MXPA00005229A

MXPA00005229A - Detergent tablet

Info

Publication number: MXPA00005229A
Application number: MXPA/A/2000/005229A
Authority: MX
Inventors: Ursula Metzgergroom Sabine
Original assignee: Ursula Metzgergroom Sabine; The Procter & Gamble Company
Priority date: 1997-11-26
Filing date: 2000-05-26
Publication date: 2001-07-31

Abstract

The present invention relates to a detergent tablet comprising a compressed portion and a non-compressed portion wherein the non-compressed portion comprises a perfume component.

Description

DETERGENT TABLET TECHNICAL FIELD OF THE INVENTION The present invention relates to a detergent tablet comprising a compressed portion and a non-compressed portion, wherein the non-compressed portion contains a perfume component.

BACKGROUND OF THE INVENTION Detergent compositions are well known in the art. However, consumer acceptance of the detergent compositions is determined not only by the detergent action achieved, but also by the aesthetics associated therewith. Perfumes are generally available in liquid form and have traditionally been incorporated in detergent compositions by spraying the liquid perfume onto a premixed particulate detergent composition. Then, detergent tablets are produced by tabletting the detergent composition, using suitable equipment, such as for example a tablet press. Perfumes are very reactive volatile chemicals. These chemicals can interact with the atmosphere or with other ingredients of the detergent composition. This interaction can cause the perfume to undergo a chemical reaction that changes its chemical formula causing it to lose its ability to emit the desired perfume. Alternatively, the perfume may also undergo a reaction that causes the chemical emission of a different perfume, which may be unpleasant or offensive. In addition to the above, volatile perfumes evaporate during storage, resulting in the loss of perfume concentration. Another problem associated with the evaporation of perfume during storage is the accumulation of perfume in the package in which the detergent composition is stored and sold. In this way, when opening the package, the consumer faces an excessively strong perfume, which can be unpleasant and undesirable. The problems described above are particularly noticeable in detergent tablets. As described above, the detergent tablets are prepared from a particulate detergent composition on which a liquid perfume component has been previously sprayed. The particulate detergent composition is poured into the tablet press and then compressed to form a tablet. The perfume component and other components of the detergent composition are forced very closely together, increasing the likelihood of interaction between components. In addition, the tablets are generally porous, trapping atmospheric gases within the detergent tablet, again increasing the likelihood of interaction of the perfume component with the atmosphere.

A solution proposed in the art to solve these problems is to encapsulate the perfume or to inhibit in some other way the emission of perfume. The encapsulation of perfume, however, does not solve the problems mentioned above with respect to detergent tablets, since it is considered that during the tabletting process, the perfume capsules are compressed and the perfume is exposed to the atmosphere and other detergent components . The applicant hereby has found that by preparing a detergent tablet comprising a compressed portion and an uncompressed portion, as described in Applicants' co-pending application No. GB 9716351.3 (Proxy Excerpt No. CM 1572F), can be incorporated a perfume encapsulated in the tablet. In addition, the applicant has also found that pro-perfumes and liquid perfumes are more stable when incorporated into the non-compressed portion.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, a detergent tablet comprising a compressed portion and a non-compressed portion is provided, wherein the compressed portion is prepared using a compression pressure of more than 6.3 KN / cm2, and the non-compressed portion comprises a perfume component.

In accordance with another aspect of the present invention, a detergent tablet comprising a compressed portion and a non-compressed portion is provided, wherein the non-compressed portion dissolves faster than the compressed portion on a weight-to-weight basis, measuring the solution by means of the SOTAX dissolving method which is described herein, and the non-compressed portion contains a detergent component. In accordance with another aspect of the present invention, there is provided a detergent tablet comprising a compressed portion and a non-compressed portion, wherein the compressed portion contains a bleaching agent and the non-compressed portion contains a perfume component. According to another aspect of the present invention, a detergent tablet is provided comprising a compressed portion, an uncompressed portion and a perfume component, wherein the perfume component is suspended or dispersed within the non-compressed portion.

DETAILED DESCRIPTION OF THE INVENTION Compressed portion The compressed portion of the detergent tablet comprises at least one, but preferably a mixture, of detergent components.

Any detergent component conventionally used in known detergents is suitable for incorporation into the compressed portion of the detergent tablets of this invention. Suitable detergent components are described below. Preferred detergent components include builder compound, surfactant, bleaching agent, bleach activator, bleach catalyst, enzyme and a source of alkalinity. The detergent components are preferably prepared in particulate form (i.e., in powder or granular form) and can be prepared by any known method, for example conventional spray, granulation or agglomeration. The detergent component or components are pre-mixed and any liquid detergent component is sprayed onto the particulate detergent components during premixing. Then, the premix is compressed using any suitable equipment to form compressed tablets, blocks, partitions or agglomerates, which are described later in the present description.

Non-compressed portion The non-compressed portion contains a perfume component, but may also comprise one or more detergent components as described below. The non-compressed portion and / or the components of the non-compressed portion may be in particulate form (i.e. in powder or granular form), in gel or in liquid form. The non-compressed portion, in addition to containing a detergent component and optional detergent components, may also optionally comprise a carrier component. In an alternative aspect of the present invention, the non-compressed portion is preferably dissolved at a temperature of less than 30 ° C and / or faster than the compressed portion, on a weight-to-weight basis by measuring by means of the test method of SOTAX solution described below.

SOTAX Dissolution Test Method: The SOTAX machine consists of a water bath with controlled temperature and lid. 7 containers are suspended in the water bath. 7 electric stirring rods are suspended from the bottom side of the lid, in positions corresponding to the position of the containers in the water bath. The lid of the water bath also serves as a lid on the containers. The SOTAX water bath is filled with water and the temperature gauge is set at 50 ° C. Then each container is filled with 1 liter of deionized water and the agitator is set to mix at 250 rpm. The lid of the water bath is closed, allowing the temperature of the deionized water in the containers to be balanced with that of the water in the water bath for 1 hour. The same weights of the compressed and non-compressed portions are weighed. The compressed portion is placed in a first container and the non-compressed portion is placed in a second container. Then the lid is closed. The compressed and non-compressed portions are monitored visually until they are completely dissolved. The time in which the compressed portion and the uncompressed portion were completely dissolved is noted. The dissolution rates of both portions are calculated as the average weight (g) of each portion dissolved in deionized water per minute. In another preferred aspect, the non-compressed portion comprises a first and a second portion, and optionally subsequent, non-compressed portions. In this aspect, it is also preferred that the first non-compressed portion and the second non-compressed portion, and the optional non-compressed optional portions, have different dissolution rates. The detergent tablet of the present invention requires that the non-compressed portion be supplied in the compressed portion in such a manner as to avoid contact between the compressed portion and the uncompressed portion. The non-compressed portion may be supplied in the compressed portion in solid form or in fluid form. In the case where the non-compressed portion is in solid form, it is prepared beforehand, optionally it is shaped, and then it is delivered in the compressed portion. Next, the non-compressed portion is fixed in a preformed compressed portion, for example, by means of adhesion or insertion of the non-compressed portion into a matched surface of the compressed portion. Preferably, the compressed portion comprises a depression or mold prepared in advance in which the non-compressed portion is dispensed. Preferably, the non-compressed portion is delivered to the compressed portion in a fluid form. Then, the non-compressed portion is fixed in the compressed portion for example, by means of adhesion, forming a coating on the non-compressed layer to secure it to the compressed portion, or by hardening, for example, (i) by cooling down the melting point when the fluid composition becomes a molten and solidified mixture; (ii) by evaporation of a solvent; (iii) by crystallization; (iv) by polymerization of a polymeric component with the fluid non-compressed portion; (v) by the pseudoplastic properties wherein the fluid non-compressed portion comprises a polymer and shear forces are applied to the non-compressed portion; (vi) combining a binder with the fluid non-compressed portion. In an alternative embodiment, the fluid non-compressed portion may be an extruded product which is fixed in the compressed portion, for example, by means of any mechanism such as those described above, or by expanding the extruded product to the parameters of a mold provided by the compressed portion. Preferably, the compressed portion comprises a previously prepared depression or mold (hereinafter referred to as "mold") into which the uncompressed portion is dispensed. In an alternative embodiment, the surface of the compressed portion comprises more than one mold in which the non-compressed portion can be dispensed. Preferably, the mold or molds at least partially accommodate one or more uncompressed portions. The non-compressed portion (s) is then delivered to the mold and fixed in the compressed portion as described above. The non-compressed portion may comprise particles. The particles can be prepared by any known method, for example conventional spray drying, granulation, encapsulation or agglomeration. The particles can be fixed in the compressed portion by incorporating a binder or forming a coating layer on the non-compressed portion. In the case where the non-compressed portion comprises an already solidified molten mixture, said molten mixture is prepared by heating a composition containing an active detergent component and optional vehicle components, above its melting point, to form a fluid molten mixture. . This fluid molten mixture is then emptied into a mold and allowed to cool. As the molten mixture cools, it becomes solid and takes the shape of the mold at room temperature. When the composition comprises one or more vehicle components, these can be heated above their melting point, and then an active detergent component can be added. Vehicle components that are suitable for preparing a molten mixture for solidification are generally inactive components that can be heated above the melting point to form a liquid and cooled to form an intermolecular matrix that can effectively trap active detergent components. A preferred inactive carrier component is an organic polymer that is solid at room temperature. Preferably, the inactive detergent components are polyethylene glycols (PEG). The compressed portion of the detergent tablet preferably provides a mold to accommodate the molten mixture. The fluid non-compressed portion may be in a form comprising a dissolved or suspended active detergent component. The fluid non-compressed portion can be hardened by allowing time to form a solid, semi-solid or highly viscous liquid, or by any of the methods described above. In particular, the fluid non-compressed portion can be hardened by evaporation of a solvent. Suitable solvents for use herein include any known solvent in which a binder or gelling agent is soluble. Preferred solvents may be polar or non-polar, non-aqueous or anhydrous, and may include for example water, glycerin, alcohol (for example ethanol), acetone, and alcohol derivatives. In an alternative embodiment, more than one solvent may be used. The fluid non-compressed portion may comprise one or more binding or gelling agents. For use herein, any binder or gelling agent that causes the composition to become solid, semi-solid or highly viscous over time is contemplated. While not wishing to be bound by theory, it is believed that the mechanisms by which the binder or gelling agent causes a non-solid composition to become solid, semi-solid or highly viscous, include: chemical reaction (such as chemical entanglement), or interaction between two or more components of the fluid composition; either chemical or physical interaction of the binder with one component of the composition. In a preferred aspect of the present invention, the non-compressed portion comprises a gel. In this aspect, the gel is dispensed into the compressed portion of the detergent tablet, but is preferably dispensed into a mold provided by the compressed portion. The gel comprises a thickener system in addition to the perfume component and other optional detergent ingredients. In addition, the gel may also comprise solid ingredients to help control the viscosity of the gel, in conjunction with the thickening system. The solid ingredients can also optionally act to break the gel, thus helping its dissolution. When included, the gel portion generally comprises at least 15% solid ingredients, preferably at least 30% solid ingredients, and preferably at least 40% solid ingredients. However, due to the need to pump and process the gel in other ways, it does not generally include more than 90% solid ingredients. As indicated above, the gel comprises a thickener system to provide the required viscosity or thickness of the gel. The thickener system typically comprises a non-aqueous liquid diluent and an organic or polymeric gelling additive. a) Liquid diluent: The term "solvent" or "diluent" is used herein to denote the liquid portion of the thickener system. Although some of the components of the non-compressed portion can actually be dissolved in the phase containing the "solvent", other components will be present as dispersed particulate material within the phase containing the "solvent". Thus, the term "solvent" does not necessarily mean that the components of the non-compressed portion are actually dissolved in the solvent. Suitable types of solvents useful in the non-aqueous thickener systems herein include ethers of monoalkyl lower alkylene glycol, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, low molecular weight polyethylene glycols, methyl esters and low molecular weight amides. A preferred type of non-aqueous solvent for use herein comprises the C2-C6 monoalkyl ethers of C2-C3 mono-, di-, tri-, or tetraalkyleneglycol. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Especially preferred are diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether. Compounds of this type are commercially available under the trademarks Dowanol, Carbitol and Cellosolve. Another preferred type of non-aqueous solvent useful herein comprises low molecular weight polyethylene glycols (PEGs). Said materials are those having molecular weights of at least about 150. PEGs of molecular weights in the range of 200 to 600 are most preferred. Another preferred type of non-aqueous solvent comprises low molecular weight methyl esters. Said materials are those of the general formula: R1-C (O) -OCH3, wherein R1 ranges from 1 to about 18. Examples of low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate and dodecanoate of methyl. Of course, the solvent or non-aqueous organic solvents employed must be compatible and non-reactive with the perfume component and other optional detergent components, for example enzymes. Said solvent component will generally be used in an amount of 10% to 60% by weight of the gel portion. Preferably, the low polarity non-aqueous organic solvent will comprise from 20% to 50% by weight of the gel portion, preferably from 30% to 50% by weight of the gel portion. b) Adding agent: An agent or gelling additive is added to the non-aqueous solvent of the present invention to complete the thickening system. To form the required gel, with adequate phase stability and acceptable rheology, the organic gelling agent will generally be present in a ratio of solvent to gelling agent, in the thickening system, which typically ranges from 99: 1 to 1: 1. Preferably, the proportions vary from 19: 1 to 4: 1. Preferred gelling agents of the present invention are selected from castor oil, polyethylene glycol, sorbitol and related organic thixotropic derivatives, organic clays, cellulose and cellulose derivatives, Pluronics, stearates and stearate derivatives, sugar / gelatin combinations, starches, glycerol and its derivatives, amides of organic acids such as di-n-butylamide of N-lauryl-L-glutamic acid, polyvinylpyrrolidone and mixtures thereof. Preferred gelling agents include castor oil derivatives. Castor oil is a triglyceride of natural occurrence obtained from the seeds of Ricinus Communis, a plant that grows mainly in tropical and subtropical areas. The primary portion of fatty acid in the triglyceride of castor oil is ricinoleic acid (12-hydroxyoleic acid). Represents 90% of the fatty acid portions. The rest consists of portions of dihydroxystearic acids, palmitic, stearic, oleic, linoleic, linolenic and eicosanoic. The hydrogenation of the oil (for example, by hydrogen under pressure) converts the double bonds of the fatty acid portions into simple bonds, thus "hardening" the oil. The hydroxyl groups are not affected by this reaction. The resulting hydrogenated castor oil, therefore, has an average of three hydroxyl groups per molecule. It is believed that the presence of these hydroxyl groups largely explains the outstanding structural properties that are imparted to the gel portion, compared to similar liquid detergent compositions that do not contain castor oil with hydroxyl groups in their fatty acid chains. For use in the compositions of the present invention, the castor oil must be hydrogenated to an iodine value of less than 20, preferably less than 10. The iodine value is a measure of the degree of unsaturation of the oil and is measured by of the "Wijis Method", which is well known in the field. Unhydrogenated castor oil has an iodine value of 80 to 90. Hydrogenated castor oil is a commercially available article and is sold, for example, in different grades under the CASTORWAX.RTM brand of NL Industries, Inc. Highstown, New Jersey Other suitable derivatives of hydrogenated castor oil are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, manufactured by Rheox, Laporte. Thixatol ST is especially preferred. When polyethylene glycols are used as gelling agents instead of solvents, they have a molecular weight ranging from 1000 to 10000, with from 3000 to 8000 being preferred. When cellulose and cellulose derivatives are employed in the present invention, they preferably include: (i) acetate of cellulose and cellulose acetate phthalate (CAP); (ii) hydroxypropylmethylcellulose (HPMC); (iii) carboxymethylcellulose (CMC); and mixtures thereof. The hydroxypropylmethylcellulose polymer preferably has a number average molecular weight of 50,000 to 125,000 and a viscosity of 50,000 to 100,000 cps in a 2% by weight aqueous solution at 25 ° C (ADTMD2363). An especially preferred polymer of hydroxypropylcellulose is Methocel® J75MS-N, which has a viscosity of about 75,000 cps in a 2.0% by weight aqueous solution at 25 ° C. The sugar can be any monosaccharide (e.g., glucose), disaccharide (e.g., sucrose or maltose) or polysaccharide. The preferred sugar is the sugar commonly available. For the purposes of the present invention, type A or type B gelatin, available for example from Sigma, may be used. Type A gelatin is preferred since it has greater stability under alkaline conditions compared to type B. Preferred gelatin also has a coating strength of between 65 and 300, preferably between 75 and 100. The gel may include a variety of other ingredients in addition to the thickening agent that was described above, and of the active detergent described in more detail below. Ingredients such as colorants, as well as structure modifying agents can be included. Structure modifying agents include various polymers and blends of polymers including polycarboxylates, carboxymethylcelluloses and starches, to aid in the adsorption of excess solvent and / or to reduce or avoid "bleeding" or leakage of the solvent from the gel portion, to reduce the shrinkage or cracking of the gel portion, or to assist in dissolving or breaking the gel portion in the wash. In addition, hardness modifying agents can be incorporated in the thickener system to adjust the gel hardness if necessary. Hardness control agents are generally selected from various polymers such as polyethylene glycols, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl alcohol, hydroxystearic acid and polyacetic acid, and when included, are generally used at levels of less than 20%, and preferably less than 10% by weight of the solvent in the thickening system. The gel is formulated in such a way that it is a fluid gel that can be pumped at slightly elevated temperatures of around 30 ° C or more, to allow greater flexibility in the production of the detergent tablet, but to become highly viscous or harden at ambient temperatures, such that the gel remains in position in the compressed portion of the detergent tablet during shipping and handling of the detergent tablet. Said hardening of the gel can be achieved, for example, by (i) cooling below the gel fluid temperature or by shear removal; (I) by solvent transfer, for example to the atmosphere of the compressed body portion; or (iii) by polymerization of the gelling agent. Preferably, the gel is formulated in such a manner that it hardens sufficiently so that the maximum force needed to push a probe into the non-compressed portion preferably ranges from 0.5N to 40N. This force can be characterized by measuring the maximum force needed to push a probe, equipped with a strain gauge, a fixed distance to the gel. The fixed distance can be between 40 and 80% of the total depth of the gel. This force can be measured in a QTS tester 25, using a 5 mm diameter probe. The typical forces measured are on the scale of 1 N to 25N. When the non-compressed portion is an extruded product, it is prepared by pre-mixing detergent components of the non-compressed portion with optional carrier components to form a viscous paste. Then, the viscous paste is extruded using any suitable commercially available extrusion equipment, such as for example a single or two wormer extruder available for example from APV Baker, Peterborough, United Kingdom. The extruded product is then cut to the desired size, either after dispensing the compressed portion, or before dispensing the compressed portion of the detergent tablet. The compressed portion of the tablet preferably comprises a mold in which the extruded uncompressed portion can be dispensed. In a preferred embodiment, the non-compressed portion is coated with a coating layer. The coating can be used to fix a non-compressed portion to the compressed portion. This can be particularly advantageous when the non-compressed portion contains fluid particles, gels or liquids. The coating layer preferably comprises a material which becomes solid by contacting the compressed and / or non-compressed portions preferably in the course of less than 15 minutes, preferably less than 10 minutes, preferably less than 5 minutes, and is very preferred less than 60 seconds. Preferably, the coating layer is soluble in water. Preferred coating layers comprise materials selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyacetic acid (PLA) , polyethylene glycol (PEG), and mixtures thereof. Preferred carboxylic or dicarboxylic acids comprise an even number of carbon atoms. Preferably, the carboxylic or dicarboxylic acids comprise at least 4, preferably at least 6, preferably at least 8 carbon atoms, and 8 to 13 carbon atoms are very preferred. Preferred dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sub-acidic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and mixtures thereof. Preferred fatty acids are those having a carbon chain length of C12 to 22, preferably C-? 8 to C22. Preferably, the coating layer may also comprise a rupture agent. When the coating layer is present, it will generally be at a level of at least 0.05%, preferably at least 0.1%, preferably at least 1%, preferably at least 2%, and at least very preferred 5% of the detergent tablet. As an alternative embodiment, the coating layer can encapsulate the detergent tablet. In this embodiment, the coating layer is present at a level of at least 4%, preferably at least 5%, and at least 10% of the detergent tablet is highly preferred.

In a preferred embodiment, the compressed and / or non-compressed portions and / or the coating layer additionally comprise a rupture agent. The breaking agent can be a disintegrating or effervescent agent. Suitable disintegrating agents include agents that swell on contact with water or facilitate the entry and / or exit of water to form channels in the compressed and / or uncompressed portions. Any known disintegrating or effervescing agent suitable for use in laundry or dishwashing applications is contemplated for use in the present invention. Suitable disintegrating agents include starch, starch derivatives, alginates, carboxymethyl cellulose (CMC), polymers based on CMC, sodium acetate, aluminum oxide. Suitable effervescent agents are those that produce a gas by contact with water. Suitable effervescent agents can be species that release oxygen, nitrogen dioxide or carbon dioxide. Examples of preferred effervescent agents can be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate, and carboxylic acids such as citric or maleic acid. The detergent tablet of the present invention is manufactured in accordance with a process described herein.

Perfume Component The perfume component of the present invention may comprise an encapsulated perfume, a properfume, or mixtures thereof. The perfume component is suspended or dispersed within the uncompressed portion of the detergent tablet of the present invention. In the context of this specification, the term "perfume" means any fragrant material or any material that acts to counteract a foul odor. In general, these materials are characterized by a vapor pressure greater than atmospheric pressure at room temperature. The perfume or deodorant materials employed herein will very often be liquid at room temperature, but may also be solids such as the various tanperaceous perfumes known in the art. A wide variety of chemical agents are known for use in perfumery, including materials such as aldehydes, ketones, esters and the like. More commonly, the oils and natural exudates of animals and vegetables, which comprise complex mixtures of various chemical components, are known to be used as perfumes, and such materials can be used here. The perfumes may be relatively simple in composition or may comprise very sophisticated complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor. Perfumes that are normally solid may also be employed in the present invention. These may be mixed with a liquefying agent such as a solvent, before their incorporation into the particles, or they may simply be melted and incorporated, as long as the perfume is not sublimed or decomposed by heating.

The invention also encompasses the use of materials that act to counteract malodors. These materials, although they are called "perfumes" below, may not have a discernible odor by themselves, but may conceal or reduce any unpleasant odors. Examples of suitable agents that counteract odors are described in the U.S.A. No. 3,102,101, issued August 27, 1963 to Hawley et al. For encapsulated perfumes, perfumes are understood to be encapsulated within a capsule comprising an encapsulating material, or a perfume that is preferably loaded onto a porous carrier material, which is then encapsulated within a capsule comprising an encapsulating material. There is a wide variety of capsules that allow the release of the perfume at different times during the use of the detergent tablet. Examples of said capsules with different encapsulated materials are the capsules provided by microencapsulation. Here the perfume comprises a capsule core that is completely coated with a material that can be polymeric. The patent of E.U.A. No. 4,145,184 of Brain et al., Issued March 20, 1979, and the patent of E.U.A. No. 4,234,627 to Schilling, issued November 18, 1980, teach the use of a resistant coating material that essentially prevents outward diffusions of the perfume.

The choice of encapsulated material for use in the perfume particles of the present invention will depend to some degree on the particular perfume to be used and the conditions under which the perfume will be released. Some perfumes will require a greater amount of protection than others and the encapsulating material to be used with it can be chosen accordingly. The encapsulating materials of the perfumed particles are preferably water-soluble or water-dispersible encapsulating material.

Non-limiting examples of suitable water-soluble coating materials include substances such as methylcellulose, maltodextrin and gelatin. Said coatings may comprise from 1% to 25% by weight of the particles. Particularly suitable water-soluble encapsulating materials are capsules consisting of a polysaccharide matrix and polyhydroxy compounds such as those described in GB 1, 464,616. Other suitable water-soluble or water-dispersible encapsulating materials comprise dextrins derived from acid esters of non-gelatinized starch of substituted dicarboxylic acids, such as those described in US Pat. No. 3,455,838. These acid ester dextrins are preferably prepared from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of such encapsulating materials are N-Lok®, manufactured by National Starch, Narlex (ST and ST2), and Capsul E®. These encapsulating materials comprise pregelatinized waxy maize starch and optionally glucose. The starch is modified by adding monofunctional substituted groups such as octenylsuccinic acid anhydride. For greater protection of the perfume particles in a liquid product, it may be more effective to encapsulate the perfume with a material that is pH sensitive, i.e., a material that remains as a coating on the particle in a pH medium, but that is removed from the particle in a medium of different pH. This would allow additional protection of the perfume especially in liquid or gel compositions during long periods of storage, i.e., the perfume will not diffuse out of the particle in the liquid medium so quickly. The diffusion of the perfume out of the particle already uncoated would take place after they came into contact with a medium of different pH. The encapsulated perfume particles can be made by mixing the perfume with the encapsulating matrix by spray drying emulsions containing the encapsulating material and the perfume. In addition, the particle size of the spray tower product can be modified. These modifications may comprise specific processing steps such as agglomeration steps after the tower (eg, fluidized bed) to enlarge the particle size, and / or processing steps in which the surface properties of the encapsulated products are modified. , for example, sprinkle with hydrophobic silica to reduce the hygroscopicity of the encapsulated products. A particularly preferred encapsulation process is an emulsification process followed by spray drying and finally sprinkling with silica. The emulsion is formed by: (a) dispersing the starch matrix in water at room temperature in a 1: 2 ratio. It is preferred that the starch be pregelatinized to perform the emulsification at this temperature. This in turn reduces the loss of perfume. It must be a "low viscosity" starch to reach high concentrations of starch in the water and high loads of perfume. (b) the perfume oil is then added to the above mixture in a ratio of 0.8-1.05: 1: 2 and the mixture is emulsified using a high shear mixer. The cutting motion should produce oil droplets less than 1 miera and the emulsion should be stable in this form for at least 20 minutes (the function of the starch is to stabilize the emulsion once it is mechanically made). (c) the mixture is spray-dried in a countercurrent tower equipped with a rotating disk atomizer. The drying air inlet temperature is less than 150-200 ° C. This type of spray drying ensures a minimum loss of perfume and a high drying speed. The granules have a particle size of 50 to 150 microns. (d) the resulting dry encapsulated products may contain up to 5% encapsulated oil on the surface of the granules.

To improve the flow characteristics, up to 2% hydrophobic silica can optionally be added to the encapsulated product by means of a ribbon mixer. Alternatively, the perfume can be loaded onto a vehicle and then optionally encapsulated. The proper vehicles are porous and do not react with the perfume. A suitable vehicle is the zeolite as described in the co-pending application PCT WO 94/28107 (Excerpt from Proxy No. 4904). The perfume component may alternatively comprise a properfume. Properfumes are precursors of perfume that release the perfume by interaction with an external stimulus, for example humidity, pH, chemical reaction. Properfumes suitable include those described in the US patent. No. 5,139,687 to Borcher et al., Issued August 18, 1992, and the US patent. No. 5,234,610 to Gardlik et al., Issued August 10, 1993, which are incorporated herein by reference. Examples of suitable pro-fumes comprise compounds having an ester of a perfume alcohol. The ester includes at least one free carboxylate group and has the formula wherein R is selected from the group consisting of a straight or branched alkyl, alkenyl, alkynyl or alkylaryl group, substituted or unsubstituted of C -? - C30, or an aryl group; R 'is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 ° C, and n and m are individually an integer of 1 or more. The perfume component may further comprise an ester of a perfume alcohol wherein the ester has at least one free carboxylate group in admixture with a fully esterified ester of a perfume alcohol. Preferably, R is selected from the group consisting of a straight or branched, substituted or unsubstituted C, -C20 alkyl, alkenyl, alkynyl or alkylaryl group, or an aryl or ring group containing a heteroatom. R 'is preferably a perfume alcohol selected from the group consisting of geraniol, nerol, phenoxanol, floralol, -citronelol, nonadol, cyclohexyl ethanol, phenylethanol, phenoxyethanol, isoborneol, fenchol, isociclogeraniol, 2-phenyl-1-propanol, 3.7 -dimethyl-1-octaneol, and combinations thereof, and the ester is preferably selected from esters of maleate, succinate, adipate, phthalate, citrate or pyromellitate of the perfume alcohol. Highly preferred esters having at least one free carboxylate group are selected from the group consisting of geranyl succinate, neryl succinate, cycronellyl maleate, nonadol maleate, phenoxanyl maleate, 3,7-dimethyl-1 succinate. -octanyl, cyclohexylethyl maleate, floralyl succinate, -citronelyl phthalate and phenylethyl adipate. Properfumes suitable for use herein include those that are known in the art. Proper properfumes can be found in the literature of the art, which includes the patents of E.U.A. Nos. 4,145,184 of Brain and Cummins, issued March 20, 1979; 4,209,417, by Whyte, issued June 24, 1980; 4,515,705 of Moeddel, issued May 7, 1985; and 4,152,272 de Young, issued May 1, 1979; All of these patents are incorporated herein by reference. It may be convenient to add additional perfume to the composition as such, without protection by the capsules. Said perfume load would by itself give a pleasant aesthetic fragrance to the detergent tablet. This perfume component is then mixed with other components of the non-compressed portion and then preferably delivered to the mold provided by the compressed portion. The detergent tablet comprises the perfume component at a level of 0.5% to 15%, preferably 1% to 10%, preferably 2% to 8% by weight of the non-compressed portion.

Process According to the present invention, there is also provided a process for preparing a detergent tablet, comprising the steps of: (a) compressing at least one detergent component using a compression pressure of more than 6.3 KN / cm2 to form a compressed portion; and (b) supplying a non-compressed portion comprising a perfume component in the compressed portion. The compressed portion comprises at least one, but preferably comprises more than one detergent component. The compressed portion is prepared by pre-mixing a composition of detergent components in a suitable mixer, for example, a pan mixer, rotating drum, vertical mixer or high shear mixer. Preferably, the dry particulate components are combined in a mixer, as described above, and the liquid components are applied to the dry particulate components, for example by spraying the liquid components directly onto the dry particulate components. Then, the resulting composition is converted into a compressed portion in a compression step, using any suitable equipment. Preferably, the composition is formed into a compressed portion using a tablet press, wherein the tablet is prepared by compressing the composition between an upper punch and a lower punch. In a preferred embodiment of the present invention, the composition is filled into a punch cavity of a tablet press and compressed to form a compressed portion preferably using a pressure greater than 6.3 KN / cm2, preferably greater than 9 KN / cm2, preferably greater than 14.4 KN / cm2. To form a preferred tablet of the invention, wherein the compressed portion has a mold for receiving the non-compressed portion, the compressed portion is prepared using a modified tablet press comprising modified upper and / or lower punches. These modified upper and lower punches of the tablet press are modified in such a way that the compressed portion provides one or more indentations forming one or more molds in which the non-compressed portion is dispensed. The non-compressed portion contains a perfume component. When the non-compressed portion additionally comprises one or more detergent components, these are premixed using any known suitable mixing equipment. The non-compressed portion can be prepared in solid or fluid form. Once the composition is prepared, it is dispensed into the compressed portion. The non-compressed portion may be supplied in the compressed portion by manual assortment or by using a nozzle feeder or extruder. When the compressed portion comprises a mold, the non-compressed portion is preferably dispensed into the mold using exact matching equipment, for example, a nozzle feeder, such as for example a weight loss screw feeder, available from Optimum, Germany. , or an extruder. When the fluid non-compressed portion is in particulate form, the method comprises filling a non-compressed fluid portion in the compressed portion in an assortment passage, and then coating at least a portion of the non-compressed portion with a coating layer of such a portion. so that the coating layer has the effect of substantially adhering the non-compressed portion in the compressed portion. When the fluid non-compressed portion (for example a gel) is fixed in the compressed portion by curing, the method comprises an assortment step in which the fluid non-compressed portion is delivered to the compressed portion, and a subsequent conditioning step in the compressed portion. where the uncompressed portion hardens. Said conditioning step may comprise drying, cooling, agglutination, polymerization, etc., of the non-compressed portion, during which the non-compressed portion becomes solid, semi-solid or highly viscous. Heat can be used in the drying step. Heat or exposure to radiation can be used to effect polymerization, in a polymerization step. It is also contemplated that the compressed portion can be prepared with a plurality of molds. The plurality of molds is then filled with a non-compressed portion. It is also contemplated that each mold may be filled with a different non-compressed portion or alternatively, each mold may be filled with a plurality of different non-compressed portions.

Detergent Components The compressed portion of the detergent tablets described herein comprises a composition of detergent ingredients. A suitable composition can include a variety of different active detergent ingredients including builders, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfume, lime soap dispersants, organic polymeric compounds including polymeric inhibitory agents. dye transfer, crystal growth inhibitors, heavy metal ions sequestrants, metal ions salts, enzyme stabilizers, corrosion inhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes. In a preferred aspect of the present invention, the non-compressed portion of the detergent tablet also comprises one or more detergent components. In a particularly preferred aspect of the present invention, the non-compressed portion additionally comprises one or more enzymes, examples of which are described below. The highly preferred active detergent ingredients include a builder, a surfactant, an enzyme and a bleaching agent.

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

Water-soluble detergent-enhancing compound Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two radicals carboxylics separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxyl group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinylcarboxylates. Polycarboxylates containing three carboxyl groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241, the lactooxysuccinates described in British Patent No. 1, 389,732 and the aminosuccinates described in Dutch application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1, 387,447. Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane-tetracarboxylates, 1,1, 3,3-propane tetracarboxylates and the 1, 1, 2,3-propanotetracarboxylates. Polycarboxylates containing sulfonyl substituents include the sulfosuccinate derivatives described in British Patents Nos. 1, 398, 441 and 1, 398, 422 and the US patent. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1, 439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1, 2,3, 4,5, 6-hexane-hexacarboxylates, and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melific acid, pyromellitic acid and phthalic acid derivatives which are described in British Patent No. 1, 425,343. Of the foregoing, preferred polycarboxylates are hydrocarboxylates containing up to three carboxyl groups per molecule, more particularly citrates. The origin acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example, citric acid or citrate / citric acid mixtures, are also contemplated as useful builders components. Borate builders can also be used, as well as builders that contain borate-forming materials that can produce borate under storage or washing conditions, but are not preferred under wash conditions of less than 50 ° C, especially less than 40 ° C. Examples of carbonate builders are the alkali metal and alkaline earth metal carbonates, which include carbonate and sodium sesquicarbonate and mixtures thereof with ultrafine calcium carbonate as described in German Patent Application No. 2,321,001, published on 15 November 1973. Very preferred builder compounds for use in the present invention are water soluble phosphate builders. Specific examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and sodium polymetaphosphate, in which Polymerization degree varies from 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound The detergent tablets of the present invention may contain a partially soluble or insoluble builder compound. The partially soluble or insoluble builder compounds are particularly suitable for use in tablets prepared for laundry washing methods. Examples of partially water-soluble detergency builders include the crystalline layered silicates which are described for example in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline layered sodium silicates of the general formula: NaMSix? 2+? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and "y" is a number from 0 to 20. Crystalline stratified sodium silicates of this type preferably have a two-dimensional "sheet" structure, such as so-called stratified structure as described in EP 0 164514 and EP 0 293640. Methods for preparing crystalline layered silicates of this type are described in DE-A-341749 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4, and is preferably 2. The preferred crystalline layered sodium silicate compound has the formula -Na2Si2O5, known as NaSKS-6 ( trade name), available from Hoechst AG. The crystalline layered sodium silicate material is preferably present in the granular detergent compositions as a particulate material intimately mixed with an ionizable water soluble solid material as described in PCT Patent Application No. WO 92/18594. The water-soluble solid ionizable material is selected from organic acids, salts of organic or inorganic acid and mixtures thereof, with citric acid being preferred. Examples of detergents mainly water-insoluble builders include sodium aluminosilicates. Suitable aluminosilicates include aluminosilicate zeolites having the unit cell formula Naz [(Al? 2) z (Si? 2) and] -xH2 ?, where z and "y" are at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28%. %, most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be materials of natural origin, but preferably are derived synthetically. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite.

HS and mixtures thereof. A preferred method of synthesis of aluminosilicate zeolites is that described by Schoeman et al. (Published in Zeolite (1994), 14 (2), 110-116, where a method for preparing colloidal aluminosilicate zeolites is described). The colloidal aluminosilicate zeolite particles should be such that preferably no more than 5% of the particles have a size smaller than 0.05 in diameter. Preferably, the aluminosilicate zeolite particles have an average particle size diameter of between 0.1 μm and 1 μm, preferably between 0.05 μm and 0.9 μm, preferably between 0.1 μm and 0.6 μm. Zeolite A has the formula: Na 12 [(Al? 2) 12 (Si? 2) 12] -xH20 where x is from 20 to 30, especially 27. Zeolite X has the formula Na86_ (Al? 2) 86 ( Si? 2) i06--276 H2 ° - as zeolites EP-B-384,070 as mentioned is a preferred detergency builder zeolite.

The preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When these are used as a component of a detergent composition, especially colloidal Zeolite A, they provide a greater detergency builder action in terms of improving soil removal. The greater detergency builder action is also seen in terms of reduced fouling in the fabrics and improved maintenance of the whiteness of the fabrics; problems that are considered associated with detergent compositions with improved detergency deficiency. A surprising finding is that the mixed aluminosilicate zeolite detergent compositions comprising colloidal zeolite A and colloidal Y zeolite, provide the same calcium ion sequestering action as an equal weight of the commercially available zeolite A. Another surprising finding is that the mixed aluminosilicate zeolite detergent compositions as described above, provide improved magnesium ion sequestering action compared to an equal weight of commercially available zeolite A.

Surfactants Surfactants are the preferred active detergent components of the compositions described herein. Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants, and mixtures thereof.

The products for automatic dishwashing should be of low foaming character, and in this way the foaming of the surfactant system should be suppressed in said methods or very preferably they should be of low foaming and generally of non-ionic character. It is not necessary to suppress to the same extent the foaming caused by the surfactant systems used in laundry laundry methods. The surfactant is generally present at a level of 0.2% to 30% by weight, preferably 0.5% to 10% by weight, preferably 1% to 5% by weight of the composition of active detergent ingredients. A typical list of classes and species of anionic, nonionic, ampholytic and zwitterionic surfactants is given in the U.S. patent. No. 3,929,678 issued to Laughiin and Heuring on December 30, 1975: A list of suitable cationic surfactants is given in the U.S. patent. No. 4,259,217 issued to Murphy on March 31, 1981. A list of surfactants typically included in automatic dishwashing detergent compositions is given for example in EP-A-0414 549 and in PCT applications Nos. WO 93/08876 and WO 93/08874.

Nonionic Surfactant Any detergent essentially including any nonionic surfactant useful for detersive purposes can be included in the tablet. Preferred non-limiting classes of useful nonionic surfactants are listed below.

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

Alkylalkoxylate surfactant blocked at its end A suitable alkylalkoxylate surfactant blocked at its end is an epoxy-blocked poly (oxyalkylated) alcohol represented by the formula: R? O [CH2CH (CH3) O] x [CH2CH2O] and [CH2CH (OH) R2] (I) wherein R-i is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of 0.5 to 1.5, preferably 1; and "y" is an integer having a value of at least 15, preferably at least 20. Preferably, the surfactant of formula I has at least 10 carbon atoms in the terminal epoxide unit [CH2CH (OH) R2]. Suitable surfactants of formula I according to the present invention are the nonionic surfactants POLY-TERGENT® SLF-18B from Olin Corporation, as described for example in WO 94/22800, published on October 13, 1994 by Olin Corporation .

Ether Blocked Polyphoxyalkylated Alcohols Preferred surfactants for use herein include ether-blocked poly (oxyalkylated alcohols having the formula: R1O [CH2CH (R3) O] x [CH2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are a linear or branched, saturated or unsaturated, or aromatic aliphatic hydrocarbon radical having from 1 to 30 carbon atoms; R3 is H, or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer that has an average value of 1 to 30, where when x is 2 or more, R3 can be the same or different, and y and y are integers that have an average value of 1 to 12, preferably 1 to 5 Preferably, R1 and R2 are linear or branched, saturated or unsaturated, or aromatic aliphatic hydrocarbon radicals, having from 6 to 22 carbon atoms, with 8 to 18 carbon atoms being preferred. For R3, H is preferred or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms. Preferably x is an integer having an average value of 1 to 20, preferably 6 to 15. As described above, when in the preferred embodiments x is greater than 2, R3 may be the same or different. That is, R3 can vary between any of the alkylenoxy units as described above. For example, if x is 3, R3 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and can vary in order of (EO) (PO) (EO), (EO) (EO) (PO), ( EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the integer three is only chosen as an example and the variation can be much greater with a larger integer value for x and include, for example, multiple units (EO) and a very small number of units (PO). Particularly preferred surfactants of those described above include those having a low cloud point of less than 20 ° C. These low cloud point surfactants can then be used in conjunction with a high cloud point surfactant as described in detail below to obtain superior fat cleaning benefits. Preferred ether-blocked poly (oxyalkylated alcohol) surfactants are those in which k is 1 and j is 1, such that the surfactants have the formula: R1O [CH2CH (R3) O] xCH2CH (OH) CH2OR2 wherein R1, R2 and R3 are as defined above and x is an integer with an average value of 1 to 30, preferably 1 to 20, and 6 to 18 is most preferred. Surfactants in which R1 is especially preferred are preferred. and R 2 range from 9 to 14, R 3 is H forming ethyleneoxy and x ranges from 6 to 15. Poly (oxyalkylated) alcohol surfactants blocked with ether comprise three general components, a linear or branched alcohol, an alkylene oxide and a block end of alkyl ether. The alkyl ether end block and the alcohol serve as an hydrophobic, oil soluble portion of the molecule, while the alkylene oxide group forms the water soluble hydrophilic portion of the molecule. When used in conjunction with high-cloud point surfactants, these surfactants exhibit significant improvements in staining and film-forming characteristics and in the removal of greasy soils from conventional surfactants. Generally speaking, the poly (oxyalkylene) alcohol surfactants blocked with ether of the present invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. This is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. The following describes examples of methods for preparing poly (oxyalkylated alcohol) surfactants blocked with ether.

Preparation of C 1 / C 1 alkyl aryl ether A C 12/14 fatty alcohol (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g, 2.23 mmol, available from Aldrich) are combined in a bottom flask. round three-neck equipped with a condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C. Epichlorohydrin (47.70 g, 0.515 moles, available from Aldrich) is added dropwise in such a way as to maintain the temperature between 60 and 65 ° C. After stirring an additional hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%), while stirring mechanically. After the addition is complete, the mixture is heated at 90 ° C for 1.5 hours and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO 4, filtered and concentrated. By distillation of the oil at 100-120 ° C (0.1 mm Hg) the glycidyl ester is produced as an oil.

Preparation of blocked alcohol surfactant with alkyl (C- ??) ether (Cg / ??) Neodol® 91-8 (20.60 g, 0.093 mole of ethoxylated alcohol available from Shell Chemical Co.) and tin chloride (IV) are combined ) (0.58 g, 2.23 mmol) in a 250 ml round bottom three-necked flask equipped with condenser, argon inlet, addition funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 ° C at which temperature glycidyl C12 / u alkyl glycidyl ether (1.00 g, 0.0393 mol) is added dropwise 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 2.5 cm pad of silica gel while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation and then steamed in a Kugeirohr oven (100 ° C, 0.5 mm Hg) to produce the surfactant as an oil.

Non-ionic surfactant of ethoxylated / propoxylated fatty alcohol The ethoxylated C6-C? 8 fatty alcohols and the ethoxylated / propoxylated C6-C-? 8 mixed fatty alcohols are suitable surfactants for use herein, in particular when they are soluble in water . Preferably, the ethoxylated fatty alcohols are ethoxylated fatty alcohols of C-IO-C-IS with an ethoxylation degree of 3 to 50, preferably they are ethoxylated fatty alcohols of C-? 2-C? 8 with an ethoxylation degree of 3. to 40. Preferably, the ethoxylated / propoxylated mixed fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30, and a degree of propoxylation of 1 to 10.

EO / PO nonionic surfactants condensed with propylene glycol For use herein, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and exhibits insolubility in water. Examples of compounds of this type include certain Pluronic ™ surfactants commercially available from BASF.

EO nonionic condensation products with propylene oxide / ethylene diamine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use here. The hydrophobic portion of these products consists of the reaction product of ethylene diamine and excess propylene oxide, and generally have a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactants include certain Tetronic ™ compounds commercially available from BASF.

Mixed nonionic surfactant system In a preferred embodiment of the present invention, the detergent tablet comprises a mixed nonionic surfactant system comprising at least one non-ionic low-haze surfactant, and at least one non-ionic surfactant of high turbidity point. "Turbidity point", as used herein, is a well-known property of non-ionic surfactants, which is the result of the surfactant becoming less soluble upon increasing the temperature, with reference to the temperature at which the appearance of a second phase, such as the "turbidity point" (see Kirk Othmer's Encyclopedia of Chemical Technology - Kirk Othmer Chemical Technology Encyclopedia - 3rd edition volume 22 pages 360-379). As used herein, a "low cloud point" nonionic surfactant is defined as an ingredient of a nonionic surfactant system having a cloud point of less than 30 ° C, preferably less than 20 ° C, and preference less than 10 ° C. Typical low-cloud point nonionic surfactants include alkoxylated nonionic surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Also, such low-cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (for example, Poly-Tergent® SLF18 from Olin Corporation), poly (oxyalkylated) alcohols blocked with epoxy (for example the Poly- Tergent® SLF 18B of non-ionic surfactants from Olin Corporation, as described for example in WO 94/22800, published October 13, 1994 by Olin Corporation) and poly (oxyalkylated) alcohol surfactants blocked with ether. The nonionic surfactants may optionally contain propylene oxide in an amount of up to 15% by weight. Other preferred nonionic surfactants can be prepared by the process described in the US patent. No. 4,223,163, issued September 16, 1980, by Builloty, incorporated herein by reference. Low cloud point nonionic surfactants additionally comprise a polymeric polyoxyethylene and polyoxypropylene block composite. The polyoxyethylene-polyoxypropylene polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as the starting reactive hydrogen compound. Some of the block polymer surfactant compounds designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® from BASF-Wyandotte Corp., Wyandotte Michigan, are suitable in ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Said surfactants are typically useful herein as non-low-cloud point nonionic surfactants.

How it is used here, a "high cloud point" nonionic surfactant is defined as an ingredient of a nonionic surfactant system having a cloud point of more than 40 ° C, preferably more than 50 ° C, and preferably more than 60 ° C. Preferably, the nonionic surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkylphenol of 8 to 20 carbon atoms with 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol in an average base. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell). For the purposes of the present invention it is also preferred that the high cloud point nonionic surfactant further has a hydrophilic-lipophilic balance value ("HLB").; see Kirk-Othmer above) within the range of 9 to 15, preferably 11 to 15. Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (Supplied by Shell). Another high cloud point nonionic preferred surfactant is derived from a straight chain or preferably branched or secondary fatty alcohol containing from 6 to 20 carbon atoms (C6-C20 alcohol), including secondary alcohols and branched chain primary alcohols. Preferably, high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, condensed with an average of 6 to 15 moles, preferably 6 to 12 moles, and preferably 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant thus derived has a narrow distribution of ethoxylate relative to the average. In a preferred embodiment, the detergent tablet comprising such a mixed surfactant system also comprises an amount of water-soluble salt to provide conductivity in deionized water measured at 25 ° C, greater than 3 milli Siemens / cm, preferably greater than 4 milli Siemens / cm, preferably greater than 4.5 milli Siemens / cm, as described in the British co-pending patent application (Proxy Extract No. CM 1573F). In another preferred embodiment, the mixed surfactant system is dissolved in water having a hardness of 1,246 mmole / liter in any suitable automatic cold-fill dishwasher, to provide a solution with a surface tension of less than 4 dynes / cm2 less than 45 ° C, preferably less than 40 ° C, preferably less than 35 ° C, as described in the US patent application copendiente (Proxy Extract No. 6252). In another preferred embodiment, the high cloud point and low cloud point surfactants of the mixed surfactant system are separated such that one of the two is present in a first matrix and the other is present in a second matrix, as described in the US patent application copendiente (Proxy Extract No. 6252). For the purposes of the present invention, the first matrix may be a first particulate material, and the second matrix may be a second particulate material. A surfactant can be applied to a particulate material by any suitable known method, preferably the surfactant is sprayed onto the particulate material. In a preferred aspect, the first matrix is the compressed portion and the second matrix is the non-compressed portion of the detergent tablet of the present invention. Preferably, the low-cloud point surfactant is present in the compressed portion, and the high-cloud point surfactant is present in the non-compressed portion of the detergent tablet of the present invention.

Anionic surfactant Essentially any anionic surfactant useful for detersive purposes is suitable. These may include salts (which include for example sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include the isethionates, such as for example the acyl isethionates, N-acyltaurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated monoesters of C 2 -d s), diesters of sulfosuccinate (especially saturated and unsaturated diesters of C-? -C? 8), N-acyl sarcosinates. Also suitable are rosin acids and hydrogenated rosin acids, such as resin, hydrogenated resin and resin acids and hydrogenated resin acids, present or derived from tallow tree oil.

Sulphonic Anion Surfactant The anionic sulfate surfactants suitable for use herein include the primary and secondary linear and branched alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ether sulfates of ethylene oxide, the acyl (C5-C? 7) -N- (alkyl C-C4) - and N- (hydroxyalkyl CrC2) glucaminesulfates, and alkylpolysaccharide sulfates such as for example the alkylpolyglucoside sulfates (the non-sulfated nonionic compounds described herein). The alkylsulfate surfactants are preferably selected from the linear and branched primary alkyl sulfates of C-IO-C-IS, preferably the C11-C15 branched chain alkyl sulphates and the straight chain alkyl sulfates of C- | 2-C-? . The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C-io-Cis alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Preferably, the alkylethylsulfate surfactant is a Cn-C18 alkyl sulfate, preferably Cn-C5, which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred surfactants of alkyl sulfate and alkyl ethoxy sulfate. Such mixtures have been described in PCT patent application No. WO 93/18124.

Sulfonate Anionic Surfactant Anionic sulphonate surfactants suitable for use herein include alkylbenzene sulfonate salts and linear Cs-C2o alkyl ether sulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C2 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates. , fatty oleyl glycerol sulfonates, and any mixture thereof.

Carboxylate Anionic Surfactant Suitable alkylethoxycarboxylates include those having the formula RO (CH 2 CH 2 O) x CH 2 COO "M +, wherein R is an alkyl group of Ce a C 8, x ranges from 0 to 10, and the ethoxylate distribution is such that, based on weight, the amount of material where x is 0, is less than 20%, and M is a cation Suitable alkylpolyethoxy polycarboxylate surfactants include those having the formula RO- (CHR -? - CHR2 -O) -R3, wherein R is an alkyl group of C6 to C18, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, acid radical hydrosuccinic, 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 soap surfactants secondary containing a carboxyl unit attached to a secondary carbon. 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 acid -1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R 1) CH 2 COOM, wherein R is a linear or branched alkyl or alkenyl group of Cs-C 7, R 1 is an alkyl group of CC and M is an alkali metal ion. Preferred examples are myristyl- and oleoylmethyl sarcosinates in the form of their sodium salts.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids.

Suitable amine oxides include compounds having the formula R3 (OR4) xN0 (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl group, or mixtures thereof, containing from 8 to 26 atoms of carbon; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing 1 to 3 ethylene oxide groups, or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Preference is given to the C 0 -C 18 alkyldimethylamine oxide, and the C 1 or C 18 acylamidoalkyldimethylamine oxide. A suitable example of an alkylalanodicarboxylic acid is Miranol (™) C2M Conc., Manufactured by Miranol, Inc., Dayton, New Jersey.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. These surfactants can generally be described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. Suitable betaines are compounds having the formula R (R ') 2N + R2COO ", wherein R is a C6-C? 8 hydrocarbyl group, each R1 is generally C? -C3 alkyl, and R2 is a hydrocarbyl group of C1-C5 The preferred betaines are the betaines of dimethylammonium hexanoate of C12-C-is, and the acylamidopropane- (or ethane) -dimethyl- or (diethyl) betaines of C? 0-C18. here the betaine complex surfactants.

Cationic Surfactants The ester cationic surfactants used in this invention are preferably water dispersible compounds having surfactant properties, comprising at least one ester linkage (ie, -COO-), and at least one cationically charged group. Other suitable cationic ester surfactants including choline ester surfactants have been described, for example in U.S. Patents. Nos. 4,228,042, 4,239,660 and 4,260,529. Suitable cationic surfactants include the quaternary ammonium surfactants selected from C 6 -C 6 mono-, N-alkyl- or alkenylammonium, preferably C 6 -C 0 0, wherein the remaining N positions are substituted with methyl, hydroxyethyl groups or hydroxypropyl.

Enzymes Enzymes may be included as ingredients of the compressed portion of the detergent tablet. In a preferred embodiment of the present invention, enzymes are present as ingredients of the non-compressed portion. When such enzymes are present, they are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, or mixtures thereof. Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase and / or cellulase, in conjunction with one or more plant cell wall degrading enzymes. Cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and an activity greater than 50 CEVU (Viscosity Unit of Cellulose). Suitable cellulases are described in the U.S.A. Do not. 4,435,307 to Bargesgoard et al., J 61078384 and WO 96/02653, which describe fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thievalia and Sporotrichum. EP 739 982 describes cellulases isolated from novel species of Bacillus. Suitable cellulases are also described in GB-A-2,075,028; GB-A- 2,095,275; DE-OS-2,247,832 and WO 95/26398.

Examples of said cellulases are the cellulases produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea.), Particularly the Humicola strain DSM 1800. Other suitable cellulases are the cellulases originated from Humicola insolens having a molecular weight of about 50. kDa, an isoelectric point of 5.5, and containing 415 amino acids, and a ~ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity, a preferred endoglucanase component having the amino acid sequence described in the application PCT Patent No. WO 91/17243 Also suitable are the EGIII cellulases of Trichoderma longibrachiatum described in WO 94/21801, by Genencor, published on September 29, 1994. Particularly suitable cellulases are cellulases that have care benefits Examples of said cellulases are the cellulases described in European Patent Application No. 91202879.2, filed on 6 November 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO 96/34092, W096 / 17994 and WO 95/24471. Said cellulases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition.

Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", that is, to avoid the transfer of dyes or pigments removed from the substrates during the washing operations, to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO 89/099813, WO 89/09813 and European Patent Application No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on February 20, 1996. The laccase enzyme is also suitable. Preferred creators are substituted phenoxyzine and phenoxazine, 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinopropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621). ) and substituted syringates (substituted C3-C5 alkylsalicylates) and phenols. Preferred sources of hydrogen peroxide are percarbonate or sodium perborate. Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, such as those described in British Patent 1, 372, 034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P " Amano ", hereinafter referred to as" Amano-P ". Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases, for example Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Netherlands and lipases from Pseudomonas gladioli. Particularly suitable lipases are lipases such as Lipase M1 ^ and Lipomax ^ (Gist-Brocades) and Lipolase ^ and Lipolase UltraR (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 of Novo Nordisk, and in WO 94/03578, WO 95/35381 and WO 96/00292 of Unilever. Also suitable are cutinases [EC 3.1.1.50] that can be considered as a special type of lipase, particularly lipases that do not require interfacial activation. The addition of cutinases to detergent compositions has been described for example in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System), and WO 94/14963 and WO 94/14964 (Unilever). The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN1). A suitable protease is obtained from a Bacillus strain that has a maximum activity on the entire pH scale of 8 to 12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, by Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal designed by protein engineering) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application No. 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98) and which is herein called " Protease B ", and in the European patent application EP 199 404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine protease that is called in the present" Protease A ". The protease called "Protease C", which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, serine, is suitable. replaces asparagine at position 123 and alanine replaces threonine at position 274. Protease C is described in EP 90915958.4, corresponding to WO 91/06637, published on May 16, 1991. They are also included in present the genetically modified variants, particularly of protease C. A preferred protease, referred to as "protease D", is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a carbonyl hydrolase precursor replacing a different amino acid with the amino acid residue in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more positions of amino acid residue equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, + 156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 in accordance with the numbering of the subtilisin from Bacillus amyloliquefaciens as described in WO 95/10591 and in the patent application of C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes" -whitening compositions containing protease enzymes-, having the serial number of USA 08 / 322,677, filed October 13, 1994. Proteases described in patent applications EP 251 446 and WO 91/06637, the BLAP® protease described in WO 91/01792, are also suitable for the present invention., and its variants, which are described in WO 95/23221. See also a high pH protease of Bacillus NCIMB 40338, which is described in WO 93/18140 A of Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A of Novo. When desired, a protease having reduced adsorption and increased hydrolysis is available, as described in WO 95/07791 of Procter & amp; amp;; Gamble. A recombinant trypsin-like protease for detergents, which is suitable for use herein, is described in WO 94/25583 by Novo. Other suitable proteases are described in EP 516 200 of Unilever. Other preferred protease enzymes include protease enzymes which are a variant of carbonyl hydrolase having an unnatural amino acid sequence, derived by replacing a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of residues of amino acid replaced in the precursor enzyme correspond to position +210, in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, + 107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, wherein the numbered positions correspond to the natural subtilisin of Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those that have changes at positions +210, +76, +103, +104, +156 and +166. The proteolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, most preferably from 0.005% to 0.1% pure enzyme by weight of the composition. Amylases (and / or ß) can be included for the removal of carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S, published on February 3, 1994, discloses detergent compositions that incorporate mutant amylases. See also WO / 94/18314, Genencor, published on August 18, 1994 and WO / 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include: β-amylases. Α-amylases are known in the art, and include those described in the US patent. No. 5,003,257; in EP 252,666; WO / 91/00353; RF 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 the amylases of improved stability described in WO94 / 18314, published on August 18, 1994 and WO 96/05295, Genencor, published on February 22, 1996, and the amylase variants having further modification in the progenitor. immediate, available from Novo Nordisk A / S and described in WO95 / 10603, published April 1995. Also suitable are the amylases described in EP 277 216, WO 95/26397 and WO 96/23873 (all from Novo Nordisk). Examples of commercial a-amylases products are Purafect Ox Am®, from Genencor, and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a value of ® pH on the scale of 8 to 10, measured by the Phadebas test of α-amylase activity. Also suitable are the variants of the above enzymes which are described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher activity level are described in WO95 / 35382. Preferred amylase enzymes include those described in WO 95/26397 and in the co-pending application of Novo Nordisk PCT / DK96 / 00056. The amylolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. In a particularly preferred embodiment, the detergent tablets of the present invention comprise amylase enzymes, particularly those described in WO 95/26397 and the co-pending application of Novo Nordisk PCT / DK96 / 00056, in combination with a complementary amylase. By "complementary" is meant the addition of one or more suitable amylases for detergent purposes. Below are examples of complementary amylases (and / or). WO 94/02597 and WO 95/10603 of Novo Nordisk A / S describe cleaning compositions incorporating mutant amylases. Other amylases known to be used in cleaning compositions include α- and β-amylases. Α-amylases are known in the art, and include those described in the US patent. 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 the amylases of improved stability described in W094 / 18314, and WO 96/05295, Genencor, and the amylase variants having further modification in the immediate parent, available from Novo Nordisk A / S and described in WO95 / 10603 . Also suitable are the amylases described in EP 277 216 (Novo Nordisk). Examples of commercial α-amylases products are Purafect Ox Am®, from Genencor, and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. WO 95/26397 describes other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a value of pH on the scale of 8 to 10, ® measured by the Phadebas test of α-amylase activity. Also suitable are the variants of the above enzymes which are described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher activity level are described in WO95 / 35382. Preferred complementary amylases for the present invention are the amylases sold under the Purafect Ox Am® trademarks, which are described in WO 94/18314, WO 96/05295, sold by Genencor; Termamyl®, Fungamyl®, Ban® and Duramyl®, all available from Novo Nordisk A / S, and Maxamyl® from Gist-Brocades. Said complementary amylases are generally incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, most preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. Preferably, the weight ratio of pure enzyme from specific amylase to complementary amylase is between 9: 1 and 1: 9, preferably between 4: 1 and 1: 4., and most preferably between 2: 1 and 1: 2. The aforementioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The origin can also be mesophilic or extremophile (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidic, halophilic, etc.). The purified or non-purified forms of these enzymes can be used. Mutants of natural enzymes are also included by definition. Mutants can be obtained, for example, by protein engineering and / or genetic engineering, and chemical and / or physical modifications of natural enzymes. It is also common practice the expression of the enzyme by host organisms in which the genetic material responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. The enzymes can be added as separate individual ingredients (pills, granules, stabilized liquids, etc., containing an enzyme) or as mixtures of two or more enzymes (for example cogranulates). Other suitable detergent ingredients that may be added are the enzyme oxidation scavengers described in co-pending European patent application 92870018.6, filed on January 31, 1992. Examples of these enzyme oxidation scavengers are the ethoxylated tetraethylene polyamines. A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also described in WO 9307263 A and WO 9307260 A of Genencor International, WO 8908694 A of Novo, and the patent of E.U.A. No. 3,553,139, January 5, 1971, by McCarty et al. Enzymes are also described in the U.S. Patents. Nos. 4,101, 457, Place et al., July 18, 1978 and 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in US Pat. No. 4,261, 868, Hora et al., April 14, 1981. The enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in the patent documents of E.U.A. No. 3,600,319, August 17, 1991, Gedge et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. No. 3,519,570. A Bacillus sp. AC13 useful and giving proteases, xylanases and cellulases is described in WO 9401532 A de Novo.

Bleaching agent In one embodiment of the present invention, a bleaching agent is present as an essential component of the compressed portion. In other embodiments, the bleaching agent is a highly preferred component of the compressed or non-compressed portions. Suitable bleaching agents include chlorine and oxygen releasing bleaches. In a preferred aspect, the oxygen-releasing bleaching agent contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of organic peroxyacid occurs by an in situ reaction of the precursor with 1 a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred aspect a preformed organic peroxyacid is directly incorporated into the composition. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and organic peroxyacid precursor, in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Bleaches The active detergent component compositions preferably include a source of hydrogen peroxide as an oxygen-liberating bleach. Suitable sources of hydrogen peroxide include the inorganic salts of perhydrate. The inorganic salts of perhydrate are normally incorporated in the form of the sodium salt at a level of from 1% to 40% by weight, preferably from 2% to 30% by weight, and preferably from 5% to 25% by weight of The compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic salts of perhydrate are usually the alkali metal salts. The inorganic salt of perhydrate can be included as the crystalline solid, without additional protection. However, for some perhydrate salts, preferred embodiments of said granular compositions utilize a coated form of the material which provides better stability during storage of the perhydrate salt in the granular product. The sodium perborate may be in the form of the monohydrate of the nominal formula NaB02H202, or the tetrahydrate NaB02H202-3H20. The alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates for inclusion in compositions according to the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H2? 2, and is commercially available as a crystalline solid. Sodium percarbonate, being an addition compound of hydrogen peroxide, tends by dissolution to release hydrogen peroxide very rapidly, which may increase the tendency to cause high localized concentrations of high bleach. The percarbonate is preferably incorporated into said compositions in a coated form that provides stability to the product. A suitable coating material that provides stability to the product comprises the mixed salt of sulfate and alkali metal carbonate soluble in water. Said coatings, together with coating processes, have been previously described in GB-1, 466,799, granted to Interox on March 9, 1977. The weight ratio of the coating material of the mixed salt to percarbonate is in the scale of 1. : 200 to 1: 4, preferably from 1: 99 to 1: 9, and preferably from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate, which has the general formula Na2SO, 4.n.Na2C? 3, 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 that provides stability to the product comprises sodium silicate, of S SO 2: Na 2 O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate, preferably applied to a level of 2% to 10% (usually 3% to 5%) of SiO2 by weight of the inorganic salt of perhydrate. Magnesium silicate may also be included in the coating. Also suitable are coatings containing silicate and borate salts or boric acids or other inorganic compounds. Other coatings containing waxes can also be advantageously used in the present invention., oils, and fatty soaps. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions present.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors can be represented as: O X-C-L wherein L is a leaving group and X is essentially any functionality, such that perhydrolysis, the structure of the produced peroxyacid is: 0 II X-C-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, preferably from 1% to 10%, preferably from 1.5% to 5% by weight of the bleaching compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, these precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups The leaving group, hereinafter group L, must be sufficiently reactive for the perhydrolysis reaction to occur within the appropriate time frame (e.g., a wash cycle). However, if L is too reactive, it will be difficult to stabilize this activator for use in a bleaching composition.

The preferred L groups are selected from the group consisting of: R3 and I I -O- CH = C- CH = CH2, - O- CH = C- CH = CH2, and mixtures thereof; wherein R1 is an alkyl, aryl, or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3; R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilization group. Any of R1, R3 and R4 can be substantially substituted with any functional group, including for example alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilization groups are -S? 3_M +, -C? 2"M +, -S? 4"M +, -N + (R3) 4X" and O < -N (R3) 3, and most preferably -S? 3"M + and -CO2" M +, wherein R is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator, and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates, including for example benzoyl oxybenzenesulfonate: Also suitable are the benzoylation products of sorbitol, glucose and all saccharides, with benzoylation agents, including for example: Ac = COCH3; Bz = Benzoyl The perbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and the N-benzoyl-substituted ureas. Suitable precursors of imidazole-type perbenzoic acid include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful prebents of perbenzoic acid containing the N-acyl group include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyrglutamic acid. Other perbenzoic acid precursors include the benzoyl diacylperoxides, the benzoyl tetraacylperoxides and the compounds having the formula: Phthalic anhydride is another perbenzoic acid precursor compound suitable herein: Suitable precursors of N-acylated lactam perbenzoic acid have the formula: wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.

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

Cationic Peroxyacid Precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids by perhydrolysis. Typically, the cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl- or methylammonium group. The cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion such as for example a halide ion or a methylsulfate ion. The peroxyacid precursor compound to be cationically substituted may be a perbenzoic acid, or a substituted derivative precursor compound thereof as described above. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in U.S. Pat. Nos: 4,904,406; 4,751, 015, 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; United Kingdom patent No. 1, 382.594; EP 475,512, 458,396 and 284,292; and in Japanese Patent 87-31,832. Suitable cationic peroxyacid precursors include any of the alkyl or benzoyl oxybenzenesulfonates substituted with ammonium or alkylammonium, N-acylated caprolactams, and monobenzoyltetraacetyl-glucose-benzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzenesulfonate is the 4- (trimethylammono) methyl benzoyl oxybenzene sulfonate derivative: A preferred cationically substituted alkyl oxybenzene sulfonate has the formula: Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium methylenebenzoylcaprolactams, particularly the trimethylammonium methylenebenzoylcaprolactam: Another preferred precursor and peroxical cation of the N-acylated caprolactam class includes trialkylammonium methylene alkyl caprolactams: wherein n is from 0 to 12, particularly from 1 to 5. Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) ethyl-sodium 4-sulfophenyl-chlorocarbonate.

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

Alkylperoxy Acid Precursors Substituted with Amide The amide substituted alkylperoxy acid precursor compounds are also suitable, including those of the following general formulas: R1_C- N- R2_ C- L R1- N- C- R2- C- L II I II I II II O R5 OR R5 O O in which R ^ is an alkyl group with 1 to 14 carbon atoms, R2 is a alkylene group containing from 1 to 14 carbon atoms, and R ^ is H or a < alkyl group containing 1 to 10 carbon atoms, and L can be essentially any outgoing group. Preferably, R ^ contains from 6 to 12 carbon atoms. Preferably, R2 contains from 4 to 8 atoms of carbon. R1 may be straight or branched chain alkyl containing branching, substitution or both, and may originate from synthetic sources or from natural sources including for example tallow fat. They are permissible analogous structural variations for R2. The substitution may include alkyl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds R5 is preferably H or methyl. R "* and R ^ should not contain more than 18 carbon atoms in total In this document EP-A-0170386 discloses bleach-activating compounds substituted with amide of this type.

Benzoxazine Organic Peroxyacid Precursors Benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807 are also suitable, particularly those having the formula: which include substituted benzoxazines of the type: wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2) R3, R4 and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino , COOR6 (where Re is H or an alkyl group) and carboxyl functions. An especially preferred precursor of the benzoxazine type is: Preformed organic peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, a precursor organic peroxyacid bleach compound, a preformed organic peroxyacid, typically at a level of 0.5% to 25% by weight, preferably 1%. % to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the substituted amine compounds of the following general formulas: R1- C- N- R2- -C- OOH R1- N- C- R2- C- OOH II L II II O ?? R? e5 O or R5 O O wherein R 1 is an alkyl, aryl or alkaryl group with 1 to 14 carbon atoms carbon, R2 is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms, and R ^ is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. Preferably, R ^ contains from 6 to 12 atoms of carbon. Preferably, R2 contains from 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl, aryl or substituted alkylaryl which contains branching, substitution or both, and may originate from synthetic sources or from natural sources including for example tallow. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur or other typical substituent groups or organic compounds. R ^ is preferably H or methyl. R ^ and R ^ must not contain more than 18 carbon atoms in total. EP-A-0170386 describes organic substituted peroxyacid compounds with amide of this type. Other organic peroxyacids include diacyl peroxides and tetraacyl peroxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is a preferred organic peroxyacid. Also suitable are mono- and diperazelaic acid, mono- and diperbrasyl acid, and N-phthaloylaminoperoxycaproic acid.

Controlled release rate media A means can be provided to control the rate of release of the bleaching agent, particularly oxygen bleach, in the wash solution. The means for controlling the rate of release of the bleach can produce the controlled release of peroxide species in the wash solution. Such means may include, for example, control of the release of any inorganic perhydrate salt that acts as a source of hydrogen peroxide in the wash solution. Suitable means of controlled release may include confinement of the bleach in the compressed portion or in the uncompressed portion. When more than one non-compressed portion is present, the bleach may be confined to the first and / or the second or subsequent optional non-compressed portions. Another mechanism for controlling the rate of release of the bleach can be by coating the bleach with a coating designed to provide controlled release. Therefore, the coating may for example comprise a poorly water soluble material, or be a coating of sufficient thickness so that the dissolution kinetics of the coarse coating provides the rate of controlled release. The coating material can be applied using various methods. Any coating material is typically present in a weight ratio of coating material to bleach of from 1: 99 to 1: 2, preferably from 1:49 to 1: 9. Suitable coating materials include triglycerides (for example partially hydrogenated vegetable oil, soybean oil, cottonseed oil), mono- or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixture thereof. Other suitable coating materials may comprise the alkali metal and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas. A preferred coating material, particularly for a source of inorganic perhydrate salt bleach, comprises sodium silicate of SiO2: Na2O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and / or sodium metasilicate. sodium, preferably applied at a level of 2% to 10% (usually 3% to 5%) of SiO by weight of the inorganic perhydrate salt. Magnesium silicate may also be included in the coating. Any inorganic salt coating material can be combined with organic binder materials to provide combined inorganic salt / organic binder coatings. Suitable binders include C ?0.C20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole of alcohol, and preferably the primary alcohol ethoxylates of C-15-Q20 containing from 20 to 100. moles of ethylene oxide per mole of alcohol. Other preferred binders include certain polymeric materials. Examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 x 106, preferably 1000 to 400,000, preferably 1000 to 10000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer, are additional examples of the polymeric materials useful as binders. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the aforementioned C10-C20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole.

Additional examples of binders include the mono- and diglycerol ethers and also the C 0 -C 20 fatty acids. Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- and copolymeric polycarboxylic acids or their salts are other examples of suitable binders for use herein. A method for applying the coating material includes agglomeration. Preferred agglomeration procedures include the use of any of the organic binder materials described above. Any conventional agglomerator / mixer can be used, including without limitation the types of pan, rotary drum and vertical mixer. Molten coating compositions can also be applied, either by voiding or sprayed on a moving bed of bleaching agent. Other means for providing the required controlled release include mechanical means to alter the physical characteristics of the bleach to control its solubility and release rate. Suitable protocols would include compression, mechanical injection, manual injection, and adjustment of the solubility of the bleaching compound by selection of the particle size of any particulate component. Although the choice of particle size will depend both on the composition of the particulate component and the need to achieve the desired kinetics of controlled release, it is desirable that the particle size be greater than 500 microns, preferably with an average particle diameter of 800. at 1200 microns. Additional protocols for providing the controlled release means include the proper choice of any other component of the detergent composition matrix, such that when the composition is introduced into the wash solution, the ionic strength medium provided therein allows achieve the controlled release kinetics required.

Metal-Containing Bleach Catalyst The compositions described herein which contain bleach as an active detergent component may additionally contain as a preferred ingredient, a metal-containing bleach catalyst. Preferably, the metal-containing bleach catalyst is a bleach catalyst containing transition metal, preferably a bleach catalyst containing manganese or cobalt. A suitable type of bleach catalyst is a catalyst consisting of a heavy metal cation of defined bleach catalytic activity, such as copper cations, iron, an auxiliary metal cation having little or no catalytic bleaching activity, such as cation zinc or aluminum, and a scavenger having defined stability constants for the auxiliary and catalytic metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylene phosphonic acid) and water soluble salts thereof. Such catalysts are described in U.S. Patent No. 4,430,243. Preferred types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and US patent. No. 5,244,594. Preferred examples of these catalysts include Mn'V2 (u-O) 3 (1, 4,7-trimethyl-1,4,7-triazacyclononane) 2- (PFe) 2. Mnm2 (u-O) < | (u-OA (1, 4,7-trimetiM, 4,7-triazacyclononane) 2 (Cl? 4) 2, MnI 4 (uO) e (1, 4,7-triazaciclonano) 4 (Cl? 4) 4, Mn ^ Mn '^ u-OJi (u-OAc) 2 (1, 4,7-trimetiI-1, 4, 7-triazacyclonone) 2 (Cl? 4) 3, and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,6-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane, 1, 2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof. Bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see the patent of E.U.A. No. 4,246,612, and the patent of E.U.A. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416, which teaches manganese (IV) mononuclear complexes such as Mn (1, 4,7-trimethyl-1, 4,7-triazacyclononane) (OCH 3) 3- (PF 6).

Another type of bleaching catalyst, as described in the patent of E.U.A. No. 5,114,606 is a water soluble complex of manganese (III), and / or (IV) with a ligand which is a polyhydroxy compound without carboxylate having at least 3 consecutive groups of C-OH. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof. The patent of E.U.A. No. 5,114,611 shows a bleach catalyst consisting of a complex of transition metals, including Mn, Co, Fe, or Cu, with a ligand that is not macrocyclic. Said ligands are of the formula: R2 R3 I I R1 _N = C-B-C = N-R4 wherein R "1, R2, R3 and R4, each, may be selected from H, and substituted aryl and alkyl groups, so that each R ^ -N = C-R2 and R3-C = N-R4 form a ring 5 or 6 members, said ring may also be substituted, B is a bridge-forming group selected from O, S, CR5R6, NR7, and C = O, wherein R5, R6, and R7 may be each, H, an alkyl, or aryl, group including substituted or unsubstituted groups Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy The preferred bleach catalysts include Co, Cu, Mn, Fe, bispyridylmethane and bispyridylamine complexes.The highly preferred catalysts include Co (2,2 '), halogenide and nitro, the 2,2'-bispyridylamine ligand being particularly preferred. bispyridyl amine) Cl 2, di (isothiocyanate) -bispyridylamine-cobalt (II), trisdipyridylamine perchlorate -cobalt (II), Co (2,2-bispyridylamine) 2? -2Cl? 4, bis- (2,2'-bispyridylamine) perchlorate-copper (ll), trichloride (di-2) perchlorate -pyridylamine) -iron (II) and mixtures thereof. Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands that include N4Mn '"(u- O) 2MnlvN) + and [Bipy2Mn "l (uO) 2Mnl bipy2HCI? 4) 3. Although the structures of the manganese complexes bleach catalysts of the present invention have not been elucidated, it can be speculated that they comprise chelates or other complexes of hydrated coordination that originate from the interaction of the carboxyl and the nitrogen atoms of the ligand with the manganese cation.Also, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and it can be the valence state ( +11), (+111), (+ IV) or (+ V) Due to the six possible binding points of the ligand with the manganese cation, it can reasonably be speculated that there may be multinuclear species and / or structures of " "cage" in the aqueous bleaching medium, whatever the actual form in which the active Mn-ligand species exist, this functions in an evidently catalytic manner to provide enhanced bleaching actions on stubborn stains such as tea, ketchup, coffee, wine, juice and the like.

Other bleach catalysts are described, for example, in the European patent application, publication No. 408,131 (cobalt complex catalysts), European patent applications, publications Nos. 384,503, and 306,089 (metalloporphyrin catalysts), patent of E.U.A. No. 4,728,455 (multidentate ligand / manganese catalyst), U.S. No. 4,71 1, 748 and European patent application, publication No. 224,952, (manganese absorbed in aluminosilicate catalyst), U.S. No. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. No. 4,626,373 (manganese / ligand catalyst), U.S. No. 4,119,557 (ferric complex catalyst), German Patent Specification No. 2,054,019 (cobalt chelating catalyst), Canadian Patent No. 866,191 (transition metal containing salts), U.S. Pat. No. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. Pat. No. 4,728,455 (manganese gluconate catalysts). Other preferred examples include cobalt catalysts (III) having the formula: CoKNHaJnM'mB'bT'tQqPplYy where the cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably 4 or 5, preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; 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 appropriately selected counter anions, present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3, preferably 2 when Y is an anion loaded with -1), to obtain a salt of balanced load; the preferred portion Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and where in addition at least one of the coordination sites linked to the cobalt is labile under the conditions of use of the automatic dishwashing, and the rest of the coordination sites stabilize the cobalt under the conditions of automatic dishwashing, of such that the potential reduction of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) against a normal hydrogen electrode. Preferred cobalt catalysts of this type have the formula: [Co (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, preferably 5); M 'is a labile coordination moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, preferably 1); m + n = 6; and Y is an appropriately selected counter anion, present in a number y, which is an integer from 1 to 3 (preferably 2 to 3, preferably 2 when Y is an anion charged with -1), to obtain a balanced charge salt. The preferred cobalt catalyst of this type is the pentaamine-cobalt chloride salt having the formula [Co (NH3) 5CI] Yy, and especially [Co (NH3) 5CI] CI2. Preferred in the present invention are compositions using cobalt bleach catalysts (III) having the formula: [Co (NH3) n (M) m (B) b] Ty, where the cobalt is in its +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated with the cobalt at one site; m is 0, 1 or 2 (preferably 1); B is a coordinated ligand in the cobalt at two sites; b is 0 or 1 (preferably o), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more appropriately selected counter anions, present in a number y, where y is an integer to obtain a balanced charge salt (preferably y is 1 to 3, preferably 2 when T is an anion with a charge of -1 ); and wherein said catalyst also has a base hydrolysis rate constant of less than 0.23 M'V1 (25 ° C). Preferred portions T are selected from the group consisting of chloride, iodide, 13, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6, BF, B (Ph) 4, phosphate, phosphite, silicate , tosylate, methanesulfonate, and combinations thereof. Optionally, T may be protonated if there is more than one anionic group in T, for example, HPO42", HCO3", H2PO4", etc. In addition, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants ( for example, linear alkylbenzenesulfonates, LAS, alkyl sulphates, AS, alkyl ethoxy sulfates, AES, etc.) and / or anionic polymers (eg, polyacrylates, polymethacrylates, etc.) The M portions include, but are not limited to, for example, F ", SO4" 2, NCS ", SCN", S2O3"2, NH3, PO43 *, and carboxylates (which are preferably monocarboxylates, but may be present in the more than one carboxylate portion, as long as the binding to cobalt is by medium of only one carboxylate per serving, in which case the other carboxylate in the M portion may be protonated or in its salt form). Optionally, M can be protonated if there is more than one anionic group in M (for example HPO42", HCO3", H2PO4", HOC (O) CH2C (O) O", etc.). Preferred M-portions are substituted and unsubstituted C?-C 30 carboxylic acids having the formulas: RC (O) O- wherein R is preferably selected from the group consisting of hydrogen and CJ-C 30 alkyl (preferably C 1 -C). C-is). unsubstituted and substituted, C6-C30 (preferably CQ-CJ Q), unsubstituted and substituted aryl, and C3-C30 heteroaryl (preferably C5-C-18). unsubstituted and substituted, wherein the substituents are selected from the group consisting of -NR'3, -NRV ", -C (0) OR \ -OR \ -C (0) NR'2, wherein R 'is selects from the group consisting of hydrogen and portions of C < \ -CQ. For the thus, said substituted R includes portions - (CH2) nOH and - (CH2) nNR'4 +, where n is an integer from 1 to 16, preferably from 2 to 10, and 2 to 5 is very preferred. Preferred M-portions are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C-12 alkyl, and benzyl. The most preferred portion R is methyl. The preferred M-moieties of carboxylic acid include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric acid , acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic acid.

Portions B include carbonate, dicarboxylates and higher carboxylates (for example oxalate, malonate, malate, succinate, maleate), picolinic acid, and alpha- and beta-amino acids (for example glycine, alanine, beta-alanine, phenylalanine). The cobalt bleach catalysts useful herein are known and described for example together with their base hydrolysis rates, in ML Tobe "Base Hydrolysis of Transition-Metal Complexes" - Base hydrolysis of transition metal complexes, Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table 1, page 17, provides base hydrolysis rates (designated there as koH) for oxallate-complexed cobalt pentaamine catalysts (koH = 2-5 x 10-4 M-V (25 ° C)), NCS "(kQH = 5.0 x 10" 4 M-V (25 ° C)), format (koH = 5.8 x 10"4 M" V1 (25 ° C)), and acetate (o H = 9-6 x 10"4 M" V1 (25 ° C)). The most preferred cobalt catalyst useful herein are the salts of cobalt pentaamineacetate having the formula [Co (NH3) 5? Ac] Tv, wherein OAc represents a portion of acetate and especially cobalt pentaamineacetate chloride, [Co (NH3) 5? Ac] Cl2, "as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5? Ac] (BF4) 2 and [Co (NH3) 5OAc] (NO3) 2 ("PAC" herein) These cobalt catalysts are readily prepared by known procedures, such as those taught by example in Tobe's article cited above and references cited therein, in the US patent No. 4,810,410 to Diakun et al., Issued March 7, 1989, in J. Chem. Ed. (1989) 66 (12), pages 1043-45; "The Synthesis and Characterization of Inorganic Compounds" - Synthesis and characterization of inorganic compounds-, W.L. Jolly (Prentice-Hall, 1970), pages 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry 56, 22-25 (1952), as well as the synthesis examples provided therein. Cobalt catalysts suitable for incorporation into the detergent tablets of the present invention can be produced in accordance with the synthetic routes described in the U.S. Patents. Nos. 5,559,261, 5,581, 005, and 5,597,936, the disclosures of which are incorporated herein by reference. These catalysts can be coprocessed with auxiliary materials to reduce the color impact, if desired, for aesthetics of the product, or they can be included in particles containing enzyme as exemplified herein below, or compositions containing "macules" of catalyst.

POLYMERIC ORGANIC COMPOUND Polymeric organic compounds can be added as preferred components of the detergent tablets according to the invention. By "polymeric organic compound" is meant essentially any polymeric organic compound commonly found in detergent compositions having dispersing, anti-redeposition, dirt removal, or other detergency properties.

The polymeric organic compound is generally incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, preferably from 1% to 10% by weight of the compositions. Examples of polymeric organic compounds include organic water-soluble homo- or copolymeric polycarboxylic acids, modified polycarboxylates, or salts thereof, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms . Polymers of the latter type are described in GB-A-1, 596,756. Examples of such salts are the polyacrylates of molecular weight 2000-10000, and their copolymers with any other suitable monomer unit, including modified acrylic acid, fumaric, maleic, taconic, acotinic, mesaconic, citraconic and methylenemalonic or salts thereof, maleic anhydride, acrylamide, alkylene, vinyl methyl ether, styrene and any mixture thereof. Copolymers of acrylic acid and maleic anhydride having a molecular weight of 20,000 to 100,000 are preferred.

Preferred acrylic acid-containing polymers that are commercially available have a molecular weight of less than 15,000 and include those sold under the trademarks Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 from BASF GmbH, and those sold under the trademark Acusol 45N, 480N, 460N from Rohm and Haas.

Preferred acrylic acid-containing copolymers include those which contain as monomer units: (a) from 90% to 10%, preferably from 80% to 20% by weight, of acrylic acid or its salts, and (b) of 10% by weight. 90%, preferably 20% to 80% by weight of a substituted acrylic monomer or its salts, having the formula - [CR2-CR -? (CO-O-R3)], wherein at least one of the substituents Ri, R2 or R3) preferably Rt or R, is an alkyl or hydroxyalkyl group of 1 to 4 carbons, Ri or R2 can be a hydrogen and R3 can be a hydrogen or an alkali metal salt. Preferred is a substituted acrylic monomer wherein Ri is methyl, R2 is hydrogen (ie, a methacrylic acid monomer). The preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid. Useful are polyamine and modified polyamine compounds which include aspartic acid derivatives such as those described in EP-A-305282, EP-A-305283, and EP-A-351629. Other optional polymers can be both modified and unmodified polyvinyl alcohols and acetates, cellulose and modified cellulose materials, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, both modified and unmodified, esters of ethylene or propylene glycol terephthalate, or mixtures thereof. same with polyoxyalkylene units. Suitable examples are described in the US patents. Nos. 5,591, 703, 5,597,789 and 4,490,271.

Soil Removal Agents Suitable polymeric soil removal agents include those agents having (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2; or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not include any oxypropylene unit unless it is linked to adjacent portions at each end by ether linkages; or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophilic segments preferably comprise at least 25% oxyethylene units and most preferably, especially for components having from 20 to 30 oxypropylene units , at least 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) segments of C3 oxyalkylene terephthalate, wherein, if said hydrophobic components also comprise oxyethylene terephthalate., the ratio of oxyethylene terephthalate: oxyalkylene terephthalate units of C3 is 2: 1 or less, (ii) C4-C6 alkylene segments or C4-C6 oxyalkylene, or mixtures thereof, (iii) segments of poly (vinyl ester), preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) substituents of C-C4 alkylether or C-hydroxyalkylether, or mixtures thereof, wherein said substituents are present in the form of C 1 -C 4 alkylether cellulose derivatives or C 4 hydroxyalkylether, or mixtures thereof, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of 200, although higher levels, preferably from 3 to 150, preferably from 6 to 100, may be used. The hydrophobic oxyalkylene segments of C4- C6 include, without limitation, blocked end polymeric soil removal agents such as MO3S (CH2) nOCH2CH2? -, where M is sodium and n is an integer from 4 to 6, as described in the US patent No. 4,721, 580, issued January 26, 1988 to Gosselink. The polymeric soil removal agents useful herein also include cellulosic derivatives such as hydroxy ether cellulosic polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, and the like. Such agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). The cellulosic soil removal agents for use herein also include those selected from the group consisting of C 1-4 alkylcellulose and C hydroxy alkylcellulose.; see also the patent of E.U.A. No. 4,000,093, issued December 28, 1976 to Nicol et al. Soil removal agents characterized by hydrophobic poly (vinyl ester) segments include poly (vinyl ester) graft copolymers, for example, C? -C6 vinyl esters, preferably poly (vinyl acetate) grafted onto oxide backbones. polyalkylene as skeletons of polyethylene oxide. See European Patent Application No. 0 219 048, published April 22, 1987 by Kud et al. Another suitable soil remover is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate (PEO). The molecular weight of this polymeric soil removal agent is in the range of 25,000 to 55,000. See also the patent of E.U.A. No. 3,959,230 to Hays, issued May 25, 1976, and the patent of E.U.A. No. 3,893,929 to Basadur, issued July 8, 1975. Another suitable soil remover is a polyester with repeated units of ethylene terephthalate containing 10 to 15% by weight of units of ethylene terephthalate, together with 90-80. % by weight of polyoxyethylene terephthalate units derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Another suitable soil remover is a sulphonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkylenoxy repeat units and terminal portions covalently attached to the backbone. These soil removal agents are fully described in the U.S. patent. No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil removal agents include the terephthalate polyesters of the U.S. Patent. No. 4,711, 730, issued December 8, 1987 to Gosselink and others; the oligomeric esters of anionic blocked ends of the U.S.A. No. 4,721, 580, issued January 26, 1988 to Gosselink, and the polyester block oligomeric compounds of the U.S.A. No. 4,702,857, issued October 27, 1987 to Gosselink. Other polymeric soil removal agents also include the soil removal agents of the U.S.A. No. 4,877,896, issued October 31, 1989 to Maldonado et al., Which discloses anionic blocked terephthalate esters, especially sulfoarolyl esters. Another soil remover is an oligomer with repeated units of terephthaloyl, sulfoisoterephthaloyl, oxyethyleneoxy and oxy-1,2-propylene. The repeating units form the skeleton of the oligomer and preferably terminate with modified isethionate end blocks. A particularly preferred soiling agent of this type comprises a unit of sulfoisophthaloyl, 5 units of terephthaloyl, oxyethyleneoxy, and units of oxy-1,2-propyleneoxy in a ratio of 1.7 to 1.8, and two end block units of 2. - Sodium (2-hydroxyethoxy) ethanesulfonate.

Heavy Metal Ion Sequestrant The detergent tablets of the invention preferably contain as an optional ingredient, a heavy metal ion sequestrant. By "heavy metal ion sequestrant" is meant herein components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably show selectivity for binding to heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, preferably from 0.25% to 7.5%, and 0.5% to 5% by weight of The compositions. Heavy metal ion sequestrants, which are acidic in nature, and have for example functionalities of phosphonic acid or carboxylic acid, may be present in their acid form or as a complex / salt with a suitable countercation such as, for example, an ion alkali metal or alkaline earth metal, ammonium ion or substituted ammonium, or any of their mixtures. Preferably, any salt / complex is soluble in water. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1: 1. Suitable sequestrants of heavy metal ions for use herein include organic phosphonates such as the alkali metal aminoalkylene poly (alkylene phosphonates), ethane 1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are penta (methylenephosphonate) of diethylenetriamine, tri (methylenephosphonate) of ethylenediamine, tetra (methylenephosphonate) of hexamethylenediamine and 1,1-d-hydroxyethylene phosphonate.

Another suitable heavy metal ion sequestrant to be used herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamineadisuccinic acid, ethylenediamineadiglutaric acid, 2-hydroxypropylenediamine acid, or any salt thereof. Especially preferred is ethylenediamine-N.N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.

Crystal Growth Inhibiting Component Detergent tablets preferably contain a crystal growth inhibiting ingredient, preferably an organodiphosphonic acid component, preferably incorporated at a level of 0.01% to 5%, preferably 0.1% to 2% by weight of the compositions By organodiaphosphonic acid is meant here an organodiphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes organo-aminophosphonates, which, however, can be included in the compositions of the invention as sequestering components of heavy metal ions.

The organodiphosphonic acid is preferably a C 1 -C 4 diphosphonic acid, preferably a C 2 diphosphonic acid, such as for example ethylene diphosphonic acid, or very preferably ethane-1-hydroxy-1,1-diphosphonic acid (HEDP), and may be present in partially or totally ionized form, particularly as a salt or complex.

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

Alkali metal silicate According to one embodiment of the present invention, an alkali metal silicate is an essential component of the detergent tablet. In other embodiments of the present invention, the presence of an alkali metal silicate is optional. A preferred alkali metal silicate is sodium silicate having a SiO2: Na2O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, preferably 2.0. The sodium silicate is preferably present at a level of less than 20%, preferably from 1% to 15%, preferably from 3% to 12% by weight of SiO2. The alkali metal silicate can be in the form of the anhydrous salt or a hydrated salt. The alkali metal silicate can also be present as a component of an alkalinity system. The alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% SiO2 by weight. Sodium metasilicate has a nominal ratio of S¡O2: Na2O of 1.0. The weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO 2, is preferably from 50: 1 to 5: 4, preferably from 15: 1 to 2: 1, preferably from 10: 1 to 5: 2. .

Colorant The term "colorant" as used herein, means any substance that absorbs specific wavelengths of light from the visible spectrum. Said colorants, when added to a detergent composition, have the effect of changing the visible color and thus the appearance of the detergent composition. The dyes can be, for example, dyes or pigments. Preferably, the dyes are stable in the composition in which they are to be incorporated. Thus, in a high pH composition the dye is preferably alkali stable, and in a low pH composition the dye is preferably acid stable.

The compressed portion and / or the non-compressed portion may contain a colorant, a mixture of colorants, coloring particles or a mixture of coloring particles, so that the compressed portion and the uncompressed portion have different visual appearances. Preferably, any of the portions, either compressed or uncompressed, comprises a colorant. When the non-compressed portion comprises two or more compositions of active detergent components, preferably at least some of the compositions, whether the first, second and / or subsequent, comprises a colorant. When both the first and second and / or subsequent compositions contain a colorant, it is preferred that the colorants have a different visual appearance. When the coating layer is present, it preferably comprises a colorant. When the compressed portion and the coating layer comprise a colorant, it is preferred that the colorants have a different visual effect. Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo, diazo, polyazo dyes. Highly preferred dyes include anthraquinone, quinoline and monoazo dyes. SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name) are all available from Clariant, United Kingdom, HEXACOL QUINOLINE YELLOW (name) commercial) and HEXACOL BRILLIANT BLUE (trade name), both available from Pointings, UK, ULTRAMARINE BLUE (trade name) available from Holliday or LEVAFIX TURQUISE BLUE EBA (trade name) available from Bayer, USA The dye may be incorporated in the compressed and / or uncompressed portion by any suitable method. Suitable methods include mixing all or a few of the selected active detergent components with a dye in a drum or spraying all, or some selected, active detergent components with the dye into a rotating drum. When a dye is present as a component of the compressed portion, it is at a level from 0.001% to 1.5%, preferably from 0.01% to 1.0%, preferably from 0.1% to 0.3%. When there is a dye as a component of the non-compressed portion, it is generally present at a level of 0.001% to 0.1%, preferably from 0.005% to 0.05%, preferably from 0.007% to 0.02%. When present as a component of the coating layer, the colorant is at a level from 0.01% to 0.5%, preferably from 0.02% to 0.1%, preferably from 0.03% to 0.06%.

Corrosion inhibiting compound The detergent tablets of the present invention suitable for use in dishwashing methods may contain corrosion inhibitors, preferably selected from organic silver coating agents, particularly paraffin, nitrogen-containing corrosion inhibiting compounds and Mn compounds. (II), particularly salts of Mn (II) of organic ligands. Organic silver coating agents are disclosed in PCT publication No. WO 94/16047 and in European co-pending application No. EP-A-690122. Nitrogen-containing corrosion inhibiting compounds are described in the co-pending European application No. EP-A-634478 Mn (II) compounds are described for use as corrosion inhibitors in European co-pending application No. AP-A-672749. The organic silver coating agent can be incorporated at a level of from 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition. The function of the silver coating agent is to form "during use" a layer of protective coating on any component of the silverware of the washing load in which the compositions of the invention are applied. The silver coating agent must, therefore, have a high binding affinity to the solid surfaces of the silver, particularly when it is present as a component of an aqueous wash and bleach solution with which the solid surfaces are treated of silver. Organic agents suitable for the silver coating include fatty esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. The fatty acid portion of the acid ester can be obtained from mono- or polycarboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, glycolic acid and ß, ß acid. '-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butylmalonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid. The fatty alcohol radical in the fatty ester can be represented by the mono- and polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, giicerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Preferably, the fatty acid and / or fatty alcohol group of the fatty ester auxiliary material has from 1 to 24 carbon atoms in the alkyl chain.

Preferred fatty esters herein are the esters of ethylene glycol, glycerol and sorbitan, wherein the fatty acid portion of the ester usually comprises a selected species of behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Glycerol esters are very preferred. These are the mono-, di-, or tri-esters of glycerol and the fatty acids defined above. Specific examples of fatty alcohol esters to be used herein include: stearyl acetate, palmityl dilactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and seboyl propionate. Fatty acid esters 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 monomiristate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mono - and mixed diesters of tallowalkylsorbitan. The glycerol esters preferred herein are glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate. Suitable organic silver coating agents include triglycerides, mono- or diglycerides and wholly or partially hydrogenated derivatives thereof, and mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil. Waxes, including microcrystalline waxes, are suitable organic silver coating agents. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally comprise from 12 to 70 carbon atoms. Preferred are paraffin and microcrystalline type petroleum waxes 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 C2-C20 methylammonium halides. Other organic silver coating agents include certain polymeric materials. Examples of these polymeric materials are polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, polyethylene glycols (PEG) with an average molecular weight of 600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxymethylcellulose.

Certain perfume materials, particularly those demonstrating high substantivity by metal surfaces, are also useful as the organic silver coating agent. The polymeric soil removal agents can also be used as an organic silver coating agent. A preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of 20 to 50; the preferred paraffin oil is selected from branched species of C25.45, with a ratio of cyclic to non-cyclic hydrocarbons from 1: 10 to 2: 1, preferably from 1: 5 to 1: 1. A paraffin oil having these characteristics has a ratio of cyclic to non-cyclic hydrocarbons of 32:68, and is sold by Wintershall, Salzbergen, Germany, under the trademark WINOG 70.

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

The pyrazole compounds and their derivatives are also suitable as nitrogen-containing corrosion inhibiting compounds, particularly those in which the pyrazole is substituted in any of positions 1, 3, 4 or 5 with substituents Ri, R3, R4 and R5, wherein R1 is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of C1-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2. Other suitable nitrogen-containing corrosion inhibiting compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1, 2,3,4-tetrazole, tionalide, morpholine, melamine, distearylamine, stearoyl-teraramide, cyanuric acid, aminotriazole, aminotetrazole and indazole. Also suitable are nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium acid citrate.

Mn (ll) Corrosion Inhibiting Compounds The detergent tablets may contain a corrosion inhibiting compound of Mn (II). The Mn (II) compound is preferably incorporated at a level of 0.005% to 5% by weight, preferably from 0.01% to 1%, preferably from 0.02% to 0.4% by weight of the compositions. Preferably, the compound of Mn (II) is incorporated at a level sufficient to provide from 0.1 ppm to 250 ppm, preferably from 0.5 ppm to 50 ppm, preferably from 1 ppm to 20 ppm by weight of Mn (II) ions in any bleaching solution. The Mn (II) compound may be an inorganic salt in anhydrous or hydrated form. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The Mn (II) compound can be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate. The Mn (II) compound may be a salt or complex of an organic ligand. In a preferred aspect, the organic ligand is a heavy metal ion sequestrant. In another preferred aspect, the organic ligand is a crystal growth inhibitor.

Other corrosion inhibiting compounds Other suitable corrosion inhibiting compounds include mercaptans and diols, especially mercaptans having 4 to 20 carbon atoms, including laurylmercaptan, thiophenol, thionephthol, tionalide and thioanthranol.

Also suitable are saturated or unsaturated C 10 -C 20 fatty acids or their salts, especially aluminum tristearate. The hydroxy fatty acids of C-? 2-C2o or their salts are also suitable. Also the phosphonated octadecane and other antioxidants such as betahydroxytoluene (BHT). It has been found that copolymers of butadiene and maleic acid, particularly those provided under commercial reference No. 07787 of Polysciences Inc., are of particular utility as corrosion inhibiting compounds.

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

Water-soluble bismuth compound 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 of 0.005% a %, preferably from 0.01% to 5%, preferably from 0.1% to 1% by weight of the compositions.

The water-soluble bismuth compound can be essentially any bismuth salt or complex, essentially with any organic or inorganic counter-anion. The preferred inorganic bismuth salts are selected from bismuth trihalogenides, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are the preferred salts with an organic counter anion.

Enzyme stabilizer system Preferred enzyme containing compositions herein can comprise from 0.001% to 10%, preferably from 0.005% to 8%, preferably from 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilizer system can be any stabilizing system compatible with the detersive enzyme. Said stabilizer systems may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers, and mixtures thereof. These stabilizer systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Lime Soap Dispersant Compound The detergent active component compositions may contain a lime soap dispersing compound, preferably at a level of 0.1% to 40% by weight, preferably 1% to 20% by weight, most preferably 2% by weight. % to 10% by weight of the compositions. A lime soap dispersant is a material that prevents the precipitation of the alkali metal, ammonium or amine salts of fatty acids caused by calcium or magnesium ions. The lime soap dispersant compounds are described in PCT Application No. WO 93/08877.

Foam suppressor system The detergent tablets of the present invention, when formulated for use in machine wash compositions, preferably comprise a foam suppressor system at a level of from 0.01% to 15%, preferably from 0.05% to 15%, preferably from 0.05% to 10%, and from 0.1% to 5% by weight of the composition is very preferred. The foam suppressor systems for use herein comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl and alkanol antifoaming compounds. Foam suppressing systems and antifoaming compounds are disclosed in PCT Application No. WO 93/08876 and EP-A-705 324.

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

Optical Brightener Detergent tablets suitable for use in laundry washing methods as described herein, also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R-j is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, Rj is anilino, R2 is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the brightener is acid 4,4,, bis [(4-aniolin-6- (N -2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and its disodium salt. This particular brightener species is marketed under the Tinopal-UNPA-GX brand by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the previous formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4I-bis [(4-anilino-6- (N- 2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the Tinopal 5BM-GX brand of Ciba-Geigy Corporation. When in the above formula Ri is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphyl) -s- triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the Tinopal AMS-GX brand of Ciba-Geigy Corporation.

Clay softening system Detergent tablets suitable for use in laundry laundry methods may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent. The clay mineral compound is preferably a smectite clay compound. Smectite clays are described in the patents of E.U.A. Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. The patents European Nos. EP-A-299,575 and EP-A-313,146, in the name of Procter & gamble Company, describe organic flocculating clay polymeric agents.

Cationic fabric softening agents Cationic fabric softening agents which are suitable for use in laundry washing methods can also be incorporated into the compositions according to the present invention. Suitable cationic fabric softening agents include water-insoluble tertiary amines or long two-chain amide materials such as those described in GB-A-1 514 276 and EP-B-0 011 340. Cationic anti-caking agents fabrics are typically incorporated at total levels of 0.5% to 15% by weight, usually from 1% to 5% by weight.

Other Optional Ingredients Other suitable ingredients for inclusion in the compositions of the invention include perfumes and filler salts, with sodium sulfate being the preferred filler salt. pH of the compositions The detergent tablets of the present invention are preferably formulated so as not to have an irregular pH; preferably they have a pH of 8.0 to 12.5, preferably of 9.0 to 1.8, and is very preferred of 9.5 to 11.5, measured as a 1% solution in distilled water. In another aspect of the present invention, the compressed and non-compressed portions are formulated to release different pH values.

Machine washing method Any suitable method for machine washing dirty tableware is contemplated. A preferred method for washing dishes in the machine comprises treating the selected dirty items of earthenware, glassware, silverware, metalware, cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispersed an effective amount of a detergent tablet in accordance with the invention By an effective amount of the detergent tablet is meant from 8 g to 60 g of dissolved or dispersed product in a volume of 3 to 10 liters of the washing solution, which are the product doses and volumes of washing solution commonly employed in the conventional methods of washing dishes in the machine. Preferably, the detergent tablets are from 15 g to 40 g in weight, preferably from 20 g to 35 g in weight.

Laundry Washing Method The machine washing methods herein typically comprise treating laundry in a washing machine with an aqueous solution having dissolved or dispersed an effective amount of a detergent tablet composition for laundry in machine in accordance with the present invention. with the invention The effective amount of the detergent tablet composition is from 40 g to 300 g of product dissolved or dispersed in a volume of 5 to 65 liters of washing solution, which are the product doses and volumes of washing solution commonly used in the methods conventional washing of clothes in machine. In a preferred use aspect, a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product, such as would 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 wash cycle, water is introduced into the drum and this rotates periodically. The design of the dispensing device must be such as to allow the containment of the dry detergent product, but to allow the release of this product during the wash cycle in response to its agitation as the drum rotates, and also as a result of its contact with the drum. wash water. To allow the release of the detergent product during washing, the device can have several openings through which the product can pass. Alternatively, the device can be made of a material that is liquid permeable but impermeable to the solid product, which will allow the release of the dissolved product. Preferably, the detergent product will be released rapidly at the beginning of the wash cycle, thereby producing high localized transient concentrations of product in the drum of the washing machine at this stage of the wash cycle. The preferred dispensing devices are reusable and are designed in such a way that the integrity of the product is maintained both in the dry state and during the wash cycle. Alternatively, the dispensing device may be a flexible container such as a bag or pouch. The bag may be of fibrous construction coated with a waterproof protective material to retain the contents, as described in published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymeric material insoluble in water with a seal or closure at its edge, designed for rupture in aqueous medium, as described in published European patent applications Nos. 001 1500, 001 1501, 0011502, and 0011968. A convenient form of water-frangible closure comprises an adhesive soluble in water. water that is along an edge to which it seals, of a pouch formed of a waterproof polymeric film in water, such as, for example, polyethylene or polypropylene.

EXAMPLES Abbreviations used in the examples In the detergent compositions, the identifications of abbreviated components have the following meanings: STPP Sodium Tripolyphosphate Citrate Trisodium citrate dihydrate Bicarbonate Carbonate Sodium acid Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate Silicate Amorphous sodium silicate (Si? 2 ratio: Na2? = 1.6-3.2) PB1 Anhydrous sodium perborate monohydrate PB4 Perborate of sodium tetrahydrate of nominal formula NaBO2 3H2O H2O2 Nonionic Nonionic surfactant of C13-C-15 of ethoxylated / propoxylated mixed fatty alcohol, with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the brand name BASF's Plurafac TAED: Tetraacetylethylenediamine HEDP Ethane-1-hydroxy-1,1-diphosphonic acid DETPMP: Diethylenetriaminepenta (methylene) phosphonate, marketed by Monsanto under the brand Dequest 2060 PAAC Cobalt pentaamineacetate salt (lll) Paraffin Paraffin oil sold under the brand name Winog 70 by Wintershall Protease Proteolytic enzyme Amylase Amylolytic enzyme BTA Benzotriazole PA30 Polyacrylic acid of average molecular weight of about 4,500 Sodium Sulphate Anhydrous Sulfate PEG 4000 Polyethylene glycol, molecular weight of about 4000, available from Hoechst PEG 8000 Polyethylene glycol, molecular weight of about 8000, available from Hoechst Sugar Homemade Gelatin Gelatin Type A, coating resistance 65, available from Sigma Modified Carboxymethylcellulose Starch sold under the Nimcel brand, available from Metcaserle Encapsulated Perfume: Encapsulated perfume oil with a composition of 37% modified starch , 11% sorbitol and 1% smoked silica, available from Drytec C.P. Triacetin: Glycerin Triacetate, sold under the trademark De Thixatrol: Derivative of castor oil sold under the brand Thixatrol of Rheox PVP: Polyvinylpyrrolidone having a molecular weight of 300,000 PEO: Polyethylene oxide having a molecular weight of 45,000 PH: Measured as a 1% solution in distilled water at 20 ° C.

In the following examples, all levels are cited as% by weight of the compressed portion, the non-compressed portion or the coating layer.

EXAMPLE 1 The following examples illustrate examples of detergent tablets of the present invention, suitable for use in machine dishwashing.

The compressed portion is prepared by supplying the composition of the detergent ingredients in a punch cavity of a modified 12-head rotary tablet press, and compressing the composition at a pressure of 13 KN / cm2. The modified tablet press provides tablets in which the compressed portion has a mold. For the purposes of Examples A to F, the non-compressed portion comprises a perfume component and a gelling agent. The non-compressed portion is then emptied into the mold of the compressed portion. Then, the detergent tablet is subjected to a conditioning step during which the non-compressed portion becomes hard.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent tablet comprising a compressed portion and a non-compressed portion, characterized in that the compressed portion is prepared using a compression pressure of more than 6.3 KN / cm 2, and the non-compressed portion contains a perfume component.

2. A detergent tablet comprising a compressed portion and a non-compressed portion, characterized in that the non-compressed portion dissolves faster than the compressed portion, on a weight-to-weight basis, by measuring the solution by means of the SOTAX dissolving method. which is indicated in the description, and wherein the non-compressed portion contains a perfume component.

3. A detergent tablet comprising a compressed portion and a non-compressed portion, characterized in that the compressed portion contains a bleaching agent and the non-compressed portion contains a perfume component.

4. A detergent tablet comprising a compressed portion, a non-compressed portion and a perfume component, characterized in that the perfume component is suspended or dispersed within the non-compressed portion.

5. - The detergent tablet according to any of the preceding claims, further characterized in that the compressed portion contains a mold.

6. The detergent tablet according to claim 5, further characterized in that the non-compressed portion is retained at least partially within the mold.

7. The detergent tablet according to any of the preceding claims, further characterized in that it comprises a first and a second, and optionally subsequent, uncompressed portions.

8. The detergent tablet according to claim 7, further characterized in that at least one of the first and / or second and / or optionally the subsequent non-compressed portions, contains a perfume component.

9. The detergent tablet according to any of the preceding claims, further characterized in that the non-compressed portion is in solid, liquid or gel form.

10. The detergent tablet according to any of the preceding claims, further characterized in that the perfume component is selected from encapsulated perfume, liquid perfume that has been loaded onto a porous vehicle and has been optionally encapsulated, properfume, or mixtures thereof. same.

11. - The detergent tablet in accordance with the claim 10, further characterized in that the encapsulated perfume comprises an encapsulating material that is water soluble or water dispersible. 12.- The detergent tablet in accordance with the claim 11, further characterized in that the encapsulating material is a composition comprising a polysaccharide and / or a polyhydroxy compound. 13. The detergent tablet according to any of the preceding claims, further characterized in that the perfume component is present at a level of 0.5% to 15% by weight of the non-compressed portion. 14. A process for preparing a detergent tablet, comprising the steps of: (a) compressing at least one detergent component using a compression pressure of more than 6.3 KN / cm2 to form a compressed portion; and (b) supplying in the compressed portion a non-compressed portion containing a perfume component.