 to 12 and an activity higher than 50 CEVU (cellulose viscosity unit). Suitable cellulases are described in U.S. Pat. 4,435,307, Barbesgoard et al. in J61078384 and in WO96 / 02653, which describe fungal cellulases produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum respectively. 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 W095 / 26398.

Examples of such cellulases are cellulases produced by a Humicola insolens strain (Humicola grisea var. Thermoidea), in particular the Humicola DSM 1800 strain. Other suitable cellulases are cellulases originating 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 has the amino acid sequence described in the patent application according to PCT No. WO 91/17243. Suitable cellulases are also EGIII cellulases obtainable from Trichoderma longibrachiatum described in WO94 / 21801, Genencor, published on 29 September 1994. Especially suitable cellulases are cellulases which offer color care benefits. Examples of such cellulases are the cellulases described in European patent application No. 91202879.2, filed on November 6th, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO91 / 17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or detergent properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

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

Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, and so on. They are used for "solution bleaching", that is, in order to prevent the transfer of dyes or pigments removed from substrates during the washing operations, to other substrates during the washing solution. Enzymes having a peroxidase character are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chloroperoxidase and bromine peroxidase. Detergent compositions containing peroxidase are described, for example, in international patent applications pursuant to PCT WÓ 89/099813, WO89 / 09813 and in European patent applications EP No. 91202882.6, filed on November 6, 19991, and EP No. 96870013.8, filed February 20, 1996. The enzyme laccase is also useful.

Preferred enhancers are substituted phenothiazine and phenoxazine, 10-phenothiazinpropionic acid (PPT), 10-ethylphenothiazin-4-carboxylic acid (EPC), 10-phenoxyazinpropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and in substituted syringes (Cj-Cs-substituted alkylsyringates), and phenols. Sodium percarbonate or sodium perborate are the preferred sources of hydrogen peroxide.

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

Other preferred enzymes which may be included in the detergent compositions of the present invention include lipases. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in British Patent 1,272,034. Suitable lipases - include those which show a positive immunological cross-reaction with the antibody directed against the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", and is referred to hereinafter as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases obtainable from Chromobacter viscosum, for example, Chromobacter viscosum var. lipoìyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; lipases obtainable from Chromobacter viscosun, available from U.S.

Biochemical Corp., U.S.A. and from Disoynt Co., the Netherlands; and lipases obtainable from Pseudomonas gladioli.

Especially suitable lipases are lipases such as MI Lipase <R> and Lipomax <R> (Gist Brocades) and Lipolase <R> and Lipolase Ultra <R> (Novo), which have been found to be very efficient when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, W0 92/05249 <'> and WO 95/22615 of Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 of Unilever.

Also suitable are cutinases [EC 3.1.50], which can be considered as a special type of lipase, namely lipases which do not require interfacial activation. The addition of cutinase to detergent compositions has been described for example in WO-A-88/09367 (Genencor); in WO 90/09446 (Plant Genetic System) and in WO 94/14963 and WO 94/14964 (Unilever).

The lipases and / or cutinases are normally incorporated into the detergent composition at levels of 0.0001% to 2% - of active enzymatic species by weight, with reference to the weight of the detergent composition.

Suitable protectors are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). A suitable protessi is obtained from a Bacillus strain, having the maximum activity throughout the pH range from 8 to 12, developed and marketed as ESPERASE © by Novo Industries A / S of Denmark, indicated below. in the present as "Novo". The preparation of this enzyme, and of similar enzymes, is described in GB 1.243.784 in the Novo. Other suitable proteases include KANNASE®, ALCALASE®, DURAZYM © AND SAVINASE® from Novo and MAXATASE®, MAXACAKL®, PROPERASE® and MAXAPEM © (Genetically engineered modified Maxacal), available from Gist-Brocades. Proteolytic enzymes include. also modified bacterial serine proteases, such as those described in European patent application No., serial number 87303761.8, filed on April 28, 1987 (in particular on pages 17, 24 and 98), and which is referred to herein as "Protease B", and in European patent application 199404, Venegas, published on October 29, 1986, which refers to a modified bacterial proteolytic serine enzyme which is referred to herein as "Protease A". Suitable is what is called in the present "Protease C", which is a variant of an alkaline serine protease obtainable from Bacillus in which a lysine has replaced an arginine at position 27, a tyrosine has replaced smallpox at position 104, a serine replaced asparagine at position 123, and an alanine replaced threonine at position 274. Protease C is described in EP 90915958.4, corresponding to WO 91/06637, published May 16, 1991 . Also included in the present are variants modified by genetic modification techniques, in particular of Protease C.

A preferred protease, referred to herein as "Protease D" is a variant of a carbonylhydrolase having an amino acid sequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid in place of a plurality of radicals aminoacyls in a position in said carbonylhydrolase equivalent to position 76, preferably also in combination with one or more radical positions of amino acids equivalent to those selected from the group consisting of,

according to

numbering of Bacillus amyloliquefaciens subtylysin, as described in WO 95/10591, and in the patent application of C. Ghosh, et al. "Bleaching Compositions Comprising Protease Enzymes" having the serial number U.S. 08 / 322.677, filed on 13 October 1994.

Proteases described in patent applications EP 251446 and WO 91/06637, the BLAP® prosthesase described in WO 95/10591 and their variants described in WO 965/23221 are also useful for the present invention.

See also a high pH protease produced by Bacillus sp. NCIMB 40338, described in WO 93 / 18140A, to Novo. Enzymatic cleaning agents comprising proteases, one or more other enzymes and a reversible protease inhibitor are disclosed in WO 92 / 03529A at Novo. When desired, a protease exhibiting reduced adsorption and increased hydrolysis characteristics is available, as described in Procter & Gamble's WO 95/07791. A recombinant trypsin-like protease for detergents useful herein is disclosed in WO 94/25583 to Novo. Other suitable proteases are described in EP 516200 by Unilever.

Other preferred protease enzymes include protease enzymes which are a variant of the carbonyl hydrolase having an amino acid sequence not found in nature, which is derived by replacing a plurality of amino acid radicals of a precursor carbonyl hydrolase with different amino acids, in wherein said plurality of amino acid radicals substituted in said precursor enzyme correspond to position 210 in combination with one or more of the following

whose numbered positions correspond to the subtilisin of natural origin produced by Bacillus amylol iquefa ciens, or to equivalent aminoacyl radicals in other carbonylhydrolases or subtilisins (such as the subtilisin of Bacillus lentus). Preferred enzymes of this type include those which exhibit variations at positions 210, 76, 103, 104, 156, and 166.

The proteolytic enzymes are incorporated into the detergent compositions of the present invention at a level of 0.0001% to 2%, preferably 0.001% to 0.2%, more preferably 0.005% to 0.1% pure enzyme by weight, with reference to the weight of the composition.

Amylase (a and / or β) can be included for the removal of carbohydrate stains. WO 94/02597 of Novo Nordisk A / S, published February 3, 1994, discloses detergent compositions which contain mutant amylases. See also WO 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known for use in detergent compositions include both cc-amylase and β-amylase. The a-amylases are known from the art and include those described in U.S. Pat. No. 5,003,257; in EP 252,666; WO / 91/00353, FR 2,676,456, EP 285,123, EP 525,610, EP 368,341, and in British patent specification No. 1,296,839 (Novo). Other suitable amylases are amylases with enhanced stability characteristics described in WO 94/18314 published on August 18, 1994 and in WO 96/05295, Genencor, published on February 22, 1996, and amylase variants having an additional modification in the immediate progenitor, available from Novo Nordisk A / S, described in WO 95/10603, published, in April 1995. Amylases described in EP 277.216, WO 95/26397 and WO 96/23873 (all from Novo Nordisk) are also suitable.

Examples of commercial a-amylase products are Purafect Ox Am © from Genencor and Termamyl®, Ban®, Fungamyl®, and Duramyl®, Natalase® all available from Novo Nordisk A / S, Denmark. WO 95/26397, describes other suitable amylases: a-amylases characterized by having a specific activity that is at least 25% greater than the specific activity of Termamyl® in a temperature range of from 25 ° C to 55 ° C and from a pH value in the range of 8 to 10, measured by means of the test for the determination of the Phadebas® α-amylase activity. Variants of the above enzymes described in WO 96/23873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO 95/35382.

Preferred amylase enzymes include those described in WO 95/26397 and in Novo Nordisk's patent application, simultaneously pending, PCT / DK96 / 00056.

The amylolytic enzymes are incorporated into the detergent compositions of the present invention at a level in the range of 0.0001% to 2%, preferably 0.00018% to 0.06%, more preferably 0.00024% to 0.048% of pure enzyme by weight, with reference to the weight of the composition.

In a particularly preferred embodiment of practical embodiment, detergent tablets of the present invention comprise enzymes having an amylase character, in particular those described in WO 95/26397. and in the concurrently pending patent application PCT / DK96 / 00056 from Novo Nordisk in combination with a complementary amylase.

By "complementary" is meant the addition of one or more amylases suitable for detergency purposes. Examples of complementary amylases (a and / or β) are described below. WO 94/02597. And WO 95/10603, Novo Nordisk A / S, disclose detergent compositions incorporating mutant amylases. Other known amylases for use in detergent compositions include both aamylase and β-amylase. The α-amylases are known in the art and include those described in U.S. Pat. No. 5,003,257; in EP 252,666; WO / 91 / 003S3; FR 2,676,456; EP 285.123; EP 525.610; EP 368.341; and in British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are amylases with enhanced stability described in WO 94/18314 and WO 96/05295, Genencor, and the amylase variants having an additional modification in the immediate parent species available from Novo Nordisk A / S, described in WO 95/10603. Amylases described in EP 277 216 (Novo Nordisk) are also suitable. Examples of commercial a-amylase products are Purafect Ox Am © from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S, Denmark. WO 95/26397 discloses other suitable amylases: a-amylases characterized by having a specific activity that is at least 25% greater than the specific activity of Termamyl © in a temperature range of 25 ° C to 55 ° C , and at a pH value in the range from 8 to 10, according to measurement carried out by testing and determining the activity of Phadebas® α-amylase. Variants of the above enzymes described in WO 96/23873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and a higher level of activity are described in WO 95/35382. Preferred complementary amylases for the present invention are the amylases marketed under the trade names Purafect Ox Am <R>, described in WO 94/18314, WO 96/05295, marketed 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 at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% of pure enzyme by weight, relative to the weight of the composition. Preferably, a weight ratio, with reference to pure enzymes, between the specific amylase and the complementary amylase is in the range from 9: 1 to 1: 9, more preferably from 4: 1 to 1: 4, and most preferably between 2: 1 and 1: 2.

The enzymes mentioned above can. be of any suitable origin, for example, of plant, animal, bacterial, fungal, and yeast origin. The origin can also be exophilic or extremophilic microorganisms (psychrophilic, psychotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, and so on). Purified or non-purified forms of these enzymes can be used. Mutant types of native enzymes are also included by definition. Mutants can be obtained for example by manipulation by protein and / or genetic engineering, chemical and / or physical modification of native enzymes. Common practice is also - the expression of the enzyme via host organisms into which the genetic material responsible for the production of the enzyme has been cloned.

Said enzymes are normally incorporated in the detergent composition at levels of from 0.0001% to 2%, of species having enzymatic activity by weight, with respect to the weight of the detergent composition. The enzymes can be added in the form of separate single ingredients (pearls, granulates, stabilized liquids, etc., containing an enzyme) or as mixtures of 2 or more enzymes (e.g., cogranulates).

Other suitable detergent ingredients that may be added are enzyme oxidant scavengers, which are disclosed in concurrently pending European Patent Application 92870018.6, filed January 31, 1992. Examples of such enzyme oxidant scavengers are ethoxylated tetraethylene polyamines.

A range of enzymatic materials and means for their incorporation into synthetic detergent compositions are also described in WO 9307263A and WO 9307260A to Genercor International, in WO 8908694

A to Novo, and in U.S. 3,553,539, January 5, 1971, a

McCarty et al. Enzymes are further described in

U.S. 4,101,457, Place et al., July 18, 1978, and in

U .S.4.507.219, Hughes, March 26, 1985. Materials

enzymatic useful for liquid detergent formulations,

and their incorporation into such formulations are

described in U.S. 4,261,868, Hora et al. April 14

1981. Enzymes for use in detergents can be

stabilized by various techniques. Techniques for

stabilization of enzymes are described and exemplified in U.S. 3,600,319, August 17, 1971, Gedge

et al., EP 199,405 and -EP 200,586 October 29, 1986, 'Venegas. Systems for the stabilization of enzymes

are also described, for example, in U.S. 3,519,570.

A Bacillus, sp. AC13 useful providing protease,

xylanase and cellulase, is described in WO 9401532 A

to the Novo.

Bleaching agent

A highly preferred component of the

composition of components of detergents is an agent

bleach. Suitable bleaching agents include

chlorinated bleaching agents and bleaching agents

releasing oxygen.

In a preferred aspect, the oxygen releasing bleaching agent contains a hydrogen peroxide source and a precursor compound of the bleach which, in this case, is an organic peroxyacid. The production of the organic peroxyacid takes place by means of an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred hydrogen peroxide sources include inorganic perhydrate bleaches. In a preferred alternative aspect, a preformed organic peroxyacid is incorporated directly into the composition. Also contemplated are compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic perhydrate bleaches

The compositions of components of. detergents preferably comprise a source of hydrogen peroxide, such as an oxygen releasing bleach. Suitable hydrogen peroxide sources include the inorganic perhydrate salts.

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

Examples of inorganic perhydrate salts include perborate salts, percarbonates, superphosphates, persulfates and persilicates. Inorganic perhydrate salts are normally alkali metal salts. The inorganic perhydrate salt can be in use in the form of a crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of such granular compositions utilize a coated form of the material, which provides improved storage stability characteristics of the perhydrate salt in the granular product.

The sodium perborate can be in the form of the monohydrate, having the nominal formula

or in the tetrahydrate formula,

The alkali metal percarbonates, in particular sodium percarbonate, are preferred perhydrates for inclusion in compositions according to the invention. Sodium percarbonate is an addition compound having a formula corresponding to and is commercially available in the formula of a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound, tends, upon dissolution, to release hydrogen peroxide rather rapidly, and this increases the tendency to develop high localized concentrations of bleach. Percarbonate is most preferably incorporated into such compositions in a coated form which provides stability in the product.

A suitable coating material that provides stability in the product comprises a mixed salt of a water-soluble alkali metal sulfate and carbonate. This coating, together with coating processes, were previously described in GB 1.466.799, granted to Interox on March 9, 1977. The weight ratio between the coating material having a mixed salt character and the percarbonate is included in the range of from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt is of sodium sulfate and sodium carbonate, and has the formula where n is from 0.1 to 3, preferably n is from 0.3 to 1.0, and most preferably n is from 0.2 to 0.5.

Another suitable coating material which provides stability in the product comprises sodium silicate with a ratio in the range of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicates, preferably applied at a level in the range of from 2% to 10% (normally from 3% to 5%) of SiO 2 by weight, with respect to the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Also suitable are coatings which contain, silicate salts of borates or boric acids, or other inorganic species.

Other coatings which contain waxes, oils, soaps of fatty acids can be used to advantage in the context of the present invention.

Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the compositions referred to herein.

The precursor of peroxyacid bleaches

The precursors of peroxyacid bleaches are compounds which act with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally, the peroxyacid bleach precursors can be represented as

where L is a leaving group and X is essentially any functionality such that upon perhydrolysis the structure of peroxyacid produced will be

Peroxyacid bleach precursor compounds are preferably incorporated at a level of 0.5% to 20% by weight, more preferably 1% to 10% by weight, most preferably 1.5% by weight. at 5% by weight, with reference to the weight of the compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oxines. Examples of materials useful within these classes are described in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170836.

Leaving groups

The leaving group, hereinafter referred to as "L", must be sufficiently reactive so that the perhydrolysis reaction can take place within the optimal time interval (for example, in a washing cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are chosen from the group consisting of:

and their mixtures, in which R <1> is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R <3> is an alkyl chain containing from 1 to 8 carbon atoms, R <4> is H or R <3>, R <5> is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R <1>, R <3> and R <4> can be substituted with essentially any functional group including, for example, alkyl, hydroxyl, alkoxy groups, halogen atoms, amino groups, nitrosyl groups, amide groups and ammonium or alkylammonium groups.

The preferred solubilizing groups are

and to an extent

most preferably, where R <3> is an alkyl chain containing 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium being most preferred, and X is an anion. halide, hydroxide, methyl sulfate or acetate.

Precursor of perbenzoic acid

Perbenzoic acid precursor compounds provide perbenzoic acid following perhydrolysis.

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

Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides, with benzoylating agents, including, for example:

where Ac = COCH3; B- = Benzoyl.

Perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoylsubstituted ureas. Suitable precursors of perbenzoic acid of the imidazole type include N-benzoylimidazole and N-benzoylbenzimidazole and other precursors of perbenzoic acid containing useful N-acyl groups include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

Other precursors of perbenzoic acid include benzoyldiacylperoxides, benzoyltetraacylperoxides and compounds having the formula:

Phthalic anhydride is another suitable perbenzoic acid precursor compound for use herein:

Suitable precursors of perbenzoic acid character of N-acylated lactams have the formula:

wherein n is from 0 to 8, preferably from 0 to 2, and R <6> is a benzoyl group.

Precursors of perbenzoic acid derivatives

Perbenzoic acid derivatives precursors provide substituted perbenzoic acids following perhydrolysis.

Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic acid precursors described herein in which the benzoyl group is substituted with essentially any non-positively charged (i.e., non-cationic) functional group including, for example, alkyl, hydroxyl, alkoxy, halogen atoms, amino groups, nitrosyl groups and amide groups.

A preferred class of precursor compounds of substituted perbenzoic acids are the amidosubstituted compounds of the following general formulas:

wherein R <1> is an aryl or alkaryl group with 1 to 14 carbon atoms, R <2> is an arylene or alkaryl group containing 1 to 14 carbon atoms, and R <5> is H or a alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and L can be essentially any leaving group. R <1> preferably contains from 6 to 12 carbon atoms. R <2> preferably contains 4 to 8 carbon atoms. R <1> can be aryl, substituted aryl or alkylaryl containing branching, substitution, or both such types of structure and radicals of this type can be produced by synthesis, or they can be obtained from natural solvents including, for example, tallow fat . Similar structural variations are allowed for R <2>. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent organic groups or compounds. R <5> preferably is H or methyl. R <1> and R <5> must not contain more than 18 carbon atoms in total. Amido-substituted bleach activating compounds of this type are disclosed in EP-A-0170386.

Precursors of cationic peroxyacids

Cationic peroxyacid precursor compounds produce cationic peroxyacids upon perhydrolysis.

Typically, the cationic 'peroxyacid' precursors are formed by replacing the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethylammonium or methylammonium group. The cationic peroxyacid precursors are typically present at the positions in the form of a suitable anion salt, such as, for example, a halide ion or a methyl sulfate ion.

The peroxyacid precursor compound which is thus to be cationically substituted may be a precursor compound of perbenzoic acid or a substituted derivative thereof as described above herein. Alternatively, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amidosubstituted alkyl peroxyacid precursor, as described hereinafter.

The cationic peroxyacid precursors are disclosed in U.S. Pat. 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475.512; 458.396 and 284.292; and in JP 87-318.332.

Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulphonates, N-acylated caprolactams, and monobenzoyltetraacetylglucosebenzoylperoxides.

A preferred cationically substituted benzoyloxybenzenesulfonate is the 4- (trimethylammonium) -methyl derivative of benzoyloxybenzenesulfonate;

A preferred cationicamerite substituted alkyloxybenzenesulfonate has the formula:

Preferred cationic peroxyacid precursors belonging to the class of N-acylated caprolactams include trialkylammoniomethylenebenzoylcaprolactams, in particular trimethylammoniomethylenebenzoylcaprolactam:

Other preferred cationic peroxyacid precursors of the class of N-acylated caprolactams include trialkylammoniomethylenalkylcaprolactams:

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

Another preferred cationic peroxyacid precursor is N- (N, N, N-trimethylammonium) ethylsodium-4-sulfophenylcarbonate chloride.

Precursors of alkylpercarboxylic acid bleaches

The precursors of alkylpercarboxylic acid bleaches form percarboxylic acids following perhydrolysis. Preferred precursors of this type yield peracetic acid upon perhydrolysis.

Preferred alkylpercarboxylic acid precursor compounds of the imide type include the N, N, N ', N'-tetraacylated alkylenediamines, in which the alkylene group contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and. 6 carbon atoms. Particularly preferred is tetraacetylenediamine (TAED).

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

Precursors of amidosubstituted alkylperoxyacids

Amidosubstituted alkylperoxyacid precursor compounds are also suitable, and include those of the following general formulas:

wherein R <:> is an alkyl group with 1 to 14 carbon atoms, R <2> is an alkylene group containing 1 to 14 carbon atoms, and R <5> is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R <1> preferably contains from 6 to 12 carbon atoms. R <2> preferably contains 4 to 8 carbon atoms. R <1> can be a straight or branched chain alkyl containing branching, substitution, or both, and can come from synthetic sources or natural sources including, for example, tallow fat. Similar structural variations are allowed for R <2>. The substitution may include alkyl groups, halogen atoms, nitrogen, sulfur and other typical substituent organic groups or compounds. R <5> is preferably H or methyl. R <1> and R <5> must not contain more than 18 carbon atoms in total. Amido-substituted bleach activating compounds of this type are disclosed in EP-A-0170386.

Organic peroxyacid precursors with benzoxazine character

Also suitable are precursor compounds of the benzoxazine type, as described, for example, in EP-A-332.294 and EP-A-482.807, in particular those having the. formula:

including substituted benzoxazines of the type

wherein R <1> is H, alkyl, alkaryl, aryl, arylkyl, and whose R2, R3, R4 and R5 can be the same substituent or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR6 (where R6 is H or an alkyl group) and carboxyl functions.

A particularly preferred precursor of the benzoxazine type is:

Preformed organic peroxyacid

The organic peroxyacid bleach system may contain in addition to an organic peroxyacid bleach precursor compound, or as an alternative thereto, a preformed organic peroxyacid, typically at a level of 0.5% to 25% by weight, plus preferably from 1% to 10% by weight, with reference to the weight of the composition.

A preferred class of organic peroxyacid compounds are the amido-substituted compounds of the following general formulas:

wherein R <2> is an alkyl, aryl or alkaryl group with 1 to 14 carbon atoms, R <2> is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R <5> is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. R <1> preferably contains from 6 to 12 carbon atoms. R 'preferably contains from 4 to 8 carbon atoms. R <2> can be straight-chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both, and can come from synthesis processes or natural sources including, for example, tallow fat. Similar structural variations are permissible for R <2>. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical organic groups or compounds or substituents. R <5> is preferably H or methyl. R <1> and R <5> must not contain more than 18 carbon atoms in total. Amido-substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl- and tetraacylperoxides, especially diperoxy-dodecanedioic acid, diperoxytetradecanediic acid and diperoxyhexadecanedium acid. Benzoyl peroxide is a preferred organic peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassyl acid, and N-phthaloylaminoperoxyapronic acid are also suitable herein.

Means for controlling the speed of release

Means can be provided for controlling the rate of release of the bleaching agent, in particular of the oxygenated bleach to the wash solution.

Means for controlling the release rate of the bleach may allow for the controlled release of the peroxidized species to the wash solution. Such means could, for example, comprise the control of the release of any inorganic perhydrate salt, acting as a source of hydrogen peroxide, to the washing solution.

Another mechanism for controlling the bleach release rate can be by coating the bleach with a coating designed to provide concentrated release. The coating may therefore, for example, comprise a poorly water-soluble material, or it may be a coating with sufficient thickness so that the dissolution kinetics of the coating combine the controlled release rate.

The coating material can be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach in the range of 1:99 to 1: 2. preferably from 1:49 to 1: 9.

Suitable coating materials include triglycerides (e.g., partially hydrogenated vegetable oil, soybean oil, cottonseed oil), monoglycerides or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixture thereof.

Other suitable coating materials may include the sulfates, silicates and carbonates of alkali metals and alkaline earth metals, including calcium carbonate and silicas.

A preferred coating material, in particular for a bleaching agent having the character of such inorganic perhydrate, comprises sodium silicate with a ratio of SiO2: Na20 by weight in the range of 1.8: 1 to 3.0: 1, preferably of 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied at a level, in the range of 2% to 10% (usually 3% to 5%) of Si02 in weight, relative to the weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating.

Any inorganic salt coating material can be combined with organic binder materials to provide composite coatings consisting of inorganic salt / organic binder. Suitable coatings include iC1 0-C20 alcohol ethoxylates containing 5 to 100 moles of ethylene oxide per mol of alcohol, and more preferably C15-C20 alcohol ethoxylates based on primary alcohol containing 20 to 100 moles of ethylene oxide per mol of alcohol. .

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight in the range of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5x10 <6>, preferably from 1000 to 400,000, most preferably from 1000 to 10,000 , are examples of such polymeric materials.

Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, wherein maleic anhydride constitutes at least 20% molar of the polymer, are further examples of polymeric materials useful as binding agents. These polymeric materials can be used as such, or in combination with solvents such as water, propylene glycol and C10-C20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mol already mentioned above. Further examples of ligands include C10-C20 mono- and diglycerol ethers and also C10-C20 fatty acids.

Cellulose derivatives, such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homopolymer or copolymer polycarboxylic acids or salts thereof are other examples of suitable binders for use herein.

One method of applying the coating material involves agglomeration. Preferred agglomeration processes include the use of any of the organic binding materials described above herein. Any conventional agglomerator / mixer can be used, including but not limited to basket, rotary drum and vertical mixer types. Fused coating compositions can also be applied by either being poured, or spray atomized onto a moving bed of bleaching agent.

Other means for providing the required controlled release characteristics include mechanical means for altering the physical characteristics of the bleach in order to control its solubility and release rate. Suitable protocols could include such means as compression, mechanical injection, manual injection, and adjusting the solubility of the bleaching compound by selecting the particle size of any particle component.

While the choice of particle size will depend on both the composition of the particle component and the desire to achieve the desired characteristics of controlled release kinetics, it is desirable that the particle size be greater than 500 micrometers, preferably that the particles have an average diameter. say from 800 to 1200 micrometers.

Additional protocols for providing the controlled release medium include a suitable selection of any other matrix component in the detergent composition, such that when the composition is introduced into the wash solution, the ionic strength provided therein enables the achievement of the required values of controlled release kinetics.

Metal-containing bleaching catalyst

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

A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation with defined bleach catalysis activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalysis activity, such as zinc cations. or aluminum, and a sequestering agent having stability constants defined for the catalytic and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts. Such catalysts are described in U.S. Pat.

4,430,243.

Preferred types of catalysts. of bleaches include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and in U.S. Pat.

5,244,594. Preferred examples of these catalysts include

and their mixtures. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl1,5,9-triazacyclododecane, 2-methyl-1, 4,7-triazaciclononane, 2-methyl-1,1,4-triazaciclononane, 1,2, 4,7-tetramethyl-1, 4,7-triazaciclononane, and mixtures thereof.

The bleaching catalysts useful in the compositions of the present can also be selected as suitable for the present invention. For examples of suitable bleaching catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416, which teaches manganese (IV) mononuclear complexes such as Mn (1,4,7-trimethyl-1,1,4-triazacyclonane) (OCH3) 3- (PF6).

Still another type of bleach catalyst, as described in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylated polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

The patent -U.S. 5,114,611 teaches a bleaching catalyst comprising a transition metal complex, comprising Mn, Co, Fe, or Cu, with a non- (macro) cyclic ligand. Such ligands are of the formula:

where R <1>, R <2>, R <3>, and R <4> can each be chosen within the range of ·. H, substituted alkyl and aryl groups, such that each grouping R <1> -N = C-R <2> and R <3> -C = N-R <4> forms a ring of 5 or 6 terms. Said ring can be further replaced. B is a bridging group chosen from 0, S, CR <5> R <6>, NR <7> and C = 0, where R <5>, R <6> and R <7> can each be H, alkyl groups or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, "pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand 2, 2'- bispyridylamine. Preferred bleaching catalysts include complexes of Co, Cu, Mn, Fe-bispyridylmethane and bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl2, di- (isothiocyanate) bispyridylamine-cobalt (II), trisdipyridylamine- cobalt (II) perchlorate, Co (2,2-bispyridylamine) 202C104, bis- (2,2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate, and mixtures thereof.

Preferred examples include Mn dinuclear complexes with tetra-N-toothed and bi-N-toothed ligands,

And

While the structures of the bleach-catalyzing manganese complexes of the present invention have not been elucidated, it can be speculated that such complexes comprise chelators or other hydrated coordination complexes that result from the interaction of the carboxyl and nitrogen atoms of the ligand. with the manganese cation. Similarly, the oxidation state of the manganese cation during the catalytic process is not known with certainty and may be the valence state (+11), (+ III), (+ IV) or (+ V). Due to the possible six attachment points of the ligands to the manganese cation, it can reasonably be speculated that multinuclear species and / or "cage" structures may exist in the aqueous bleaching medium. Whatever the actual existing form of the active Mn-ligand species, it functions in an apparently catalytic manner by providing improved bleaching performance on difficult stains such as tea, tomato sauce, coffee, wine, fruit and vegetable juices, and the like.

Other bleaching catalysts are described, for example, in the European patent application, Publication No. 408.131 (cobalt complex catalysts), in the European patent application publications Ni. 384.503 and 306.089 (metalloporphyrin catalysts), U.S. 4,728,455 (manganese catalyst / multidentate ligand) y U.S. 4,711,748 and publication of European patent application No.

224.952 (manganese catalyst adsorbed on aluminosilicate), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salts), U.S. 4,626,273 (manganese / ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German patent description 2,054,019 (cobalt-chelating catalysts), Canadian patent 866,191 (salts containing transition metals), U.S. Pat. 4,430,243 (chelators with manganeseum cations and non-catalytic metal cations), and U.S.

4,728,455 (manganese gluconate-based catalysts).

Other preferred examples include cobalt (III) catalysts having the formula:

in which the cobalt is in the oxidation state 3; n is an integer with a value in the range of from 0 to 5 (preferably it is equal to 4 or 5; more preferably 5); M 'represents a monodentate ligand; m is an integer with a value in the range of from 0 to 5 (preferably it is equal to 1 or 2, most preferably it is equal to 1); B 'represents a bidentate ligand; b is an integer having a value of from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more suitably chosen counterions present in a number y, where. y is an integer having a value in the range of from 1 to 3 (preferably from 2 to 3; more preferably it is equal to 2 when Y is an anion having a -1 charge), in order to obtain a salt with charges balanced, preferably the Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof; and in which at least one of the cobalt-bound coordination sites is also labile under the conditions of use during dishwashing operations in automatic dishwashing machines, and the remaining coordination types stabilize the cobalt in the dishwashing conditions in the dishwashing machines. automatic washing machines in such a way that the reduction potential of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) against a normal hydrogen electrode.

Preferred cobalt catalysts of this type have the formula:

wherein n is an integer having a value of from 3 to 5 (preferably 4 or 5; more preferably equal to 5); M 'is a labile coordinating grouping, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) their combinations; m is an integer having a value of 1 to 3 (preferably 1 or 2; more preferably it is equal to 1); m + n = 6 and Y is a suitably chosen counteranion present in a number y of units, where y is an integer having a value of from 1 to 3 (preferably from 2 to 3; most preferably equal to 2 when Y is an anion with charge -1) in order to obtain a salt with balanced charges.

The cobalt catalyst of this type useful in the present preferred are salts of pentaamine cobalt chloride having the formula, and especially

Most preferred are the compositions of the present invention which use bleaching catalysts containing cobalt (III) having the formula:

in which the cobalt is in the oxidation state 3; n is 4 or 5 (preferably 5); M is 1 or more ligands coordinated to cobalt by means of a coordination site; m is 0, 1 or 2 (preferably 1); B is a cobalt-coordinated ligand by means of two sites; b is 0 or 1 (preferably 0) and when b = 0, then m + n = 6, and when b = l, then m = 0 and n = 4; and T is one or more suitably selected counteranions present in a number y of units, where y is an integer such as to obtain a salt with balanced charges (preferably y is from 1 to 3; most preferably it is equal to 2 when T is a -1 charge anion); and wherein further said catalyst has a basic hydrolysis rate constant of less than 0.23 M <'> V <1> (25 ° C). Preferred T are selected from the group consisting of chloride, iodide, I3-, formate, nitrate, nitrite sulfate, sulphite, citrate, acetate, carbonate, bromide, phosphate, phosphite, silicate, tosylate, methanesolionate and their combinations. Optionally, T can be protonated if there are more than one anionic group in T, for example, and so on. Furthermore, T can be selected from the group consisting of <'> non-traditional inorganic anions, such as anionic surfactants [e.g., linear alkyl-radical alkylbenzenesulfonates (LAS), alkylsulfdates (AS), <'> alkyl-oxysulfonates (AES), and so on ] and / or anionic polymers (for example, polyacrylates, polymethacrylates, and so on).

M radicals include, but are not limited to, for example, and carboxylates (which are preferably monocarboxylates, however more than one carboxyl group may be present in the group, provided that binding to cobalt occurs only via one group carboxylic group for each grouping, in which case the other carboxylic group for the M group can be protonated or in its saline form). Optionally, M can be protonated if more than one anionic group exists in M (e.g.,

and so on). Preferred M radicals are substituted and unsubstituted C1-C3 carboxylic acids having the formulas:

wherein R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably C1-C1) unsubstituted and substituted alkyl, C6-C30 (preferably C1-C1) substituted and unsubstituted aryl, and C3-C30 ( preferably unsubstituted and substituted C5-C1} heteroaryl, in which the substituents are selected from the group consisting of -NR'5, -NR'4 <+>, - C (0) OR ', -OR', - C (0) NR'2, where R 'is selected from the group consisting of hydrogen and C1-C6 groupings. Therefore this substituted R includes the groupings - (CH2) n0H and' - (CH2) nNR'4, wherein n is an integer having a value in the range of 1 to 16, preferably 2 to 10, and most preferably 2 to 5.

Mostly preferred are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, linear or branched C4-C12 alkyl, and benzyl. Most preferably, R is methyl. M groupings of preferred carboxylic acids include formic acid, benzoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, mayionic acid, maleic acid, succinic acid, adipic acid, phthalic acid, 2-ethylhexanoic acid, naphthenoic acid, oleic acid, paimitic acid, triflate, tartrate, stearic acid, butyric acid, citric acid, acrylic acid, aspartic acid, fumaric acid, lauric acid, linoleic acid, lactic acid, malic acid and especially acetic acid.

Groupings B include higher carbonate, dicarboxylates and carboxylates (e.g., oxalate, mayionate, malic, succinate, maleate), picolinic acid and alpha and beta amino acids (e.g., glyein, alanine, beta-alanine, phenylalanine).

Cobalt-based bleaching catalysts useful herein are known, and are described, for example, together with their basic hydrolysis rates, in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2 pages 1-94. For example, Table 1 on page 17 gives the basic hydrolysis rates (referred to in that reference as "kon") for cobalt pentamine catalysts complexed with oxalate.

The cobalt catalysts useful herein most preferred are cobaltopentamine acetate salts having the formula wherein OAc represents an acetate moiety, and especially chloride of

These cobalt-based catalysts are readily prepared by known procedures, as taught for example in the Tobe article referred to above herein and in the bibliography mentioned therein, - in U.S. Pat. 4,810,410 to 'Diakun et al, issued March 7, 1989, in J. Chem. Ed. (1989), 66 (12), 1043-45; in The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970) pages 461-463; in Inorg. Chem., 18, 1497-1502 (1979); in Inorg. Chem., 21, 2881-2885 (1982); in Inorg. Chem., 18, 2023-2025 (1979); in Inorg. Synthesis, 173-176 (1960); and in Journal of Physical Chemistry, 56, 22-25 (1952); as well as in the summary examples provided below herein.

The cobalt catalysts useful for incorporation into the detergent tablets of the present invention can be produced according to the synthesis routes described in U.S. Pat. Ni.

5,559,261, 5,581,005, and 5,597,936, the descriptions of which are incorporated herein by reference.

These catalysts can be coprocessed with additional materials, so as to reduce the impact of color, if desired for the purposes of the aesthetic characteristics of the product, or to be included in enzyme-containing particles, as exemplified hereinafter, or the compositions can be manufactured with the inclusion of catalyst "colored particles".

Organic polymeric compound

Organic polymeric compounds can be added as preferred components of the detergent tablets according to the present invention. The term "organic polymeric compound" essentially refers to any polymeric organic compound commonly used in detergent compositions, having dispersing properties, anti-re-exposure of dirt, acting as agents for the facilitated reproduction of dirt, or having other properties useful in the field of detergency. .

The organic polymeric compound is typically incorporated into the detergent compositions of the present invention at a level in the range of 0.1% to 30%, preferably 0.5% to 15%, most preferably 1% to 10%. % by weight, with reference to the weight of the compositions.

Examples of organic polymeric compounds include water-soluble organic homopolymer or copolymer polycarboxylic acids, modified polycarboxylates or salts thereof, wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by no more than two carbon atoms. Polymers of the latter type are described in GB-A-1.596.756. Examples of such salts are polyacrylates with molecular weight 2000-10,000 and their copolymers with any other suitable monomer unit including modified acrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenmalonic acid. salts, maleic anhydride, acrylamide, vinyl methyl ether, styrene and any mixture of them. Copolymers of acrylic acid and maleic anhydride having a molecular weight in the range 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 marketed under the trade names Sokalan .PA30, PA20, PA1 5, PA10 and Sokalan CP10 by BASF GmbH, and those marketed under the trade name Acusol 45N, 48N, 460N from Rohm and Haas.

Preferred acrylic acid-containing copolymers include those which contain, as monomer units: (a) 90% to 10%, preferably 80% to 20% by weight, of acrylic acid or its salts, and (b) 10% at 90%, preferably from 20% to 80%, by weight, of a substituted acrylic monomer or its salts, having the formula in which at least one of the substituents R1, R2 or R3, preferably R1 or R2, is an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms, R1 or R2 can be a hydrogen atom and R3 can be hydrogen or an alkali metal. Most preferred is a substituted acrylic monomer where R 1 is methyl, R 2 is hydrogen (i.e., a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500 and contains from 60% to 80% by weight of acrylic acid and from 40% to 20% by weight of methacrylic acid.

Modified polyamine and polyamine compounds are useful herein; among them are included those derived from aspartic acid, such as those described in EP-A-305282, EP-A-305283, and EP-A-351629.

Other optional polymers can be polyvinyl alcohols and polyvinyl acetates, both modified and unmodified, cellulosic polymers and modified cellulosic polymers, polyoxyethylenes, polyoxypropylenes, and their copolymers, both modified and unmodified, terephthalic esters of ethylene glycol or propylene glycol or their mixtures with polyoxyalkylene units .

Suitable examples are described in U.S. Pat. Ni.

5,591,703, 5,597,789 and 4,490,271.

Suitable dirt removal agents Polymeric dirt removal agents suitable include those agents for easy dirt removal having: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) .oxypropylene or polyoxypropylene segments with a degree of polymerization in the range of 2 to 10, wherein said hydrophilic segment does not comprise any oxypropylene unit, unless it is bound to adjacent groups at of each end by ether bonds, or (iii) a mixture of oxyalkylene units comprising oxyethylene and 1 to 30 oxypropylene units, said hydrophilic segments preferably comprising at least 25% oxyethylene units and more preferably, especially for those components which contain from 20 to 30 oxypropylene units, at least 50% of units oxyethylene; or (b) one or more hydrophobic components comprising (i) segments having a character of C3-oxyalkylene terephthalate, wherein, if said hydrophobic components also include oxyethylene terephthalate, the ratio of oxyethylene terephthalate units: C3-oxyalkylenterephthalate units is 2: 1 or less, {ii) segments of C4-C6-alkylene or oxy-C4-C6-alkylene, or mixtures thereof, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) substituents of C1-C4 alkyl ether or C4-hydroxyalkyl ether, or their mixtures,. wherein said substituents are present in the form of C1-C4-alkyl ether to C4-hydroxyalkyl ether derivatives of cellulose, or mixtures thereof, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization starting from 200, although higher levels can be used, preferably 3 to 150, more preferably 6 to 100. Hydrophobic segments oxy-C4-C6- Suitable alkylenes include, without limitation, terminal capping units of polymeric agents for easy dirt removal, such as where M is sodium and n is an integer having a value of 4-6, as described in U.S. Pat. 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric agents for facilitated dirt removal useful herein also include cellulose derivatives, such as hydroxyethercellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or propylene oxide terephthalate, and the like. Such agents are commercially available and include cellulose hydroxyethers, such as METHOCEL (Dow). Cellulosic agents for facilitated dirt removal for use herein also include those selected from the group consisting of -C1-C4-alkyl and C4 hydroxyalkylcellulose; see U.S. Patent 4,000,093 issued December 28, 1976 to Nicol et al.

The agents for the facilitated removal of dirt characterized by the presence of hydrophobic segments having a poly (vinyl ester) character include grafting copolymers of poly (vinyl ester), for example, C1-C6 vinyl esters, preferably poly (vinyl acetate) grafted on main chains of polyalkylene oxide, as the main chains of polyethylene oxide. See European patent application 0 219 048, published on 22 April 1987, by Kud et al.

Another suitable dirt removal agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric agent for facilitated dirt removal is in the range of 25,000 to 55,000. See U.S. Pat. 3,959,230 to Hays, issued May 25, 1976, and U.S. Pat. 3,893,929 to Basadur, issued July 8, 1975.

Another suitable polymeric agent for easy dirt removal is a polyester with repeating units of ethylene terephthalate units, containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol with an average molecular weight of 300-5000.

Another polymeric agent for the facilitated removal of dirt is a sulfonated product of a substantially linear ester oligomer consisting of an oligomeric main chain of terephthaloyl and oxylachyleneoxy repeating units, and terminal clusters linked covalently to the main chain. These agents for easy dirt removal are fully described in U.S. Pat. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric agents for easy dirt removal include the terephthalic polyesters of U.S. Pat. 4,711,730, - issued December 8, 1987 to Gosselink et al., The oligomeric esters with anionic terminal capping units of U.S. Pat.

4,721,580 issued January 26, 1988 to Gosselink and the block oligomeric polyester compounds of U.S. Pat. 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric dirt removal agents also include the dirt removal agents of U.S. Pat. 4,877,896, issued October 31, 1989 to Maldonado et al., Which describes terephthalic esters with anionic terminal capping units, especially soliaroyl.

Another agent for facilitated dirt removal is an oligomer with repeating terephthalic, sulfoisoterephthaloyl, oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form a main chain of the oligomer, and are preferably terminated with capping end groups having a modified isethionate character. A particularly preferred agent for facilitated dirt removal of this type includes a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 1.7 to 1.8, and two terminal capping units. of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

Heavy metal ion sequestering agents The tablets of the present invention preferably contain, as an optional component, a heavy metal ion sequestering agent. The term "heavy metal ion sequestrator" refers to those components which act by sequestering (chelating) heavy metal ions. These components may also have chelating capacity towards calcium and magnesium, however they preferably show binding selectivity towards heavy metal ions, such as iron, manganese, copper.

Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably 0.1% to 10%, more preferably 0.25% to 7.5%, and most preferably from 0.5% to 5% by weight, with reference to the weight of the compositions.

Heavy metal ion sequestrants, which are acidic in nature, having, for example, phosphonic acid or carboxylic acid functionality, may be present in their acidic form, or in the form of a complex / salt with a suitable counter-cation such as a alkali metal or alkaline earth metal ion, an ammonium ion, or one. substituted ammonium ion, or any mixture thereof. Preferably, any salt / complex is soluble in water. The molar ratio between said countercathion and the heavy metal ion sequestering agent is preferably 1: 1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxyphosphonates and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminopenta (methylenephosphonate), ethylenediaminotri (methylenephosphonate), hexamethyldiaminetetra (methylenephosphonate) and hydroxy-ethylene-1,1-diphosphonate.

Other heavy metal ion sequestrants suitable for use herein include nitrilotriacetic acid and polyamino carboxylic acids, such as ethylenediaminetetraacetic acid, ethylenetriaminopentaacetic acid, ethylenediaminodisuccinic acid, ethylenediaminodiglutaric acid, 2-hydroxypropylenediaminodisuccinic acid, or any salt thereof.

Especially preferred are ethylenediamino-N, N'-disuccinic acid (EDDS) or its salts of alkali metals, alkaline earth metals, ammonium or substituted ammonium, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.

Crystal growth inhibitor component

The detergent tablets preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, preferably incorporated at a level in the range of 0.001% to 5%, more preferably 0.1% to 2% in weight, with reference to the weight of the compositions.

By the term "organodisphosphonic acid" is meant herein an organodisphosphonic acid which does not contain nitrogen as part of its chemical structure. Therefore, this definition excludes organoaminophosphonates, which however may be included in the compositions of the present invention as sequestering components of heavy metal ions.

The organodifosphonic acid is preferably a C1-C4-diphosphonic acid, more preferably a C2 <~> diphosphonic acid, such as ethylene diphosphonic acid, or, most preferably, ethan-1-hydroxy-1,1-diphosphonic acid. (HEDP) and can be <'> present in partially or totally ionized form, particularly in the form of a salt or complex.

Water-soluble sulphate salt

The cleaning tablet optionally contains a water-soluble sulfate salt. When present, the water-soluble sulfate salt is contained at a level of from 0.1% to 40%, more preferably from 1% to 30%, most preferably from 5% to 25% by weight, with reference to the weight of the compositions.

The water-soluble sulfate salt can be essentially any sulfate ion salt with any countercathion. Preferred salts are selected from the alkali metal and alkaline earth metal sulphates, in particular sodium sulphate.

Alkali metal silicate

An alkali metal silicate is a preferred component of the tablet of the present invention. A preferred alkali metal silicate is sodium silicate having a SiO2: Na20 ratio in the range of 1.8 to 3.0, preferably 1.8 to 2.4, most preferably 2.0. the sodium silicate is preferably present at a level lower than 20%, preferably in the range of from 1% to 15%, most preferably from 3% to 12% by weight of Si02. The alkali metal silicate can be in the form of an anhydrous salt or a hydrated salt.

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

The alkalinity supply system also preferably contains sodium metasilicate, present at a level of at least 0.4% by weight of SiO 2. Sodium metasilicate has a nominal SiO2: Na20 ratio of 1.0. The weight ratio between said sodium silicate and said sodium metasilicate, measured as SiO 2, is preferably comprised in the range of from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, most preferably 10: 1 to 5: 2.

Color conferring agent

The term "color conferring agent", as used herein, means any substance that absorbs specific wavelengths of light radiation from the visible light spectrum. Such color imparting agents, when added to a detergent composition, have the effect of changing the visible color, and hence the appearance of the detergent composition. The color conferring agents can be, for example, dyes and pigments. Preferably, the color imparting agents are stable in the composition in which they are to be incorporated. Thus, in a high pH-value composition the color-imparting agent is preferably alkali-stable and in a low-pH-value composition, the color-imparting agent is preferably acid-stable.

The first phase and / or second phase and / or further phases occasionally present may contain a color conferring agent, a mixture of color conferring agents, colored particles or mixtures of colored particles, so that the various phases have visual aspects. different. Preferably, one of the first or second phases comprises a color conferring agent. When both the first step, and the second step and / or optional subsequent steps comprise a color agent, it is preferred that said color imparting agents provide a different visual appearance.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline dyes, monoazo, disazo and polyazo dyes. The most preferred dyes include anthraquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name) all available from Clariant UK, HEXACOL QUINOLINE YELLOW (trade name) and HEXACOL BRILLIANT BLUE (trade name) both available from Pointings, UK, ULTRAMARINE BLUE (trade name) available from Holliday or LEVAFIX TURQUOISE BLUE EBA (trade name) available from Bayer, USA.

The color imparting agent can be incorporated into the steps by any suitable method. Suitable methods include mixing all detergent components or selected detergent components with a color-enhancing agent in a drum, or spraying all of the detergent components or selected detergent components with the color-adding agent in a rotating drum.

The color conferring agent, when present as a component of the first phase, is present, at a level in the range of from 0.001% to 1.5%, preferably from 0.01% to 1.0%, most preferably from 0.1% to 0.3%; When present as a component of the second phase, and / or of further optional phases, the color conferring agent. it is generally present at a level in the range of from 0.001% to 0.1%, more preferably from 0.005% to 0.05%, most preferably from 0.007% to 0.02%.

Corrosion inhibiting compound

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

Organic silver coating agents are disclosed in PCT publication number W094 / 16047 and concurrently pending European patent application No. EP-A-690122. The nitrogen-containing corrosion inhibiting compounds are disclosed in concurrently pending European patent application No. EP-A-634.478. Compounds containing Mn (II) for use in corrosion inhibition are disclosed in concurrently pending European Patent Application No. EP-A-672749.

The organic silver coating agents can be incorporated at a level in the range of 0.05% to 10%, preferably 0.1% to 5% by weight, based on the weight of the total composition.

The functional role of the silver coating agent is to form "in use" a protective coating layer on any silver article component of the dishes loaded in the dishwashing machine to which the compositions of the invention are coming. applied.

The silver coating agent will therefore need to have a high affinity for solid silver surfaces in order to fix it, particularly when it is present in the form of a component of an aqueous washing and bleaching solution with which solid surfaces d silver are being treated.

Suitable organic silver coating agents for use herein include fatty esters of monohydroxylated or polyhydroxylated alcohols having 1 to 40 carbon atoms in the hydrocarbon chain.

The fatty acid portion of the fatty ester can be obtained starting 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, paimitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and β acid. β'-hydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

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

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

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

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

Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl dilactate, coccoyl isobutyrate, oleyl maleate, oleyl dimaleate and tallow alkyl propionate. Esters of fatty acids useful herein include xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobeenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibeenate, sorbitan dioleate, and also monoesteri dioleate. of mixed tallowalkyl-sorbitan.

Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobeenate and glycerol distearate are preferred glycerol esters herein.

Suitable organic silver coating agents include triglycerides, mono or diglycerides, and their totally or partially hydrogenated derivatives, and any mixture thereof. Suitable sources of fatty acid esters include vegetable oils and animal fat fish oils. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, canola oil, grapeseed oil, palm oil and corn oil.

Waxes, including microcrystalline waxes, are organic silver coating agents suitable for use herein. The preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise 12 to 70 carbon atoms. Petroleum waxes of the paraffinic and microcrystalline type are preferred, which are composed of long-chain saturated hydrocarbon compounds.

Alginates and gelatin are organic silver coating agents suitable for use herein.

Also suitable are dialkylamine oxides, such as C12-C20 methylamine oxide, and quaternary dialkylammonium compounds and their salts, such as 12-20 methylammonium halides.

Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight in the range of 12,700 to 700,000, polyethylene glycols (PEG) with an average molecular weight in the range of 600 to 10,000, polyamine-N-oxide polymers, N-vinylpyrrolidone and N copolymers -vinylimidazole, and cellulose derivatives, such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such polymeric materials.

Certain perfume materials, especially those which exhibit a high substantivity for metallic surfaces, are also useful as organic silver coating agents useful herein.

Polymeric agents for the easy removal of dirt can also be used as an organic agent for the coating of silver.

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 paraffinic oil selected from the predominantly branched C25-45 species with a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons in the range of from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. A paraffinic oil that satisfies these characteristics, having a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons of 32:68, is marketed by the company Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Nitrogen-Containing Corrosion Inhibitor Compounds Suitable nitrogen-containing corrosion inhibitory compounds include imidazole and its derivatives, such as benzimidazole, 2-heptadecylimidazole, and those imidazole derivatives which are described in Czechoslovakia Patent No. 139,279 and British Patent GB-A- 1 .137 .741, which also describes a method for the production of imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibiting compounds are pyrazole compounds and their derivatives, particularly those in which the pyrazole is substituted in any of the positions of 1, 3, 4 or 5 with substituents R1, R3, R, and R5 in which R1 is any of H, CH20H, CONH3, or COCH3, R3 and R5 are any of C1-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or N02.

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

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

Corrosion inhibiting compounds containing Mn (II) The cleaning tablets may contain a corrosion inhibiting compound containing Mn (II). The compound of Mn (II) is preferably incorporated at a level in the range of from 0.005% to 5% by weight, more preferably from 0.01% to 1%, most preferably from 0.02% to 0 4% by weight, based on the weight of the compositions. Preferably, the compound of Mn (II) is incorporated in a level such as to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm. most preferably from 1 ppm to 20 ppm by weight of Mn (II) ion, in any bleaching solution.

The compound of Mn (II) can be an inorganic salt in anhydrous form, or in any hydrated form. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. Manganese (II) compounds 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 a complex of a. organic ligand. · In a preferred aspect, the organic ligand is a sequestering agent for heavy metal ions. In another preferred aspect, the organic ligand is a crystal growth inhibitor.

Other corrosion inhibiting compounds

Other suitable additional corrosion inhibiting compounds include mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms, including lauryl mercaptan, thiophenol, thionaphthol, thionalide and thioanthanol. Also suitable are .C10-C20 saturated or unsaturated fatty acids, or their salts, especially aluminum tristearate. C12-C20 fatty hydroxy acids or their salts are also suitable. Octadecane phosphonate and other antioxidants, such as beta hydroxytoluene (BHT), are also suitable.

It has been found that copolymers of butadiene and maleic acid, in particular those that can be purchased from Polysciences Ine. with commercial code No. 07787 they are of particular use as corrosion inhibiting compounds.

Hydrocarbon oils

Another preferred detergent component for use in the present invention is a hydrocarbon oil, typically predominantly long chain aliphatic hydrocarbons having carbon numbers in the range of 20 to 50; preferred hydrocarbons are saturated and / or branched; a hydrocarbon oil selected from predominantly branched C25-45 species with a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons in the range between 1:10 and 2: 1, preferably between 1: 5 and 1: 1, is preferred. A preferred hydrocarbon oil is a paraffin. A paraffinic oil that meets the above characteristics, with a ratio of cyclic hydrocarbons to non-cyclic hydrocarbons of 32:68, is marketed by the company Wintershall, Salzbergen, Germany, under the trade name WINOG 70.

Water-soluble compound of bismuth

The detergent tablets of the present invention suitable for use in dishwashing methods may contain a water-soluble bismuth compound, preferably present at a level in the range of 0.005% to 20%, more preferably 0.01% and 5%, most preferably between 0.1% and 1% by weight, with reference to the weight of the compositions.

The water-soluble bismuth compound can be essentially any bismuth salt or complex with essentially any inorganic or organic counterion. Preferred inorganic bismuth salts are selected from bismuth trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and bismuth citrate are preferred salts with an organic counteranion.

Stabilizing enzyme system

Preferred enzyme-containing compositions herein may comprise 0.001% to 10%, preferably 0.005% to 8%, most preferably 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system that is compatible with the cleaning enzyme. Such stabilizing systems may include calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, uptake agents for the elimination of chlorinated bleaches, and mixtures thereof. Such stabilizing systems may also comprise reversible inhibitors of enzymes, such as reversible inhibitors of the proteins.

Dispersing compound of calcium soaps

The tablets of the present invention can contain a dispersing compound of calcium soaps, preferably present at a level in the range from 0.1% to 40% by weight, more preferably from 1% to 20% by weight. , most preferably between 2% and 10% by weight, with reference to the weight of the compositions.

A dispersant of calcium soaps is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. Dispersing compounds of the preferred calcium soaps are described in the patent application according to PCT No. WO 93/08877.

Foaming suppression system

The detergent tablets of the present invention, when formulated for use in compositions for washing in washing machines, preferably comprise a foaming suppression system present at a level in the range of 0.01% to 15%, preferably 0, 05% to 10%, most preferably from 0.1% to 5% by weight, with reference to the weight of the composition.

Suitable foaming suppressant systems for use herein may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds, 2-alkyl and alkanol antifoam compounds. Foam suppression systems and preferred antifoam compounds are disclosed in PCT patent application No. WO 93/08876 and in EP-A-705324.

Polymeric agents that inhibit the transfer of dyes

The detergent tablets of the present invention can also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight, of polymeric agents which inhibit the transfer of dyes.

The polymeric agents which inhibit the transfer of dyes are preferably selected from polyamine-N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, polyvinylpyrrolidone polymers or combinations thereof.

Optical brightener

Detergent tablets suitable for use in laundry washing methods as described herein also optionally contain 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R1 is selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bishydroxyethyl, N-2-hydroxyethyl-N-methylamine, morpholino, chlorine and amino; and M is a salt-forming cation, such as sodium or potassium.

When in the above formula Ri is aniline, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the whitener is 4,4'-bis acid [(4-anilino-6- (N-2- bishydroxyethyl) -sd-triazin-2-yl) amino] -2,2'-stilbendisulfonic, and disodium salt. This particular kind of optical brightener is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula R1 is aniline, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the optical brightener is 4,4'-bis acid [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2 -stylbendisulfonic, disodium salt.

This particular species of optical brightener is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula R1 is aniline, R2 is morpholino and M is a cation like sodium, the optical brightener is 4,4'-bis acid [{4-anilino-6-morpholino-striazin-2-yl) animino] 2,2'-stilbendisulfonic, sodium salt. This particular species of optical brightener is marketed under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Clay-based softening system

The detergent tablets suitable for use in laundry washing methods may contain a clay-based softening system comprising a mineral compound of clay character and optionally a clay flocculent agent.

The mineral compound with a clayey character is preferably a compound with a smectitic clay character. Smectite clays are described in U.S. Pat. Ni. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patents Ni. EP-A-299.575 and EP-A-313.146 in the name of the Procter and Gamble Company disclose clay flocculating agents of suitable organic polymer character.

tissue softening cations

Cationic type fabric softening agents may also be incorporated into the compositions in accordance with the present invention which are suitable for use in laundry washing methods. Suitable cationic type fabric softening agents include water insoluble tertiary amines, or two long chain amide materials, as described in GB-A-1.514.276 and EP-B-0011 340.

Cationic fabric softening agents are typically incorporated at total levels of 0.5% to 15% by weight, normally 1% to 5% by weight. '

Other optional ingredients

Other optional ingredients suitable for inclusion in the. compositions of the present invention comprise perfumes and filler salts, in which context sodium sulfate is a preferred filler salt.

pH of the compositions

The detergent tablets of the present invention are preferably not formulated to have an undesirably high pH value, preferably having a pH, measured in the form of a 1% solution in distilled water, in the range from 8.0 to 12. , 5, more preferably between 9.0 and 11.8, most preferably between 9.5 and 11.5.

Method for washing dishes by machine

There is any suitable method for washing or cleaning dirty dishes in the washing machine.

A preferred machine washing method includes treating items selected from crockery / tableware, glassware, silver items, 'metal objects, cutlery and mixtures thereof, soiled with an aqueous liquid containing, dissolved or dispersed in it is an effective amount of a detergent tablet according to the present invention. The expression "effective quantity of the detergent tablet" means from 8 grams to 60 grams of product dissolved or dispersed in a washing solution of from 3 to 10 liters in volume, which are the typical doses of product, and the typical volumes of washing solutions commonly employed in conventional methods for machine washing dishes. Preferably, the cleansing tablets weigh from 15 grams to 50 grams, more preferably from 20 grams to 35 grams.

Method for washing laundry (laundry)

Methods for machine washing laundry herein typically include treating soiled laundry with an aqueous washing solution, in a washing machine, having dissolved or dispersed therein, an effective amount of a laundry detergent tablet composition. machine according to the present invention. The expression "effective quantity of the composition as a detergent tablet" means from 40 g to 300 g of product dissolved or dispersed in a washing solution of from 5 to 65 liters of volume, which are the typical product doses and the typical volumes of wash solution commonly employed in conventional or machine washing methods of laundry.

In a preferred aspect of use, a dispensing device is employed in the washing method. The dispensing device is loaded with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its capacity, by volume, must be such as to be able to contain the sufficient quantity of detergent product which will normally be used in the washing method.

Once the washing machine has been loaded with the laundry to be washed, 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 begins to rotate periodically, the configuration of the dispensing device must be such as to allow the containment of the dry detergent product, however at the same time allowing the subsequent release of this product during the washing cycle in response to its agitation as the drum rotates, and also as a result of its contact with the washing water.

In order to allow the release of the detergent product during washing, the device may have a number of openings through which the product can pass. Alternatively, the device may be made of a material which is permeable to liquid, but is impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be rapidly released at the start of the wash cycle, thereby providing transient localized high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that the container will retain its integrity both in the dry state and during the wash cycle.

Alternatively, the dispensing device can be a flexible container, such as a bag or tub. The pouch can be of a fibrous structure coated with a protective material impermeable to water so as to retain the contents, as described in published European Patent Application No. 0018678. Alternatively, it can be formed of a water-insoluble synthetic polymeric material. equipped with an edge seal or seal designed to rupture in aqueous medium as described in published European patent applications Ni. 0011500, 0011501, 0011502, and 0011968. An advantageous form of water-breakable closure comprises a water-soluble adhesive disposed along an edge, and sealing / sealing said edge, of a tray formed from a water-impermeable polymeric film, such as polyethylene or polypropylene.

E s e m p i

Abbreviations used in the examples

In detergent compositions, the abbreviated identifications used for the components have the following meanings:

STPP sodium tripolyphosphate

Sodium hydrogen carbonate bicarbonate

Citric acid Anhydrous citric acid

Anhydrous sodium carbonate carbonate

Amorphous sodium silicate silicate

(ratio Si02: Na20 = 2.0)

SKS-6 layered crystalline silicate of the formula δ-Na2Si205

PB1 sodium perborate anhydrous monohydrate Non ionic C13-C15 ethoxylated / propoxylated mixed fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, marketed under the trade name Plurfac by BASF

TAED tetraacetylethylenediamine

HEDP ethan-1-hydroxy-1,1-diphosphonic acid PAAC cobalt (III) pentamine salt

acetate

Paraffin: paraffinic oil marketed under the trade name Winog 70 by Wintershall.

Protease: proteolytic enzyme

Amylase: amylolytic enzyme

BTA: benzotriazole

Sulphate: anhydrous sodium sulphate

PEG 3000: polyethylene glycol with a molecular weight of about 3000 available from Hoechst

PEG 6000: polyethylene glycol with a molecular weight of about 6000 available from Hoechst

PH: measured in the form of a 1% solution in distilled water at 20 ° C In the following examples all levels are expressed in parts by weight:

Examples I-IV

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

Total

Multi-phase tablet compositions are prepared as follows. The detergent activity composition of step 1 is prepared by mixing the granular and liquid components and then passing the mixture through the mold of a conventional rotary press. The press comprises a punch of suitable shape for forming the impression in the tablet. The cross section of the mold is approximately 30 x 8 mm. The composition is subsequently subjected to a compressive force of 940 kg / cm <2>, and the punch is then raised exposing the first phase of the tablet containing the impression in its upper surface. The detergent activity composition of step 2 is prepared in a similar manner and is loaded into the mold. The particle active composition is then subjected to a compression force of 170 kg / cm <2>, the punch is lifted, and the multiphase tablet is ejected from the tablet press. The resulting tablets dissolve or disintegrate in a washing machine as described above within 12 minutes, phase 2 of the tablets dissolving within 5 minutes. The tablets provide excellent dissolving and cleansing characteristics, associated with good integrity and strength characteristics of the tablet.

Claims (8)

R i v e n d i c a c t i o n i 1. A multiphase detergent tablet for use in a washing machine, the tablet comprising: a] a first step in the form of a formed body having at least one imprint therein; And b) a second step in the form of an adhesively compressed body contained within said impression, wherein the tablet composition comprises one or more detergent activity species which are predominantly concentrated in the second step, and wherein the second step additionally comprises a binder . 2. A multiphase detergent tablet for use in a washing machine, the tablet comprising. a) a first step in the form of a compressed formed body having at least one imprint therein, the formed body being prepared for a compression pressure of at least about 350 kg / cm 2; and b) a second step in the form of an adhesively compressed body contained within said impression, wherein the tablet composition comprises one or more detergent activity species which are predominantly concentrated in the second step, and wherein the second step additionally comprises a binder . 3. A multiphase detergent tablet according to any of the preceding claims, in which the one or more species endowed with detergent activity are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, growth inhibitors crystals and their mixtures. A multiphase detergent tablet according to any of the preceding claims, wherein the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic polymers and organic polymers. A multiphase detergent tablet according to any of the preceding claims, additionally comprising a barrier phase between the first and second phase. A multiphase cleaning tablet according to claim 5, wherein the barrier layer comprises a binder applied in liquid form. A washing method in a washing machine comprising loading a washing machine with one or more multiphase detergent tablets according to any of the preceding claims. A method according to claim 7, wherein the multiphase cleaning tablet dissolves or disintegrates in less than 15 minutes in a dish washing machine according to the dissolution test method described herein.