MXPA00007270A - Multi-layer detergent tablet - Google Patents

Abstract

A multi-layered detergent tablet comprising:a) a core having a first detergent active agent;b) a first encapsulating layer surrounding said core, having a second detergent active agent;c) a scond encapsulating layer surrounding said first encapsulating layer, having a third detergent active agent and a disruption system;wherein disruption of said second encapsulating layer is such that at least 25%of said third detergent active agent is released prior to release of said second detergent active agent.

Description

DETERGENT TABLET OF MULTIPLE LAYERS TECHNICAL FIELD The present invention relates to detergent tablets having multiple layers.

BACKGROUND OF THE INVENTION Detergent compositions in tablet form are known in the art. Detergent compositions in tablet form maintain several advantages over detergent compositions in the form of particles or liquids, such as ease of handling, transportation and storage. Thanks to these advantages, detergent compositions in tablet form have become increasingly popular among consumers of detergent products. Detergent tablets are very commonly prepared by premixing the components in the composition and giving the premixed components the form of a tablet by use in a tablet press and compression of the components. However, traditional tablet compression methods have significant disadvantages, including but not limited to the fact that the selected components of a detergent composition may be adversely affected by the compression pressure in the tablet press. Accordingly, these selected components were typically not included in the detergent tablets of the prior art without obtaining a loss in performance. In some cases, these selected components could even become unstable or inactive as a result of compression. In addition, when the components of the detergent composition are compressed in the tablet press, they are brought into close proximity to each other, resulting in the reaction of the selected component, instability, inactivity or depletion of the active form of the components. To avoid the aforementioned disadvantages, detergent tablets of the prior art have attempted to separate the components of the detergent composition that could potentially react with each other when the detergent composition was compressed to create a tablet. The separation of the components has been achieved, for example, by preparing multilayer tablets in which the reactive components are contained in different layers of the tablet, or by encapsulating and coating the reactive components. These multi-layer tablets of the prior art are traditionally prepared using multiple compression steps. Accordingly, layers of the tablet that are subjected to more than one compression step may be subjected to a cumulative and potentially larger total compression pressure. Furthermore, it is known that an increase in the compression pressure of the tapping press decreases the dissolution rate of the tablet with the effect that said multilayer tablets may not dissolve satisfactorily during use. Accordingly, there remains a need for an improved detergent tablet that can deliver active detergent ingredients to a domestic laundry process, thereby providing superior performance benefits.

BRIEF DESCRIPTION OF THE INVENTION This need is met by the present invention, in which a detergent tablet having a center, a first encapsulating layer and a second encapsulating layer is provided. The tablet of the present invention provides detergent components previously considered unacceptable for detergent tablets, in addition to effectively separating the potentially reactive ingredients. In addition, the detergent tablet of the present invention provides superior cleaning performance, particularly in household automatic dishwashing machines over the prior art tablets. According to a first embodiment of the present invention, a detergent tablet is provided. The tablet comprises a multi-layer detergent tablet comprising: a) a center having a first active detergent agent; b) a first encapsulating layer surrounding said center, which has a second active detergent agent, and optionally an interruption system; c) a second encapsulating layer surrounding said first encapsulating layer, which has a third active detergent agent and an interruption system; wherein the interruption of said second encapsulating layer is such that at least 25%, preferably 35%, most preferably 45%, more preferably even 50% of said third active detergent agent is released before releasing said second active detergent agent, and when the first encapsulating layer contains the optionally preferred interruption system, the interruption of said first encapsulating layer is such that at least 25%, preferably 35%, most preferably 45%, more preferably even 50% of said second active detergent agent is released before releasing said second active detergent agent According to a second embodiment of the present invention, a detergent tablet is provided. The tablet comprises a multi-layer detergent tablet comprising: a) a center having a first active detergent agent; b) a first encapsulating layer surrounding said center, which has a second active detergent agent, and optionally an interruption system; c) a second encapsulating layer surrounding said first encapsulating layer, which has a third active detergent agent and an interruption system; wherein the interruption of said second encapsulating layer is such that said third active detergent agent is released for at least 2 minutes, preferably at least 3 minutes, most preferably for at least 5 minutes, even very preferably at least 10 minutes, before releasing said second active detergent agent. According to a third embodiment of the present invention, a detergent tablet is provided. The tablet comprises a multi-layer detergent tablet comprising: a) a center having a first active detergent agent; b) a first encapsulating layer surrounding said center, which has a second active detergent agent, and optionally an interruption system; c) a second encapsulating layer surrounding said first encapsulating layer, which has a third active detergent agent and an interruption system; wherein the interruption of said second encapsulating layer occurs in an aqueous cleaning environment at a temperature of 25 ° C or less, preferably 15 ° C or less, most preferably 10 ° C or less, and wherein the release of said second agent Active detergent occurs in an aqueous cleaning environment at a temperature of 30 ° C or more, preferably 35 ° C or more, most preferably 40 ° C or more.

According to a fourth embodiment of the present invention, a kitchen utensil washing method is provided. The method comprises washing a kitchen utensil in a domestic appliance for automatic dishwashing, said method comprising treating the dirty kitchen utensil in an automatic dishwasher with a multi-layer detergent tablet according to any of the above embodiments. Accordingly, a further aspect of the present invention is to provide a multi-layer detergent tablet that can deliver detergent actives quickly and efficiently to a domestic laundry process. These and other aspects, features and advantages of the present invention will be readily apparent to one skilled in the art from the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise indicated. All temperatures are in degrees centigrade (° C) unless otherwise specified. All the cited documents are incorporated herein by way of reference in relevant part.

Definition "Encapsulant" as used herein means that the layer completely encloses or encloses the previous layer or center. That is, the layer or center that is encapsulated and the detergent active agents in these do not have direct access to the outside environment. Access to the outside environment can only occur when the encapsulating layer is removed, either partially or totally, as would occur in an aqueous wash environment. For example, the second encapsulating layer completely surrounds the first encapsulating layer and nothing of the second active detergent agent is released until the first encapsulating layer has direct access to the external environment. This occurs either after a set time or after a quantity of the third active detergent agent has been released.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The present invention comprises a multi-layer detergent tablet and in particular an automatic dishwashing detergent tablet having a center, a first encapsulating layer and a second encapsulating layer. Accordingly, by means of the present invention, the active detergent components of a detergent tablet previously adversely affected by the compression pressure used to form the tablets can now be included in a detergent tablet. Examples of these components include bleaching agents and enzymes. In addition, these active detergent components can be separated from each other by having one or more compatible components contained in either the center, the first encapsulating layer or the second encapsulating layer of the tablet. Examples of components that can interact and therefore require separation include bleaching agents, bleach or catalyst activators or enzymes; bleaching agents and bleach catalysts, or activators; bleaching agents and surfactants; alkalinity sources and enzymes. It could be advantageous to provide that the center, the first encapsulating layer and the second encapsulating layer dissolve in the wash water with different dissolution rates. By controlling the rate of dissolution of each in relation to the other, and by selecting the active detergent components in the respective portions, one can control their order of release in the wash water and improve the cleaning performance of the detergent tablet. . For example, it is commonly preferred that the enzymes are supplied to the wash prior to the bleaching agent and / or bleach activator. It may also be preferred that a source of alkalinity be released into the wash water more quickly than other components of the detergent tablet. It is also envisioned that it could be advantageous to prepare a detergent tablet according to the present invention wherein the release of certain components of the tablet relative to other components is delayed. It is also preferred that the first active detergent agent is not released until the rinse cycle, of any washed machine, i.e., an automatic laundry washing machine or dishwasher. It is preferred that the detergent tablets of the present invention be free from malodorous or noxious odors. If they are present, they can disguise or eliminate such odors. This includes the addition of disguising agents, perfumes, odor absorbers, such as cyclodextrins, etc. The detergent tablet can be transparent, opaque or of any possible intermediate tone between these two ends. The center, the first encapsulating layer and the second encapsulating layer may have the same or different degree of transparency, that is to say, vary from completely transparent to opaque. However, it is preferred that they be different. The different layers and the center can also have any color, it being preferred that each layer be of a different color. The detergent tablets described herein preferably weigh between 15 g and 100 g, more preferably between 18 g and 80 g, more preferably between 20 g and 60 g of weight. The detergent tablets described herein that are suitable for use in automatic dishwashing methods are preferably between 20 g and 40 g in weight. Detergent tablets suitable for use in laundry washing methods are preferably between 40 g and 100 g, more preferably between 40 g and 80 g, most preferably between 40 g and 65 g in weight.

Tablet form The center must contain a first active detergent agent, but may comprise a mixture of one or more active detergent components. The center may also contain an interruption system. The first encapsulating layer must contain a second active detergent agent, but may comprise a mixture of one or more active detergent components. The first encapsulating layer must also contain an interruption system. The second encapsulating layer must contain a third active detergent agent, but may comprise a mixture of one or more active detergent components. The second encapsulating layer must also contain an interruption system. The center, the first encapsulating layer and the second encapsulating layer can have any physical form that is suitable for use in tablets. That is, for example, they can be solid, either compressed or uncompressed, gels, liquids, liquids-gels. Furthermore, it is preferred that when any of the center, the first encapsulating layer and the second encapsulating layer are a solid, they are a "compressed solid". By "compressed solid" is meant that the detergent agents active in the first encapsulating layer, the second encapsulating layer or the center are matched to one another, preferably in the form of particulate material, optionally in combination with a carrier and / or a binder (for example, PEG), and are then compressed using any suitable equipment to form compressed tablets, blocks, bricks or agglomerates; as described in more detail below. The multi-layer detergent tablet may have any possible combination of physical forms, for example, the center is a liquid or a gel and the first encapsulating layer and second encapsulating layer are solids, which may optionally be a compressed solid. Alternatively, the center could be a solid, either a compressed or non-compressed solid, and the first encapsulating layer and second encapsulating layer are both non-compressed gels. The compressed solid portions of the detergent tablets described herein have a Child Bite Resistance (CBS) which is generally greater than 10 kg, preferably more than 12 kg, most preferably more than 14 kg. The CBS is measured according to the Test Specification of the Consumer Product Safety Commission of E.U.A.

Child Bite Resistance Test Method According to this method the tablet is placed horizontally between two strips / metal plates. The upper and lower plates are hinged on one side, so that the plates simulate a human jaw. An increasingly higher descending force is applied to the upper plate, mimicking the closing action of the jaw, until the tablet breaks. The CBS tablet is a measurement of the force in kilograms, required to break the tablet. Moreover, it is preferred that when any of the center, the first encapsulating layer and the second encapsulating layer are a gel or a liquid gel, they are "not compressed". By "non-compressed" it is meant that the detergent actives in the first encapsulating layer, second encapsulating layer or center are combined together, and are not compressed, as described in more detail hereinafter.

Compressed solid The first encapsulating layer, second encapsulating layer and / or center of the detergent tablet comprises at least one active detergent component but may comprise a mixture of more than one active detergent component, which may optionally be a compressed solid. Any detergent tablet component conventionally used in known detergent tablets is suitable for incorporation into a compressed solid of the detergent tablets of this invention. The active detergent components are described hereinafter. Examples of such active detergent components include, but are not limited to, builder, dispersant polymer, dye, surface active agent, bleaching agent, bleach activator, chelators, bleach scrubbers, foam suppression systems, bleach catalyst, enzyme, pH regulator, alkalinity source and mixtures thereof.

Non-compressed Active detergent components suitable for incorporation into the first encapsulating layer, second encapsulating layer and / or center when they are non-compressed, include components that interact with one or more active detergent components present in the other layers or core. In particular, the components that are preferred when the first encapsulating layer, second encapsulating layer and / or center are not compressed are those active detergent agents that are adversely affected by the compression pressure of for example a tablet compression press. Examples of said active detergent components include, but are not limited to, surfactant, bleaching agent, bleach activator, bleach catalyst, enzyme, corrosion inhibitor, perfume and a source of alkalinity. These components are described in more detail below. In addition, enzymes in the form of pellets can now be included in the detergent tablets without the pellet being destroyed or damaged during the production of the detergent tablet. The active detergent component can be in any form, for example in the form of gel or liquid. In addition to comprising an active detergent component, when the first encapsulating layer, the second encapsulating layer and / or the center are non-compressed they may optionally also comprise a vehicle component. The active detergent component can be present in the form of a solid, gel or liquid, before its combination with a vehicle component. When the first encapsulating layer, second encapsulating layer and / or center are not compressed, these portions of the detergent tablet may be solid, gel, liquid or liquid-gel. When the first encapsulating layer, second encapsulating layer and / or center are not compressed, they may comprise particulate materials, such as powders or granules. The particulate materials can be prepared by any known method, for example conventional spray drying, granulation, encapsulation or agglomeration. The particulate materials can be attached to any compressed solid layer or center by incorporating a binding agent or forming a coating layer on the first encapsulating layer, the second encapsulating layer and / or the center. When more than one of the center, the first encapsulating layer and the second encapsulating layer is a non-compressed gel, these different and / or non-compressed non-compressed layers may comprise particulate materials having a substantially different average particle size. By substantially different average particle size it is tried to say that the difference between the average particle size of the first and second and / or subsequent compositions is more than 5%, preferably more than 10%, most preferably more than 15% or even 20% of the smallest average particle size. The average particle size of the active detergent components in particles used herein is calculated using a series of Tyler sieves. The series consist of a number of sieves each having different opening sizes. The samples of a composition of active detergent components are screened through the series of sieves (typically 5 sieves). The weight of a sample of composition retained on the screen is plotted against the size of the screen opening. The average particle size of the composition is defined as the aperture size through which 50% by weight of the sample of the composition would pass. Alternatively, the layers and / or the center containing more than one active detergent component may have substantially different density. For example, the difference between the density of two active detergent agents in one layer and / or center may be more than about 5%, preferably more than about 10%, even most preferably more than about 15%, or even about of 20% of the smallest density. The density of the particulate composition of active detergent components can be measured by any known method suitable for measuring density of particulate material. Preferably the density of the composition of active detergent components is measured using a simple funnel and cup device consisting of a conical funnel rigidly molded on a base and provided with a fin valve at its lower end to allow the contents The funnel is emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower ends. It is mounted so that the lower end is 140 mm above the upper surface of the base. The cup has a total height of 90mm, an internal height of 87mm and an internal diameter of 84mm. Its nominal volume is 500 ml.

A measure of density is taken by pouring the composition into the funnel by hand. Once the funnel is full, the flap valve is open and the powder is allowed to run through the funnel. Overfilled the cup. The full cup is removed after the structure and the excess powder is removed from the cup by passing a straight edge implement, for example a knife through its upper edge. The filled cup is then weighed and the value obtained for the powder weight is doubled to provide a volumetric density in grams / liter. Repeated measurements are made as required. Tablets in which one or more of the center, the first encapsulating layer and the second encapsulating layer are not compressed and comprise particulate materials, the average particle size and / or density will preferably be different in each of the center, the first layer encapsulant and the second encapsulating layer. When the center, the first encapsulating layer and / or the second encapsulating layer are uncompressed and comprise a solidified molten material, the molten material is prepared by heating a composition comprising an active detergent component and optional carrier component (s) above its melting point to form a flowable molten material. The meltable melt is then poured into a mold and allowed to cool. As the molten material cools it becomes solid, taking the form of the mold at room temperature. If the center of the tablet is to be a compressed solid, and the first encapsulating layer is to be uncompressed, then the center is placed in the mold such that the first encapsulating layer completely surrounds the center. In addition, the optional vehicles and the temperature at which the liquid is heated are selected in such a way that they do not significantly alter the active composition, although in some cases, a little solvent will be transferred to the center. In the same way when the second encapsulating layer is uncompressed. If the layer or core to be encapsulated by an uncompressed layer is also made uncompressed by means of a flowable melt, then the optional vehicles and the temperature at which the composition is heated are selected so that they do not react, cause that the center of the encapsulated layer remelts, damages or alters the composition or performance of the center or of the first active agent contained therein. 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. Suitable vehicle components for preparing a solidified melt are typically non-active components that can be heated above their melting point to form a liquid and cooled to form an intermolecular matrix that can effectively trap active detergent components. A preferred non-active carrier component is an organic polymer that is solid at room temperature. Preferably, the active detergent component is polyethylene glycol (PEG). The compressed portion of the detergent tablet preferably provides a mold to accommodate the molten material. The center, the first encapsulating layer and / or second encapsulating fluidizable and non-compressed layer may be in a form comprising a dissolved or suspended active detergent component. The center, first encapsulating layer and / or second encapsulant flowable and uncompressed can harden over time to form a solid, semi-solid or highly viscous encapsulating center and / or second encapsulating layer non-compressed by any of the described methods previously. In particular, the center, the first encapsulating layer and / or the second encapsulating layer can be cured by evaporation of a solvent, or the transfer of solvent into the center. Suitable solvents for use herein may include any known solvent in which a binder is soluble. Preferred solvents may be polar or non-polar and may include water, alcohol, (for example ethanol, acetone) and alcohol derivatives, preferring more non-polar. In an alternate mode, more than one solvent may be used. The center, first encapsulating layer and / or second flowable and non-compressed encapsulating layer may consist of one or more binding agents. Any binder that has the effect of causing the composition to become solid, semi-solid or highly viscous over time is contemplated for use herein. While not wishing to be bound by theory, it is believed that the mechanism by which the binder causes a non-solid composition to become solid, semi-solid or highly viscous include: chemical reaction (as with chemical entanglement), or interaction of effect between two or more components of the flowable composition either. The binding agents include a combination of sugar / gelatin, starch, glycerol and organic polymers. The sugar can be any monosaccharide (for example glucose), disaccharide (for example sucrose or maltose) or polysaccharide. The most preferred sugar is commonly available sucrose. For the purposes of the present invention, type A or B gelatin, available for example from Sigma, may be used. Type A gelatin is preferred because it has greater stability under alkaline conditions compared to type B. The preferred gelatin also has an efflorescence resistance of between 65 and 300, more preferably between 75 and 100. Preferred organic polymers include polyethylene glycol (PEG) of molecular weight from 500 to 10,000, preferably from 750 to 8000, more preferably from 1000 to 6000 available from Hoechst. Alternatively, mixtures of high molecular weight PEG, preferably with a molecular weight of 10,000 to 20.00, and low molecular weight PEG, preferably with a molecular weight of 2,000 to 8,000, can be used to maximize processing capacity and hardness. When the center, first encapsulating layer and / or second non-compressed encapsulating layer is an extruded material, the extruded material is prepared by premixing the active detergent components with optional carrier components to form a viscous paste. The viscous paste is then extruded using any commonly available suitable extrusion equipment such as for example a single or twin screw extruder available for example from APV Baker, Peterborough, U.K. The extruded material is then configured into the center, first encapsulating layer and / or second encapsulating layer by conventional methods. The center, first encapsulating layer and / or second non-compressed encapsulating layer may additionally contain a drying agent. Any conventional drying agent can be used. See Vogels Textbook of Practical Organic Chemistry, 5th edition (1989) Longman Scientific &; Technical, pp. 165-168, incorporated herein by reference. For example, suitable drying agents are anhydrous CaSO 4, anhydrous Na 2 SO 4, sodium sulfite, calcium chloride and MGSO 4. The selection of suitable drying agents may depend on the final use of the tablet. A drying agent for a detergent tablet for an automatic dishwashing composition for low temperatures is preferably sodium sulfite or calcium chloride, but CaSO 4 can be used for higher usage temperatures. When present, the drying agents will vary from about 0.1% to about 15%, preferably about 0.1% to about 10%, more preferably about 0.5% to about 7%, by weight. It is preferred that the drying agent be selected such that its dehydration temperature exceeds the process temperature. When the center, first encapsulating layer and / or second non-compressed encapsulating layer is a gel or a liquid-gel, it may include solid ingredients that are dispersed or suspended in the gel. The solid ingredients help control the viscosity of the gel formulation in conjunction with the thickening system. When included, the center, first encapsulating layer and / or second non-compressed encapsulating layer typically comprise at least about 15% solid ingredients, most preferably at least about 30% solid ingredients and more preferably at least about 30% solid ingredients. 40% solid ingredients. However, due to the pumping capacity and other processing concerns, the non-compressed gelatinous body or any of the plurality of non-compressed gelatinous portions of the present invention typically does not include more than about 90% solid ingredients.

Thickening System As mentioned above, the detergent tablet of the present invention comprises a thickening system in the center, first encapsulating layer and / or second encapsulating layer not compressed when it is a gel, to provide the viscosity or thickness suitable for the portion of gel. The thickening system typically comprises a non-aqueous liquid diluent and an organic or polymeric gelling additive. a) Liquid diluent The term "diluent" is used herein to denote the liquid portion of the thickening system. Although some of the essential and / or optional components of the compositions herein can actually be dissolved in the "diluent" containing phase, other components will be present as dispersed particulate material in the "diluent" containing phase. Thus, the term "diluent" does not intend to require that the solvent material be capable of actually dissolving all of the components of the detergent composition added thereto. Suitable types of diluent useful in the nonaqueous thickening systems herein include lower monoalkyl ethers of alkylene glycol, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, low molecular weight polyethylene glycols, low weight methyl esters molecular and amides, and the like, with more glycerol triacetate being preferred. One type of non-aqueous diluent which is preferred to be used herein comprises the C2-C3 mono-, di-, tri- or tetraalkylene glycol monoalkyl ethers of C2-C3. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of the type have been marketed under the trademarks Dowanol, Carbitol and Cellosolve. Another type of non-aqueous diluent which is preferred and useful herein comprises low molecular weight polyethylene glycols (PEGs).

Such materials are those having molecular weights of at least about 150. PEGs with a molecular weight ranging from about 200 to 600 are more preferred. Yet another type of non-aqueous diluent that is preferred 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 methyl. The non-aqueous organic diluents employed should, of course, be compatible and non-reactive with other components of the composition, eg, enzymes, used in the detergent tablets herein. Said diluent component will generally be used in an amount of about 10% to 60% by weight of the composition. Most preferably, the non-aqueous, low polarity organic diluent will comprise about 20% to 50% by weight, most preferably about 30% to 50% by weight of the composition. b) Qelification additive As mentioned above, a gelling agent or additive is added to the non-aqueous diluent of the present invention to complete the thickening system. To form the gel required for adequate phase stability and acceptable rheology of the gel portion, the organic gelling agent is generally present to the extent of a ratio of solvent to gelling agent in the thickening system which typically ranges from about 99. : 1 to about 1: 1. Most preferably, the ratios vary from about 19: 1 to about 4: 1. Preferred gelling agents of the present invention are selected from castor oil, polyethylene glycol, sorbitol and related organic tixatropo derivatives, organic clays, cellulose and cellulose derivatives, pluronic, stearates and stearate derivatives, sugar / gelatin combinations, starches, glycerol and derivatives thereof, organic acid amides such as N-lauryl-di-n-butylamide L-glutamic, polyvinylpyrrolidone and mixtures thereof. Preferred gelling agents include castor oil derivatives. Castor oil is a naturally occurring triglyceride obtained from the seeds of Ricinus Communis, a plant that grows in most tropical or subtropical areas. The primary fatty acid portion in the triglyceride of castor oil is ricinoleic acid (12-hydroxy oleic acid). This corresponds to approximately 90% of the fatty acid portions. The rest consists of dihydroxystearic, palmitic, etheric, oleic, linoleic, linolenic and eicosanoic portions. The hydrogenation of the oil (for example, by means of hydrogen under pressure) converts the double bonds in the fatty acid portions into individual bonds, thus "hardening" the oil. The hydroxyl groups are not affected by this reaction. Therefore, the resulting hydrogenated castor oil has an average of about three hydroxyl groups per molecule. It is believed that the presence of these hydroxyl groups is responsible in large part for the softening structuring properties imparted to the gel portion, compared to similar liquid detergent compositions that do not contain castor oil with hydroxyl groups in their chains. fatty acid. For use in the compositions of the present invention, the castor oil must be hydrogenated at an iodine value of less than about 20, and preferably less than about 10. The iodine value is a measure of the degree of oil establishment and it is measured by the "Wijis Method", which is well known in the art. Unhydrogenated castor oil has an iodine value of about 80 to 90. Hydrogenated castor oil is a commercially available product that is sold, for example, in various grades under the trademark CASTO RWAX. RTM. by NL Industries, Inc., Highstown, New Jersey. Other suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, made by Rheox, Laporte. Thixatol ST is especially preferred. When polyethylene glycols are used as gelling agents instead of solvents, they have a molecular weight scale of about 1,000 to about 20,000, preferably about 2,000 to about 12,000, most preferably about 4,000 to about 10,000. When employed in the present invention, cellulose and cellulose derivatives preferably include: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropylmethylcellulose (HPMC); iii) carboxymethylcellulose (CMC) and mixtures thereof. The hydroxypropylmethylcellulose polymer that is preferred has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2% by weight aqueous solution at 25 ° C (ADTMD2363) of about 50,000 to about 100,000 cps. A hydroxypropylcellulose polymer that is especially preferred is Methocel® J75MS-N wherein a 20% by weight aqueous solution at 25 ° C has a viscosity of about 75,000 cps. The sugar can be any monosaccharide (e.g., glucose), disaccharide (e.g., sucrose or maltose) or polysaccharide. The sugar that is most preferred is commercially available sucrose. For the purposes of the present invention, type A or B gelatin, available for example from Sigma, can be used. Type A gelatin is preferred because it has a higher stability in alkaline conditions compared to type B. The gelatin which is preferred also has a blooming resistance of between 65 and 300, most preferably between 75 and 100. However, the polyethylene glycols are the gelling agents that are preferred. The center, first encapsulating layer and / or second non-compressed encapsulating layer of the present invention may include a variety of other ingredients in addition to the thickening agent as described above, and the active detergent described in greater detail below. Ingredients such as perfumes and colorants, as well as swelling / adsorption agents such as carboxymethylcelluloses and starches may be included to aid in the adsorption of the excess diluent or assist in the dissolution or degradation of the center, first encapsulating layer and / or second encapsulating layer. tablets in the wash. In addition, hardness modifying agents may be incorporated into the thickening system to adjust the hardness of the gel if desired. These hardness control agents are typically selected from various polymers and polyethylene glycols, and when included they are typically employed at levels of less than about 20% and most preferably less than about 10% by weight of the solvent in the thickening system. For example, hardening agents such as high molecular weight PEG, preferably with a molecular weight of 10,000 to 20,000 or possibly an even higher molecular weight, can be added to decrease the hardening time of the center, first encapsulating layer and / or second non-compressed encapsulating layer When it is a gel or a liquid-gel, the center, first encapsulating layer and / or second non-compressed encapsulating layer of the present invention is formulated such that the gel is a pumpable and flowable gel at slightly elevated temperatures. high about 30 ° C or more, to allow for increased flexibility in the production of the detergent tablet, but it becomes highly viscous at ambient temperatures such that the shape of the detergent tablet is maintained during shipping and handling. detergent tablet. Said hardening of the center, first encapsulating layer and / or second non-compressed encapsulating layer can be achieved, for example, by (i) cooling to less than the flowable temperature of the gel; (I) by evaporating the diluent or (iii) by polymerization of the gelling agent. Preferably, the gel is formulated such that it hardens sufficiently so that the maximum force needed to push a probe into the detergent tablet preferably ranges from about 0.5 N to about 40 N. This force can be characterized by measuring the maximum force required to push a probe, equipped with a tension gauge, a set distance within the gel. The established 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 probe with a diameter of 5 mm. The typical forces measured are on the scale of 1 N to 25N.

Coating In a preferred embodiment, the center, first encapsulating layer and / or second non-compressed encapsulating layer are coated with a coating layer. The coating layer can be used to fix a first encapsulating layer and / or second non-compressed encapsulating layer to the compressed solid or uncompressed center and / or first encapsulating layer. This could be particularly advantageous when the first encapsulating layer and / or second non-compressed encapsulating layer comprises flowable particles, gels or liquids. When present, the coating layer generally does so at a level preferably of at least about 0.05%, most preferably at least about 0.1%, more preferably at least about 1%, even more preferably at least about of 2% or even at least about 5% of the center, first encapsulating layer and / or second encapsulating layer. However, when the detergent tablet is an automatic dishwashing composition, it is preferred that the coating is not a fatty acid. In an alternative embodiment, the coating layer can encapsulate the multi-layer detergent tablet. In this embodiment, the coating layer is present at a level of at least about 4%, most preferably at least about 5% and more preferably at least about 10% of the detergent tablet.

The first encapsulating layer, second encapsulating layer and / or center may also be provided with a coating of a water-soluble material to protect it. The coating layer preferably comprises a material that becomes solid upon contacting preferably within less than 15 minutes, most preferably less than 10 minutes, still more preferably less than 5 minutes, much more preferably 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, polyethylene glycol (PEG) and mixtures thereof. Preferred carboxylic or dicarboxylic acids preferably comprise an even number of carbon atoms. Preferred carboxylic or dicarboxylic acids preferably comprise at least 4, most preferably at least 6, even very preferably at least 8 carbon atoms, more preferably between 8 and 13 carbon atoms. Preferred dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, and mixtures thereof. Preferred fatty acids are those having a carbon chain length of C12 to C22, more preferably C18 to C22. The coating layer may also preferably comprise a disintegrating agent. When present, the coating layer will generally be present at a level of at least about 0.05%, most preferably at least about 0.1%, more preferably at least about 1%, still more preferably at least about 2% or even at least about 5% of the detergent tablet. However, when the detergent tablet is an automatic dishwashing composition, the coating can not be a fatty acid.

Disintegration system The first encapsulating layer and the second encapsulating layer must contain a disintegrating agent. The center may optionally contain a disintegration system. The disintegrating agent can be a disintegrating or effervescent agent. Suitable disintegrating agents include agents that swell upon contact with water or the flow and / or emission of facilitated water to form channels in non-encapsulating portions., compressed and / or uncompressed. Any known disintegrant or effervescent agent suitable for use in laundry or dishwashing applications is intended for use herein. The disintegrating agent includes starch, starch derivatives, alginates, carboxymethyl cellulose (CMC), cellulosic based polymers, sodium acetate, aluminum oxide. Suitable effervescent agents are those that produce a gas in contact with water. Suitable effervescent agents can be species comprising 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. An advantage of including a disintegration system in the detergent tablet of the present invention are the benefits of transportation, storage and handling can be achieved by increasing the hardness of the detergent tablet without adversely affecting the cleaning performance.

Active detergent agents The center must contain a first active detergent agent. The first encapsulating layer must contain a second active detergent agent. The second encapsulating layer must contain a third active detergent agent. These three active detergent agents can be any conventional ingredient used in cleaning compositions, such as laundry or automatic dishwashing compositions. When the active detergent agent is in a layer or center which is a compressed solid the active detergent agent can be a variety of ingredients including builders, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfume, dispersants lime soap, organic polymeric compounds for example dye transfer inhibiting polymeric agents, crystal growth inhibitors, heavy metal ion sequestrants, chelating agents, bleach scavengers, metal ion salts, enzyme stabilizers, inhibitors of corrosion, foam suppressors, solvents, fabric softening agents, optical brighteners and hydrotropes. When the active detergent agent is in a layer or center which is uncompressed, the active detergent agent may be a variety of ingredients including surfactants, enzymes, enzyme pellets, bleaching agents, polymeric dispersants, colorants, perfume, chelators, bleach scrubbers, silver care agents, enzyme stabilizers, corrosion inhibitors, suds suppressors and builders. Detergent agents active in a compressed solid are typically detergency builders, surfactants, silicates, pH control agents or regulators, chelators, chlorine scavengers, polymeric dispersants, enzymes and bleaching agents. The following is a description of the detergent actives useful in the present invention.

Surfactants Suitable surfactants are selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof. Automatic dishwashing products should have a low foaming character and thus the foaming of the surfactant system for use in dishwashing methods should be suppressed or most preferably should be low-voiding. foam, typically non-ionic in character. The foaming caused by the surfactant systems used in fabric cleaning methods does not have to be suppressed to the same extent as is necessary for dishwashing. A typical listing of anionic, non-ionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the US patent. No. 3,929,678, issued to Laughiin and Heuring on December 30, 1975. A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. A list of surfactants typically included in detergent compositions for automatic dishwashing machine is given, for example, in EP-A-0414 549 and PCT applications Nos. WO. 93/08876 and WO 93/08874. The detersive surfactants included in the fully formulated detergent compositions produced by the present invention comprise about 0.01%, preferably about 0.5% to about 50% by weight of the detergent composition, depending on the particular surfactants used and the desired effects . In a mode that is too preferred, the detersive surfactant comprises about 0.5% to about 20% by weight of the composition.

The detersive surfactant may be nonionic, anionic, ampholytic, zwitterionic or cationic. Mixtures of these surfactants can also be used. Preferred detergent compositions comprise anionic detersive surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants.

Nonionic Surfactants The surfactants which are particularly preferred in the preferred automatic dishwashing detergent compositions (ADD) of the present invention are the low foaming nonionic surfactants (LFNI). The LFNI may be present in amounts of 0.01% to about 10% by weight, preferably about 0.1% to about 10%, most preferably about 0.25% to about 4%. LFNIs are very typically used in ADDs due to the improved water-rolling action (especially of glass) that they give to the ADD product. They also include non-silicone and non-phosphate polymeric materials illustrated hereinafter which are known to defoam food soils found in automatic dishwashing. Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and mixtures thereof with more sophisticated surfactants, such as polyoxypropylene / polyoxyethylene / polyoxypropylene reverse block copolymers (PO / EO / PO). ). The PO / EO / PO polymer surfactants are well known because they have suppressive or defoaming action, especially in relation to the ingredients of common food soils such as egg. The invention encompasses preferred embodiments in which LFNI is present, and wherein this component is solid at about 35 ° C, most preferably solid at about 25 ° C. For ease of manufacture, a preferred LFNI has a melting point of between about 25 ° C and about 60 ° C, most preferably between about 26.6 ° C and 43.3 ° C. In a preferred embodiment, the LFNI is an ethoxylated surfactant derived from the reaction of an alcohol or alkyl monohydric alkylphenol containing about 8 to about 20 carbon atoms, with about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis. A particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 6 -C 20 alcohol), preferably a C 8 alcohol, condensed with an average from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant derived in this manner has a limited ethoxylated distribution relative to the average. The LFNI may optionally contain propylene oxide in an amount of up to about 15% by weight. Other preferred LFNI surfactants can be prepared by the methods described in the U.S.A. 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. The ADDs that are highly preferred herein in which the LFNI is present, make use of ethoxylated monohydric alcohol or alkylphenol and further comprise a polymeric polyoxyethylene and polyoxypropylene block compound; the ethoxylated alkyl alcohol or alkylphenol fraction of the LFNI comprising from about 20% to about 100%, preferably from about 30% to about 70%, of the total LFNI. The polyoxyethylene-polyoxypropylene block polymer compounds which can satisfy the needs described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as reactive initiator hydrogen compound. Polymeric compounds made from sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as the C 2? 8 aliphatic alcohols, generally do not provide satisfactory foam control in the present ADDs. Certain block polymer surfactant compounds designated PLURONIC® and TETRONIC® by the BASF Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. A particularly preferred LFN1 contains about 40% to about 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer comprising about 75% by weight of the blend, of a polyoxyethylene and polyoxypropylene reverse block copolymer containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25% by weight of the blend, of a polyoxyethylene-polyoxypropylene block copolymer initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane. Suitable for use as LFNI in ADD compositions are those LFNIs that have relatively low turbidity points and a high hydrophilic-lipofilic (HLB) balance. Turbidity points of 1% solutions in water are typically less than about 32 ° C and preferably less than 0 ° C, for optimum control of foaming along a full scale of water temperatures. LFNIs that may also be used include those POLY-TERGENT® SLF-18 nonionic surfactants from Olin Corp, and any biodegradable LFNI having the melting point properties described hereinbefore. These and other nonionic surfactants are known in the art, described in greater detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd ed., Vol. 22, pp 360-379, "Surfactants and Detersive Systems ", incorporated herein by reference, ADD compositions comprising mixed surfactants are preferred in which foaming (absent any silicone foam control agent) is less than 5.08 centimeters, preferably less of 2.54 centimeters, determined by the following description.The useful equipment for these measurements is: a dishwasher Whirlpool (model 900) equipped with a transparent plexiglass door, an IBM computer data collection with Labview program and Excel, proximity sensor (Newark Corp. - model 95F5203) using an SCXI interface and a plastic ruler. The data is gathered as follows. The proximity sensor is fixed to the bottom of the dishwasher tray on a metal bracket. The sensor points downwards in the direction of the rotating arm of the dishwasher on the bottom of the machine (distance of approximately 2 cm from the rotating arm). Each pass of the rotating arm is measured by the proximity sensor and recorded. The pulses recorded by the computer are converted to turns per minute (RPM) of the lower arm by counting the pulses during a 30-second interval. The speed of rotation of the arm is directly proportional to the amount of foam in the machine and the pump of the dishwasher (for example, the more foam is produced, the slower the arm rotation).

The plastic ruler is attached to the bottom tray of the dishwasher and extends to the floor of the machine. At the end of the wash cycle, the height of the foam is measured using the plastic ruler (seen through the transparent door) and recorded as the foam height. The following procedure is followed to evaluate ADD compositions for foam production as well as to evaluate the utility of nonionic surfactants. (For a separate evaluation of the nonionic surfactant, an ADD base formula, such as Cascade Powder, is used together with the nonionic surfactants that are added separately in glass jars to the dishwashing machine). First, the machine is filled with water (the water is adjusted for suitable temperature and hardness) and a rinsing cycle is carried out. The RPM is monitored during the cycle (approximately 2 min.) Without any ADD product (or surfactants) being added (a quality control check to ensure the machine works properly). When the machine begins to fill for the wash cycle, the water is adjusted again for temperature and hardness, and then the ADD product is added to the bottom of the machine (in the case of surfactants evaluated separately, the base formula of ADD is first added to the bottom of the machine and then the surfactants are added by placing the glass jars containing inverted surfactant on the upper tray of the machine). The RPM is monitored later throughout the wash cycle. At the end of the wash cycle, the height of the foam is recorded using the plastic ruler. The machine is again filled with water (the water is adjusted for suitable temperature and hardness) and runs through another rinse cycle. The RPM is monitored throughout this cycle. An average RPM is calculated for the first rinse, main wash and final rinse. The percentage efficiency of RPM is then calculated by dividing the average RPM for the test surfactants by the average RPM for the control system (base formulation of ADD without the nonionic surfactant). RPM efficiency and foam height measurements are used to size the general foam profile of the surfactant.

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

Surface-active alkoxylated end-alkoxylate surfactant A suitable blocked end alkyl alkoxylate surfactant is the poly (oxyalkylated) alcohols represented by the formula: R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] and [CH 2 CH (OH) R 2] (I) wherein Ri is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of 0.5 to 1.5, more preferably 1; and "y" is an integer having a value of at least 15, more preferably at least 20. Preferably, the surfactant of formula I, at least 10 carbon atoms in the terminal epoxy unit [CH2CH (OH) R2]. Suitable surfactants of formula I, according to the present invention, are the nonionic surfactants POLY-TERGENT® SLF-18B from Olin Corporation, as described in, for example, WO 94/22800, published on October 13 of 1994, by Olin Corporation.

Poly (Oxyalkylated) Alcohols Blocked at the Ends with Ether Preferred surfactants for use herein include blocked ether poly (oxyalkylated) alcohols having the formula: R 1 O [CH 2 CH (R 3) O] x [CH 2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are an aliphatic or aromatic hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30, in which when x is 2 or larger R3 may be the same or different ykyj are integers having an average value of about 1 to about 12, and more preferably about from 1 to about 5. R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals, having from 6 to 22 carbon atoms, with from 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms is more preferred for R3. Preferably x is an integer having an average value of 1 to 20, more preferably 6 to 15. As described above, when, in the preferred embodiments, and x is greater than 2, R3 may be the same or different. That is, R3 can vary between any of the alkyleneoxy units as described above. For example, if x is 3, R3 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and can vary in order of (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the integer three is selected for example only and the variation can be much longer with a value of integer more aito for x and includes, for example, multiple units (EO) and a much smaller number of units (PO). Particularly preferred surfactants as described above include those that have a low cloud point of less than 20 ° C. These low cloud point surfactants can be used in conjunction with a high point of turbidity surfactant as described in detail below for superior fat cleaning benefits. The most preferred blocked ether poly (oxyalkylated alcohol) surfactants are those in which k is 1 and j is 1 such that the surfactants have the formula: R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2 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 even more preferably 6 to 18. More preferred are the surfactants in which R1 and R2 are in the scale of 9 to 14, R3 is H forming ethyleneoxy and x is in the range of 6 to 15. The ether-blocked poly (oxyalkylated) alcohol surfactants comprise three general components, ie a linear or branched alcohol, an oxide of alkylene and a blocked end of alkyl ether. The alkyl ether and alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the water-soluble, hydrophilic portion of the molecule.

These surfactants exhibit significant improvements in film formation characteristics and stain removal and removal of greasy stains, when used in conjunction with high-cloud point surfactants, in relation to conventional surfactants. Generally speaking, the blocked ether poly (oxyalkylene) surfactants of the present invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Examples of methods for preparing the blocked ether poly (oxyalkylated alcohol) surfactants are described below: Preparation of C ?? /? Alkylglycidyl ether A fatty alcohol of Ci ^ u (100.00 g, 0.515 mol), and tin chloride (IV) (0.58 g, 2.23 mmol, available from Aldrich) are combined in a 500 ml round bottom, three-necked flask, equipped with a condenser, argon outlet, additional 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 to maintain the temperature between 60-65 ° C. After stirring an additional hour at 60 ° C, the mixture is cooled to room temperature. The mixture is treated with a 50% sodium hydroxide solution (61.80 g, 0.773 mol, 50%) while being mechanically stirred. After the addition is complete, the mixture is heated at 90 ° C for 1.5 hours, cooled, and filtered with the aid of ethanol. The filtrate is separated and the organic phase is washed with water (100 ml), dried over MgSO 4, filtered and concentrated. Distillation of the oil at 100-120 ° C (0.1 mm Hg) provides the glycidyl ether as an oil.

Preparation of C alcohol surfactant ?? ? 4 of C9 / 11 algane, which is end-capped with Neodol® 91-8 ether (20.60 g, 0.0393 moles ethoxylated alcohol available from Shell Chemical Co. and tin (IV) chloride (0.58 g, 2.23 mmoles) are combined in a 250 ml round bottom, three-necked flask, equipped with a condenser, argon tap, addition funnel, magnetic stirrer and internal temperature probe.The mixture is heated to 60 ° C at which point C12 alkyl ether / 14 glycidyl (1.0 g, 0.0393 mol) is added dropwise for 15 minutes.After stirring for 18 h at 60 ° C the mixture is cooled to room temperature and dissolved in an equal portion of dichloromethane. through a 2.54 cm pad of silica gel while eluting with dichloromethane The filtrate is concentrated by rotary evaporation and then released in a kugeirohr oven (100 ° C, 0.5 mm Hg) to yield the surfactant as an oil .

For more details of these and other suitable nonionic surfactants see U.S. Pat. with Nos. of series 60 / 054,702 (Case No. 6781 P), 60 / 054,688 (Case No. 6779P) and 60 / 057,025 (Case No. 6780P), which are incorporated herein by reference.

Non-ionic ethoxylated / propoxylated fatty alcohol surfactant The ethoxylated Cβ-C-is fatty alcohols and the mixed ethoxylated / propoxylated C 6 -C 8 fatty alcohols are suitable surfactants for use herein, particularly where water-soluble. preferably the ethoxylated fatty alcohols are the ethoxylated fatty alcohols of C-IO-C-IS with an ethoxylation degree of 3 to 50, more preferably those are the ethoxylated fatty alcohols of C? 2-C? b with a degree of ethoxylation of 3 to 40. Preferably the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

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

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

Mixed Non-ionic Surfactants System In a preferred embodiment of the present invention, the detergent tablet comprises a system of mixed non-ionic surfactants comprising at least one low-cloud point nonionic surfactant and a high non-ionic surfactant. turbidity point. "Turbidity point", as used herein, is a well-known property of nonionic surfactants which is the result of the surfactant becoming less soluble with an increase in temperature, the temperature at which the appearance of a second phase referred to as "turbidity point" (See Kirk Othmer Encyclopedia of Chemical Technology, 3rd Ed. Voi. 22, pp. 360-379). As used herein, a "low cloud point" nonionic surfactant is defined as an ingredient of a surfactant system having a cloud point of less than 30 ° C, preferably less than 20 ° C. , and more preferably less than 10 ° C. Typical low cloud point nonionic surfactants include alkoxylated, especially ethoxylated nonionic surfactants derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. In addition, such non-ionic low-cloud point surfactants include, for example, ethoxylated / propoxylated alcohol (for example Poly-Tergent® SLF 18 from Olin Corporation), poly (oxyalkylated blocked epoxy alcohols (for example the Poly non-ion series). -Tergent® SLF 18B from Olin Corporation, as described for example in WO 94/22800, dated October 13, 1994 by Olin Corporation), and poly (oxyalkylated) alcohol surfactants blocked with ether. can 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 U.S. Patent No. 4,223,163, dated September 16, 1980, Builloty, incorporated herein by reference. presently by reference, the low-cloud point nonionic surfactants additionally comprise a polyoxyethylene block polymeric compound, pol ioxypropylene. The polyoxyethylene-polyoxypropylene block polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylpropane and ethylenediamine as a reactive hydrogen reactant compound. Some of the surfactant block polymer compounds designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in the ADD compositions of the invention. Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Such surfactants are typically useful herein as low-cloud point nonionic surfactants. As used herein, a "high cloud point" nonionic surfactant is defined as an ingredient of a nonionic surfactant system having a cloud point greater than 40 ° C, preferably more than 50 ° C. ° C, and more preferably more than 60 ° C. Preferably the system of nonionic surfactants comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis. Such high-cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell). It is also preferred for purposes of the present invention that the high-cloud point nonionic surfactant further has a hydrophilic-lipophilic balance value ("HLB").; see Kirk Othmer here above) within the range of 9 to 15, pref of 1 to 15. Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell). Another preferred high-cloud point nonionic surfactant is derived from a straight-chain or preferably branched secondary fatty alcohol containing from 6 to 20 carbon atoms (C6-C2o alcohol), including secondary alcohols and branched-chain primary alcohols. . Preferably the non-ionic high-cloud point surfactants are ethoxylated or branched secondary alcohols, more preferably branched alcohol ethoxylates of C9 / 11 or C11 / 15 mixed, condensed with an average of 6 to 15 moles, preferably 6 to 12 moles , and more preferably from 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant derived in this way has a narrow ethoxylate distribution in relation to the average.

In a preferred embodiment, the detergent tablet comprising said 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 larger than 4 milli Siemens / cm, more preferably larger than 4.5 milli Siemens / cm, as described in GB co-pending patent application (attorney's file number CM 1573F). In another preferred embodiment, the blended surfactant system is dissolved in water having a hardness of 1,246 mmole / L in any suitable cold-filled automatic dishwashing machine to provide a solution with a surface tension of less than 4 Dynes / cm2 at less than 45 ° C, preferably less than 40 ° C, more preferably less than 35 ° C as described in the co-pending US patent application (case number 6252). In another preferred embodiment, the high cloud point and low cloud point surfactants of the mixed surfactant system are separated so that one of any of the high cloud point or low cloud point surfactants is present in a first matrix and the other is present in a second matrix as described in the co-pending US patent application (lawyer's file number 6252). For purposes of the present invention, the first matrix can be a first particle and the second matrix can be a second particle. A surfactant can be applied to a particle by any known suitable method, preferably the surfactant is sprayed on the particle. In a preferred aspect the first matrix is the center of the first encapsulating layer and the second matrix is the first encapsulating layer or the second encapsulating layer of the detergent tablet of the present invention. Preferably the low cloud point surfactant is present in the center or in the first encapsulating layer, and the high cloud point surfactant is present in the first encapsulating layer or the second encapsulating layer of the detergent tablet of the present invention. . Also suitable are the branched nonionic surfactants described in the U.S. patent application. serial number 60/031, 917 (Case No. 6404) all of which is incorporated herein by reference. These branched nonionic surfactants show in some applications improved stain and film reduction benefits over conventional linear surfactants.

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

Non-limiting examples of surfactants useful herein include the C 8 -C 8 alkylbenzenesulfonates and conventional primary, secondary and random alkyl sulfates, the C 1 or C 18 alkylakoxy sulfates, the C 0 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides. aliphatic acid fatty esters of C-? 2-C? 8, C? 2-C? 8 alkoxylated alkyl and alkylphenol (especially ethoxylated and mixed ethoxy / propoxy), C? 2-C? 8 betaines and sulfobetaines ( "sultaines"), amine oxides of C-io-C-is and the like. Other conventional useful surfactants are listed in standard texts. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-C18 monoesters), sulfosuccinate diesters (especially saturated and unsaturated C6-C-14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and hydrogenated resin acids and resin acids present in or derived from tallow oil. Especially suitable surfactants are the branched surfactants in the middle region of the chain. These include branched alkyl salts in the middle region of the chain, alkylalkoxy sulfates branched in the middle region of the chain and branched alkylalkoxylates in the middle region of the chain. There are two types of branched surfactants that are especially preferred: the sasol type and the shell type. The sasol surfactants are a system of surfactants comprising a mixture of branched surfactants in the middle region of the chain, said mixture of branched surfactants comprising linear and branched surfactant compounds in the medium chain, said linear compounds exceeding less about 25% and less than about 70% by weight of the branched surfactant mixture, wherein the branched surfactant compounds in the middle region of the chain have the formula: Ab-B wherein Ab is a hydrophobic moiety having about from 10 to about 18 total carbon atoms divided by a longer chain and at least one short chain, the longest chain being on the scale of about 9 to about 17 carbon atoms, having one or more alkyl portions of C? -C3 branching off from the longest chain, as long as at least one of the portions The branching alkyl is attached directly to a carbon of the longest linear carbon chain at a position within the carbon scale of position 3, counting from carbon # 1 which is attached to the -B portion, to the carbon the portion? -2, where? is the terminal carbon, B is a hydrophilic portion selected from the group consisting of OSO3M, (EO / PO) mOH, (EO / PO) mOSO3M and mixtures thereof, wherein EO / PO are alkoxy portions selected from the group consisting of in ethoxy, propoxy and mixtures thereof, wherein m is at least about 1 to about 30 and M is hydrogen or a salt-forming cation, as long as the total average number of carbon atoms in the Ab portion in the The mixture of branched surfactants is within the range of about 11 to 14.5. The shell-type surfactant system comprises a mixture of branched surfactants, said mixture of branched surfactants comprising linear and branched surfactant compounds in the middle chain, said linear compounds representing less than about 25% by weight of the branched surfactant mixture. , wherein the branched surfactant compounds in the middle region of the chain have the formula: Ab-B wherein Ab is a hydrophobic moiety having from about 10 to about 18 total carbon atoms divided by a longer chain and at least a short chain, the longest chain being on the scale of about 9 to about 17 carbon atoms, with one or more C1-C3 alkyl portions branching from the longer chain, provided at least one of the alkyl portions of the branch is attached directly to a carbon of the linear carbon chain plus l arga in a position within the carbon scale of position 3, counting from carbon # 1 which is attached to the portion -B, to the carbon of the portion? -2, where? is the terminal carbon, B is a hydrophilic portion selected from the group consisting of OSO3M, (EO / PO) mOH, (EO / PO) mOSO3M and mixtures thereof, wherein EO / PO are alkoxy portions selected from the group consisting of in ethoxy, propoxy and mixtures thereof, wherein m is at least about 1 to about 30 and M is hydrogen or a salt-forming cationas long as the total average number of carbon atoms in the Ab portion in the branched surfactant mixture is within the range of about 1 1 to 14.5. See the patent applications of E.U.A. Nos. 60/061, 971 (Case No. 6881 P), filed on October 14, 1997, 60/061, 975 (Case No. 6882P), filed on October 14, 1997, 60 / 062,086 (Case No. 6883P), filed on October 14, 1997, 60/061, 916 (Case No. 6884P), filed on October 14, 1997, 60/061, 970 (Case No. 6885P), filed on October 14, 1997 and 60 / 062,407 (Case No. 6886P), filed on October 14, 1997, all of which are incorporated herein by reference. Other branched surfactants in the middle region of the chain can be found in the patent applications of E.U.A. Nos. 60/031, 845 (Case No. 6402P) and 60/031, 916 (Case No. 6403P). Suitable anionic sulfate surfactants for use in the present invention include linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty acid oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, acyl sulfates (C5-C-? 7) -N-alkyl (C? -C) glucamine and acyl (C5-C17) -N-hydroxyalkyl (C? -C2) glucamine, and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (unsulfated compounds are described herein) non-ionic). The alkyl sulfate surfactants are preferably selected from linear and branched C 1 or C 8 primary alkyl sulfates, more preferred from branched chain C 11 -C 15 alkyl sulfates and C 2 -C 20 alkyl sulfates linear chain. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferred, the alkylethylsulfate surfactant is a C-H-C-is alkyl sulfate, more preferred C 11 -C 15 alkyl sulfate, which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been described in PCT application No. WO 93/18124. Sulfonate anionic surfactants suitable for use in the present invention include the linear C5-C2al alkylbenzene sulphonate salts, alkyl ether sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefin sulphonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, acyl glycerol sulphonates, fatty acid, fatty acid oleylglycerolsulphonates and any of the mixtures thereof. Suitable carboxylate anionic surfactants include the alkyleoxycarboxylates, the alkylpolyethoxy polycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps such as those described in the present invention. Suitable alkylethoxycarboxylates include those with the formula RO (CH2CH2?) XCH2COO-M + in which R is an alkyl group of CQ to C- | 8-? It is in the range of 0 to 10, and the ethoxylate distribution is such that, on a basis by weight, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula RO- (CHR- | -CHR2-O) -R3 in which R is an alkyl group of CQ at C- | 8. x is from 1 to 25, R-] and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of it consists of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use in the present invention are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl- 1-nonanoic, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors. Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (RI) CH2COOM, in which R is a linear or branched C5-C-17 alkyl or alkenyl group, R ^ is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Amphoteric Surfactant Amphoteric surfactants suitable for use in the present invention include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) XN0 (R5) 2, in which R ^ is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R ^ is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Alkyl dimethylamine oxide of C ^ o-Ci s and acylamidodimethylamine oxide are preferred of C? o-C- | 8- A suitable example of an alkylalanodicarboxylic acid is Miranol (MR) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants which can be used in the present invention. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- in which R is a hydrocarbyl group of CQ-CJ Q, each R1 is typically C-1-C3 alkyl, and R2 is a hydrocarbyl group of C-j-Cs. Preferred betaines are the dimethylammoniohexanoate-dimethyl (or diethyl) betaines of C- | 2-C- | 8 and acetylamidopropane (or ethane) dimethyl (or diethyl) betaines of C- | o_Ci8 - Complex betaine surfactants are also suitable for use in the present invention.

Cationic Surfactants The cationic ester surfactants used in this invention preferably compounds that can be dispersed in water having surfactant properties and comprising at least one ester linkage (i.e., -COO-) and at least one group cationically charged. Other suitable cationic ester surfactants, including choline ester surfactants, have been described for example in the U.S. Patents. Nos. 422,8042, 4239660 and 4260529. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono-N-alkyl or alkenylammonium surfactants of C 6 -C 6+, preferably mono-N-alkyl or C6-C? al alkenyl ammonium, in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups.

Detergency builders The present invention may include an optional builder in the product composition. The level of detergent / builder salt may vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder and very typically from about 10% to about 80%, even very typically from about 15% to about 50% by weight, of builder. However, no attempt is made to exclude lower or higher levels. Inorganic or phosphate-containing builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates) and sesquicarbonate), sulfates and aluminosilicates. However, non-phosphate builders are required in certain places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" detergency builders (as compared to phosphate builders) such as citrates, or in the so-called "lower detergency enhancement" situation that It can occur with zeolite builders or stratified silicate. Examples of silicate builders are alkali metal silicates, particularly those having a Si 2: Na 2 ratio. in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in the US patent. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological form of delta-Na2Si? 5 layered silicate. It can be prepared by methods such as those described in the German application DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred stratified silicate for use herein, but other layered silicates, such as those having the general formula NaMSix? 2? +? yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1 as the alpha, beta and gamma forms. As indicated above, the delta-Na2Si? 5 (NaSKS-6) form is most preferred for use herein. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate salts as builders are alkali metal and alkali metal carbonates such as those described in German Patent Application No. 2,321,001 published November 15, 1973. Aluminosilicate builders can also be added to the present invention as a detergent salt. Aluminosilicate builders are of great importance in most heavy duty granular detergent compositions currently marketed. The aluminosilicate builders include those that have the empirical formula: Mz [(SiO2) w (AIO2) and] xH2O where z, w and (y) are integers of at least 6, the molar ratio of zayy of zaw is in the scale of about 1.0 to about 0.5, and x is an integer of about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically derived aluminosilicates. A method for producing aluminosilicate ion exchange materials is described in the U.S.A. 3,985,669, Krummel et al. Issued October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a Especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12 [(Al? 2) i2 (Si? 2) i2] H2O wherein x is from about 20 to about 30, especially from about 27 The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders comprises ether polycarboxylates, including oxydisuccinate, as described in Berg, U.S. 3,128,287, issued April 7, 1964, and Lamberti et al., Patent of E.U.A. 3,635,830, issued January 18, 1972. See also detergency builders of "TMS / TDS" of the U.S. patent. No. 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrate builders, ie, citric acid and soluble salts thereof (particularly sodium salts), are polycarboxylate builders of particular importance. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanediates and the related compounds described in US Pat. No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C2o alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristiisuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263, published November 5, 1986.

Other suitable polycarboxylates are described in the patent of E.U.A. 4, 144,226, Crutchfield et al., Issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, see also Diehl Patent of US Pat. No. 3,723,322. The fatty acids are, for example, monocarboxylic acids of C-? 2-Ci8, they can also be incorporated into the compositions alone, or in combination with the aforementioned builders, especially the citrate and / or succinate builders, to provide additional detergency builder activity. Said use of fatty acids will generally result in a decrease in foaming, which should be taken into account by the formulator.

Bleaching Agents Bleaching agents according to the present invention may include both chlorinated bleach systems and oxygenated bleach systems. The sources of hydrogen peroxide are described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, 4a. Ed (1992, John Wiiey &Sons), Vol. 4 pp. 271-300"Bleaching Agents (Survey)" incorporated in the present invention, and includes the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms. An "effective amount" of a source of hydrogen peroxide is any amount that can measurably improve the removal of stains (especially tea stains) from the dirty tableware compared to free hydrogen peroxide source when the consumer washes the dishes dirty in a domestic automatic dishwasher in the presence of alkali. More generally, a source of hydrogen peroxide in the present invention is any convenient compound or mixture that, under the conditions of consumer use, provides an effective amount of hydrogen peroxide. The levels may vary widely and are generally in the range of about 0.1% to about 70%, more typically from about 0.5% to about 30% by weight of the compositions of the present invention. The preferred source of hydrogen peroxide used in the present invention can be any convenient source, including hydrogen peroxide itself. For example, perborate can be used in the present invention, for example sodium perborate (any of the hydrates, but preferably the mono- or tetrahydrate), sodium carbonate peroxyhydrate or equivalent salts of percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide. Also available are available oxygen sources such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monihydrate and sodium percabonate are particularly preferred. Mixtures of any of the suitable sources of hydrogen peroxide can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, more than about 10% by weight of said particles being less than about 200 microns and being no more of about 10% by weight of said particles greater than about 1.250 microns. Optionally, the percarbonate can be coated with a silicate, borate or water soluble surfactants. Percarbonate can be obtained from various commercial sources such as FMC, Solvay and Tokai Denka. The compositions of the present invention may also comprise as the bleaching agent a chlorinated bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"), or sodium hypochlorite (NaOCI). When chlorinated bleaching agents are present it is important that they are separated from any of the enzymes or any of the detergent active agents that are sensitive to the bleach. In addition, when using a chlorine bleach, it is important that the bleach be removed or neutralized by a bleach scrubber, before any of the enzymes or any of the detergent active agents that are sensitive to the bleach are released into the bleach solution. washed. (a) Bleach Activators Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The activator is present at levels from about 0.01% to about 15%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 8% by weight of the composition. Preferred activators are selected from the group consisting of tetracetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C10-OBS), benzoylvalerolactam (BZVL), octanolioxybenzenesulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of from about 8 to about 9.5 are those that are selected to have an OBS or VL leaving group. Preferred bleach activators are those described in the U.S. Patent. 5,130,045, Mitchel et al., And 4,412,934, Chung et al., And copending U.S. patent applications. with serial numbers 08 / 064,624, 08 / 064,623, 08 / 064,621, 08 / 064,562, 08 / 064,564, 08 / 082,270 and co-pending application to M. Burns, Willey AD, Hartshom RT, CK Ghosh, subtitled "Bleaching Compounds Comprising Peroxiacid Activators Used With Enzimes "and that has the US serial number 08 / 133,691 (P & G Case 4890R), which are all incorporated in the present invention as a reference. The molar ratio of the peroxygen bleach compound (as AvO) to the bleach activator in the present invention generally ranges from at least 1: 1, preferably from about 20: 1 to about 1: 1, more preferably from about 10: 1. up to about 3: 1. The substituted quaternary bleach activators can also be included. The present detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a substituted quaternary peracid (QSP); more preferably, the first. Preferred QSBA structures are further described in U.S. Pat. copending with Nos. 5,460,747, 5,584,888 and 5,578,136, incorporated by reference in the present invention. (b) Organic peroxides, especially diacyl peroxides. These peroxides are illustrated extensively in Kirk Othmer, Encyclopedia of Chemical Techonology, Vol. 17, John Wiley and Sons, 1982 on pages 27-90 and especially on pages 63-72, which are incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one that exerts a minimal impact on the formation of spots / film. The preferred is dibenzoyl peroxide. (c) Metal-containing bleach catalysts The compositions and methods of the present invention utilize metal-containing bleach catalysts that are effective for use in ADD compositions. Preferred are bleach catalysts containing manganese and cobalt. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese, an auxiliary metal cation. having little or no catalytic bleach activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylene phosphonic acid) and water-soluble salts of the same. Said catalysts are described in E.U.A. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594 Preferred examples of these catalysts include MnlV2 (uO) 3 (1, 4J-trimethyl-1, 4,7-triazacyclononane) 2 (PF6) 2 ("MnTACN"), Mnl "2 (uO)? (U-) Oac) 2 (1, 4,7-trimethyl-1, 4J-triazacyclononane) 2 (CIO4) 2, MnIV4 (uO) 6 (1, 4,7-triazaclononan) 4 (CIO4) 2, Mn ' "Mnlv4 (uO)? (U-Oac) 2- (1, 4J-trimethyl-1, 4,7-triazacyclononane) 2 (CIO4) 3 and mixtures thereof. See also European patent application Publication No. 549,272. Other ligands suitable for use herein include 1, 5,9-triazacyclododecane, 2-methyl-1, 4,7-triazacyclononane, 2-methyl-1, 4,7-triazacyclononane and mixtures thereof. Bleach catalysts useful in automatic dishwashing compositions and concentrated powder detergent compositions may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. No. 4,246,612 and US patent. No. 5,227,084. Other bleach catalysts are described, for example, in European Patent Application Publication No. 408,131 (Cobalt Complex Catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (Metalloporphyrin Catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), E.U.A. 4.71 1, 748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), E.U.A. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U.A. 4,728,455 (manganese gluconate catalysts).

Cobalt-based catalysts having the formula: [Co (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, most preferred 5) are preferred; M 'is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, most preferred 1); m + n = 6; and Y is an appropriately selected counter-ion present in a number y, which is an integer from 1 to 3 (preferably from 2 to 3; more preferred 2 when Y is an anion with charge -1), to obtain a balanced salt in terms of charges. The preferred cobalt-based catalyst of this type useful herein are cobalt pentaamincloride salts having the formula [Co (NH3) 5CI] Yy, and especially [Co (NH3) CI] CI2. Most preferred are the compositions of the present invention which utilize cobalt-based bleach catalysts (III) having the formula: [Co (NH3) n (M) m (B) b] Ty wherein the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated with the cobalt by a site; m is 0, 1 or 2 (preferably 1), B is a ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is 1 or more appropriately selected counterions present in a number y, where y is an integer to obtain a balanced salt in terms of charges (preferably y is 1 to 3, more preferred 2 when T is an anion with charge - 1 ); and wherein further said catalyst has a hydrolysis rate constant in basic medium of less than 0.23 M "1 s" 1 (25 ° C). The preferred T is selected from the group consisting of chloride, iodide, l3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF4", B (Ph) 4", phosphate, phosphite, silicate, tosylate methanesulfonate and combinations thereof. Optionally T may be protonated if there is more than one anionic group in T, for example, HPO42", HCO3", H2PO4", etc. 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 sulfates (AS), alkyl ethoxysulfonates (AES), etc.) and / or anionic polymers (for example, polyacrylates, polymethacrylates, etc.) The M-portions include, but are not limited to , for example, F ", SO" 2, NCS ", SCN", S2O3"2, NH3, PO43", and carboxylates (which are preferably monocarboxylates, but more than one carboxylate may be present in the portion while the cobalt binding is made only by one carboxylate per portion, in which case the other carboxylate in the M portion may be protonated or in salt form.) M may optionally be protonated if more than one anionic group exists in M (eg example, HPO42", HCO3", H2PO4", HOC (O) C H2C (O) O ", etc.). Preferred M-portions are substituted and unsubstituted C 3 -C 3 carboxylic acids having the formulas: RC (O) O- wherein R is preferably selected from the group consisting of hydrogen and C-α-C 30 alkyl (preferably C) -? - C? 8) unsubstituted and substituted, unsubstituted and substituted C ar-C3o aryl (preferably Cβ-C ?8) and unsubstituted and substituted C3-C3o heteroaryl (preferably C5-C ?8), wherein the substituents are selected from the group consisting of -NR'3, -NR'4 +, -C (O) OR ', -OR', -C (O) NR'2 > wherein R 'is selected from the group consisting of hydrogen and portions of C? -C6. Such substituted R thus includes the portions - (CH2) nOH and - (CH2) nNR'4 +, wherein n is an integer of 1 about 16, preferably from about 2 to about 10 and more preferred from about 2 to approximately 5. Most preferred M are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C-t2 alkyl, and benzyl. The most preferred 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 (e.g., oxalate, malonate, malic, succinate, maleate) picolinic acid and alpha and beta amino acids (for example glycine, alanine, beta-alanine, phenylalanine). The cobalt-based bleach catalysts useful herein are known, being described for example together with their rates of hydrolysis in basic medium, in M. L. Tobe, "Hydrolysis-Base Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table 1 on page 17, provides the hydrolysis rates in basic medium (designated in that reference as ko? -?) For pentamincobalt-based catalysts complexed with oxalate (koH = 2.5 x 10"4 M" 1 s "1 (25 ° C)), NCS" (kOH = 5.0 x 10"4 M'1 s" 1 (25 ° C), formate (kO = 5.8 x 10"4 M" 1 s "1 (25 ° C) C)), and acetate (kO = 9.6 x 10"4 M" 1 s "1 (25 ° C).) The most preferred cobalt-based catalysts useful herein are the cobalt pentamine acetate salts having the formula [Co (NH3) 5OAc] Ty, wherein OAc represents an acetate portion, and especially cobalt pentamine acetate chloride, [Co (NH3) 5OAc] CI2; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2. The cobalt-based catalysts according to the present invention can be produced in accordance with the synthetic routes described in US Pat. do not. 5,559,261, 5,581, 005 and 5,597,936, the descriptions of which are incorporated herein by reference. These catalysts can be coprocessed with auxiliary materials if it is desired to reduce the impact on the color for the aesthetic appearance of the product, or they can be included in particles containing enzyme as hereinafter exemplified, or the compositions can be manufactured so that contain "specks" of catalyst. As a practical aspect, and not by way of limitation, the cleaning compositions and cleaning methods herein can be adjusted to provide in the order of at least one part per one hundred million of the active bleach catalyst species in the aqueous washing medium, and preferably will provide from 0.01 ppm to about 25 ppm, more preferred from 0.05 ppm to about 10 ppm and more preferably even from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the liquor of washing. In order to obtain such levels in the washing solution of an automatic dishwashing process, the typical automatic dishwashing compositions herein will consist of from about 0.0005% to about 0.2%, more preferred from about 0.004% to about 0.08% bleach catalyst by weight of the cleaning compositions.

Controlled release rate The detergent tablet may be provided with a form for controlling the rate of release of the bleaching agent, particularly oxygen bleach to the washing solution.

The bleach release rate control can be provided for the controlled release of peroxide species to the wash solution. The foregoing could, for example, include controlling the release of any inorganic perhydrate salt, acting as a source of hydrogen peroxide, to the wash solution. Suitable forms of controlled release of the bleaching agent can include the confinement of the bleach to the core layer, the first encapsulating layer or the second encapsulating layer. Another way to control the rate of bleach release can be by coating the bleach with a coating designed to provide the controlled rate. The coating may therefore, for example, comprise a material poorly soluble in water, or be a coating of sufficient thickness for the kinetics of thick coating solution to provide the controlled rate of release. The coating material can be applied using several methods. Any coating material is typically present in a weight ratio of coating material to bleach from 1: 99 to 1: 2, preferably from 1:49 to 1: 9. Suitable coating materials include triglyceride (for example, partially) of hydrogenated vegetable oil, soybean oil, cottonseed oil, or 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 from 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 3.0: 1, and / or sodium metasilicate, preferably applied at a level of 2% to 10%, (usually 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Any inorganic salt coating material can be combined with organic binder materials to provide mixed inorganic salt materials / organic binder coatings. Suitable binders include C-? 0-C2o ethoxylated alcohols containing 5-100 moles of ethylene oxide per mole of alcohol and most preferred the C-i5-C2o ethoxylated primary alcohols containing 20-100 moles of ethylene oxide per mole of alcohol. Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of 12,000 to 00,000 and polyethylene glycols (PEG) with an average molecular weight of 600 to 5 x 106, preferably 1000 to 400,000, most preferably 1000 to 10,000, are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, in which the maleic anhydride constitutes at least 20 mol% of the polymer are also examples of polymeric materials useful as binders. Said polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the aforementioned C10-C20 ethoxylates containing from 5-100 moles of ethylene oxide per mole. Other examples of binders include the C10-C20 mono- and diglycerol ethers and also the C0-C2o fatty acids- The cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein. A method for the application of the coating material involves agglomeration. Preferred agglomeration procedures include the use of any organic binder material described above. Any conventional agglomerator / mixer can be used including, but not limited to a tray, rotating cylinder and vertical mixer types. The melt coating compositions can also be applied either by pouring on or by spraying onto a moving bed of bleaching agent. Other ways of providing the required controlled release include altering the physical characteristics of the bleach to control its solubility and release rate. Suitable forms can include compression, mechanical injection, manual injection and adjustment of the solubility of the bleaching compound by selecting the particle size of any particulate component. Although the selection of the particle size will depend both on the composition of the particulate component and the desire to comply with the desired controlled release kinetics, it is desirable that the particle size should be greater than 500 microns, preferably having a particle diameter average of 800 to 1200 microns. Additional ways to provide controlled release include the proper choice of any of the other components of the detergent composition matrix, so that when the composition is introduced into the wash solution, the ionic strength environment provided therein will allow the required controlled release kinetics is achieved.

Bleach scrubbers The compositions of the present invention which contain chlorine-based bleach may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, more preferably from about 0.01% to about 6%, in weight of a bleach scrubber. The bleach scrubber can be any bleach scrubber that is compatible with the detersive enzyme. Suitable bleach scrubbers include perborate, reducing agents, such as thiosulfate and ammonium salts such as ammonium sulfate, with perborate being preferred.

Detersive Enzymes The compositions of the present invention may also include the presence of at least one detersive enzyme. "Detersive enzyme", as used herein, refers to any enzyme that has a beneficial effect of cleaning, stain removal or other beneficial effect in a composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. The highly preferred for automatic dishwashing are the amylases and / or proteases including both the currently commercially available types and the improved types which, although more compatible with the bleach, have some remaining degree of susceptibility to inactivation by bleach In general, as noted, the preferred compositions herein comprise one or more detersive enzymes. If only one enzyme is used, it is preferably an amolytic enzyme when the composition is for the use of automatic dishwashing. The highly preferred for automatic dishwashing is a mixture of proteolytic enzymes and amyloid enzymes. More generally, the enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. These can be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. However, its selection is controlled by several factors such as optimum pH-activity and / or stability, thermostability, stability against active detergents, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Enzymes are normally incorporated in the detergent compositions herein at levels sufficient to provide an "effective amount of cleaning". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal or dirt removal effect on substrates such as fabrics, tableware and the like. Because the enzymes are catalytic materials, these amounts can be very small. In practical terms for the current commercial preparations, typical amounts are up to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. In other words, the compositions herein will typically comprise from about 0.001% to about 6%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For the purpose of automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparations, in order to minimize the total amount of non-catalytically active materials supplied and thereby improve the stain formation results. movie.

Suitable examples of proteases are the subtilisins that are obtained from particular strains of f. subtilis and B. licheniformis. Another suitable protease is obtained from a Bacillus strain, having maximum activity in the pH range of 8-12, developed and sold by Novo Industries A / S as ESPERASE®. The preparation of said enzyme and analogous enzymes is described in the specification of British Patent No. 1, 243,784 of Novo. Suitable proteolytic enzymes for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE® and SAVINASE® by Novo Industries A / S (Denmark), MAXATASE® by International Bio-Synthetics, Inc. ( Netherlands) and PURAFECT®, by GCI. Other proteases include protease A (see European patent application 130,756, published January 9, 1985) and protease B (see European patent application serial number 8J303761.8, issued April 28, 1987, and patent application) European 130,756, Bott et al., published on January 9, 1985). An especially preferred protease, referred to as "protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by substitution of a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104 , +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, + 217, +218, +222, +260, +265, and / or +274 according to the subtilisin numbering of Bacillus amyloliquefaciens, as described in WO 95/10615 published April 20, 1995 by Genencor International . Other preferred protease enzymes include protease enzymes which are a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived by the replacement of a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme corresponds to the +210 position in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217 , +218 and +222, where the numbered positions correspond to the naturally occurring subtilisin of Bacillus amyloliquefaciens or the equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes include those that have position changes +210, +76, +103, +104, +156, and +166. Useful proteases are also described in the PCT publications: WO 95/30010 published November 9, 1995 by The Procter & amp; amp;; Gamble Company; WO 95/3001 1 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company. Amylases suitable herein include, for example, α-amylases described in British Patent Specification No. 1, 296,839 (Novo), RAPIDASE®, International Bio-Synthetics, Inc. ENDOLASE, by Novo Industries and TERMAMYL®, Novo Industries. Preferred amylases herein have the similarity of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus α-amylases, regardless of whether 1, 2 or multiple amylase strains are the precursors. immediate. As noted, amylases of "increased stability to oxidation" are preferred for use herein despite the fact that the invention makes them "optional but preferred" materials rather than essential ones. Said amylases are illustrated in a non-limiting manner by the following: a) An amylase according to the previously incorporated WO / 94/02597, Novo Nordisk A / S, published on February 3, 1994, as further illustrated by a mutant whose substitution is made using alanine or threonine (preferably threonine), of the methionine residue located at position 197 of the α-amylase B. licheniformis, known as TERMAMYL®, or the homologous position variation of a similar original amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; b) Amylases of improved stability as described by Genencor International in a document entitled "Oxidatively Resistant a-amylases" presented at the 20th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. It was observed that the bleaches in the automatic dishwashing detergents inactivate the α-amylases, but that the amylases of improved oxidative stability have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue that could be modified more easily. The Met was substituted, one at a time, in the positions 8,15,197,256,304,366 and 438 leading to specific mutants, particularly being important the M197L and M197T with the variant M197T being the variant expressed more stable. The stability was measured in CASCADE® and SUNLIGHT®; c) Also preferred herein are the amylase variants having the additional modification in the immediate relative available from Novo Nordisk A / S and those referred by the supplier under the trade name DURMAMYL®; d) Particularly preferred are the amylase variants as described in WO95 / 26397 and in the co-pending application to Novo Nordisk PCT / DK96 / 00056 and characterized by having a specific activity of at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a pH value in the range of 8 to 10, as measured by the Phadebas® α-amylase activity assay and obtained from a Bacillus alkalophilic species (such such as strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935) comprising the following amino acid sequence at the N-terminus: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr -Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp. The cellulases usable in, but not preferred, the present invention include bacterial or fungal cellulases. Typically, they will have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the U.S.A. 4,435,307, Barbesgoard et al., Issued March 6, 1984, which describes the fungal cellulase produced from Humicola insolens and strain Humicola DSM1800 or a cellulase 212 that produces fungi belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricular Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® (Novo) which are especially useful. Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372,034. See also lipases in Japanese Patent Application 53,20487, open to the public for inspection, from February 24, 1978. Said lipase is available from Amano Pharmaceutical Co Ltd., Nagoya, Japan, under the trade name Lipase P " Amano ", hereinafter referred to as" Amano-P ". Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipoliticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and in addition Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands, and Pseudomonas gladioli lipases. The LIPOLASE® enzyme obtained from Humícola lanuginosa and commercially available from Novo (see also EPO 341, 947) is a preferred lipase for use herein. Another preferred lipase enzyme is the D96L variant of the native Humicola lanuginosa lipase, as described in WO 92/05249 and research description No 35944, March 10, 1994, both published by Novo. In general, lipolytic enzymes are less preferred than amylases and / or proteases for the automatic dish washing embodiments of the present invention. Peroxidase enzymes can be used in combination with an oxygen source, that is, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically used for "bleaching in solution", 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, haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A / S. The present invention comprises peroxidase-free automatic dishwashing composition embodiments. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in the U.S.A. 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are also described in the U.S. patent. 4,101, 457, Place et al., Issued July 18, 1978, in the patent of E.U.A. 4,507,219, Hughes, issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in US Patent 3,600,319, issued August 17, 1971 to Gedge, et al., And European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published on 29 October 1986, Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. 3,519,570.pH and variation of pH regulation The detergent tablet compositions herein can be regulated in their pH, that is, they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low pH regulation capacity, or may substantially not be regulated in their pH. Techniques for controlling or varying the pH to recommended levels of use more generally include the use of not only pH regulators, but alkalis, acids, pH jump systems, additional dual compartment containers, etc., and are well known to those skilled in the art. Preferred compositions herein comprise a pH adjusting component selected from the water soluble alkaline inorganic salts and water soluble organic or inorganic binders. The pH adjusting components are selected so that when the composition is dissolved in water at a concentration of 1,000-10,000 ppm, the pH remains in the range above about 8, preferably from about 9.5 to about 11. The preferred non-phosphate pH adjustment component of the invention is selected from the group consisting of: (i) sodium carbonate or sesquicarbonate; (ii) sodium silicate, preferably sodium silicate hydrate having the ratio S0O2: Na2O of from about 1: 1 to about 2: 1, and mixtures thereof with limited amounts of sodium metasilicate; (iii) sodium citrate; (iv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably borax; (vii) sodium hydroxide; (viii) mixtures of (i) - (vii). Preferred embodiments contain low levels of silicate (eg, from about 3% to about 10% SiO 2). The amount of the pH adjustment component in the instant composition preferably is from about 1% to about 50% by weight of the composition. In a preferred embodiment, the pH adjusting component is present in the composition in an amount of from about 5% to about 40%, preferably from about 10% to about 30% by weight.

Water-soluble silicates The present compositions may further comprise water-soluble silicates. The water soluble silicates herein are any silicate that is soluble until it does not adversely affect the stain / film formation characteristics of the ADD composition. Silicate examples are sodium metasilicate and, more generally, alkali metal silicates. , particularly those having an SiO2: Na2O ratio in the range of 1.6: 1 to 3.2: 1, preferably having an SiO2: Na2O ratio of about 1.0 to about 3.0; and stratified silicates, such as the layered sodium silicates described in the U.S. Patent. 4,664,839, issued May 12, 1987 to H.P Rieck. NaSKS-6R is a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite binders, Na SKS-6 and other water-soluble silicates useful herein do not contain aluminum. NaSKS-6 is the d-Na2SiO5 form of layered silicate and can be prepared by methods such as those described in German Patents DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicate for use herein, but other layered silicates, such as those having the general formula NaMSix? 2? +? Can be used. and H 2 O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Several other Hoechst stratified silicates include NaSKS-5; NaSKS-7 and NaSKS-1 1, as the forms a-, ß- and? -. Other silicates may also be useful, such as for example magnesium silicate, which can serve as a bridging agent in the granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Silicates particularly useful in automatic dishwashing (ADD) applications include hydrated ratio 2 silicates, granulates such as BRITESIL® H2O from PQ Corp, and the commonly preferred BRITESIL® H24 although the liquid grades of various silicates can be used when the composition ADD has liquid form. Within safe limits, the sodium metasilicate or sodium hydroxide, alone or in combination with other silicates can be used in an ADD context to boost the wash pH to a desired level.

Chelating Agents The compositions herein may also optionally contain one or more selective transition metal sequestrants, "chelating agents" or "chelating agents", i.e., iron and / or copper and / or manganese chelating agents. Chelating agents suitable for use herein may be selected from the group consisting of aminocarboxylates, phosphonates (especially aminophosphonates), polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Without intending to be limited by theory, it is believed that the benefit of such materials is due in part to their exceptional ability to control iron, copper and manganese in washing solutions which are known to decompose hydrogen peroxide and / or activators. bleach; Other benefits include the prevention of inorganic film or inhibition of incrustation. Commercial chelating agents for use herein include the DEQUESTR series, and chelators of Monsanto, DuPont, and Nalco, Inc. Useful aminocarboxylates such as optional chelating agents are further illustrated by ethylenediaminetetracetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetraproprinates, triethylenetetraminehexacetates, diethylenetriamin pentaacetates, and ethanoldiglicins, alkali metal, ammonium, and substituted ammonium salts thereof. In general, the chelating mixtures can be used for a combination of functions, such as control of multiple transition metal, long-term product stabilization, and / or control of precipitated metal oxides and / or hydroxides of transition. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions of the present invention. See Patent of E.U.A. 3,812,044, issued on May 21, 1974, to Connor and others. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A highly preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS"), especially (but not limited to) the [S, S] isomer as described in the U.S.A. 4,704,233, November 3, 1987, to Hartman and Perkins. The salt is preferred to be trisodium, although other forms, such as the magnesium salts, may also be useful. Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are acceptable in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonate) and dithylenetriaminpentakis (methylene phosphonates). Preferably, said aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. If used, selective transition metal chelating agents or sequestrants will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight of the compositions of the present invention.

Crystal Growth Inhibiting Component Detergent tablets may preferably contain a crystal growth inhibiting component, preferably an organodiphosphonic acid component, more preferably incorporated at a level of 0.01% to 5%, even more preferably from 0.1% to 2%. % by weight of the compositions. Organodiphosphonic acid refers herein to an organodiphosphonic acid that does not contain nitrogen as part of its chemical structure. The definition therefore excludes organo-phosphonates, which however, can be included in compositions of the invention as heavy metal ion sequestering components. The organodiphosphonic acid is preferably a diphosphonic acid of C? -C4, more preferably a diphosphonic acid of C2, such as ethylene diphosphonic acid, or most preferably ethan-1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present partially or totally ionized, particularly as a salt or complex.

Dispersant polymer The preferred compositions herein may additionally contain a dispersant polymer. When present, a dispersant polymer in the compositions herein is typically found at levels in the range of 0 to about 25%, preferably about 0.5% to about 20%, more preferably from about 1% to about 8% in weight of the composition. Dispersing polymers are useful for the improved film development of the present compositions, especially in higher pH embodiments, such as those in which the wash pH exceeds about 9.5. Particularly preferred are polymers that inhibit the deposition of calcium carbonate or magnesium silicate in dishwashing. Dispersing polymers suitable for use herein are further illustrated by the film-forming polymers described in the U.S.A. No. 4,379,080 (Murphy), issued April 5, 1983. Suitable polymers are, at least preferably, partially neutralized or alkali metal, substituted ammonium or ammonium salts (ie mono-, di- or triethanolammonium) of polycarboxylic acids. The alkali metal, especially the sodium salts, are most preferred. Although the molecular weight of the polymer can vary in a wide variety, it is preferably from about 1,000 to about 500,000, more preferably from about 1,000 to about 250,000, and most preferably, especially if the composition is for use in Automatic dishwashing applications in North America, is from about 1, 000 to about 5,000. Other suitable dispersing polymers include those described in the U.S.A. No. 3,308,067 issued on March 7, 1967, to Diehi. The unsaturated monomeric acids which can be polymerized to form suitable dispersing polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, metaconic acid, citraconic acid and methylenemalonic acid.

The presence of monomeric segments that do not contain carboxylate radicals such as methylvinyl ether, styrene, ethylene, etc., is suitable as long as said segments do not constitute more than about 50% by weight of the dispersant polymer. Acrylamide and acrylate copolymers having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, can also be used. weight of the dispersant polymer. Most preferably, said dispersant polymer has a molecular weight of about 4,000 to about 20,000 and an acrylamide content of about 0% to about 15% by weight of the polymer. Particularly preferred dispersing polymers are low molecular weight modified polyacrylate copolymers. Said compolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight of acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and has the general formula: - [(C (R2) C (R1) (C (O) OR3)] wherein the valences appear to be unfilled they are in fact occupied by hydrogen and at least one of the substituents R, R2 or R3, preferably R1 or R2, is an alkyl or hydroxyalkyl group of 1 to 4 carbons, R1 or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt The most preferred is a substituted acrylic monomer wherein R 1 is methyl, R 2 is hydrogen and R 3 is sodium The preferably low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than about 15., 000 preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid. Other suitable modified polyacrylate copolymers include the low molecular weight copolymers of the unsaturated aliphatic carboxylic acids described in U.S. Pat. 4,530,766, and 5,084,535. The agglomerated forms of the present compositions can employ aqueous solutions of polymer dispersants as liquid binders to make the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate). Especially preferred are polyacrylates with an average molecular weight of from about 1,000 to about 10,000, and acrylate / maleate or acrylate / fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and an acrylate ratio to maleate segments or of fumarate from about 30: 1 to about 1: 2. Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are described in European Patent Application No. 66,915, published on December 15, 1982. Other dispersion polymers useful herein include polyethylene glycols and polypropylene glycols which they have a molecular weight of about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds, for example, having a melting point in the range of about 30 ° C to about 100 ° C, can be obtained at molecular weights of 1, 450, 3,400, 4,500, 6,000, 7,400, 9,500 and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the required number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. Reference is made to polyethylene, polypropylene and mixed glycols using the formula: HO (CH 2 CH 2 O) m (CH 2 CH (CH 3) O) n (CH (CH 3) CH 2 O) 0 OH wherein m, n, I are integers that satisfy the molecular weight and the temperature requirement given above. Still other dispersing polymers useful herein include cellulose sulfate ethers such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate, and hydroxypropyl cellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of said group. Also suitable are cellulose derivatives, such as cellulose acetate, cellulose, hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose and carboxymethylcellulose. Said dispersing polymers also have the other advantage that they also reduce the formation of stains and film on hydrophobic surfaces such as plastic. Other suitable dispersing polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates, described in U.S. Patent No. 3,723,322, Diehl, issued March 27, 1973.; the dextrin esters of polycarboxylic acids described in U.S. Patent No. 3,929,107, Thompson, issued November 1, 1975; the hydroxyalkyl starch esters, starch esters, oxidized starches, dextrin and starch hydrolysates described in U.S. Patent No. 3,803,285, Jensen, issued April 9, 1974; the carboxylated starches described in U.S. Patent No. 3,629,121, Eldib issued December 21, 1971; and the dextrin starches described in U.S. Patent No. 4,141,841, McDonald, issued February 27, 1979. Preferred cellulose-derived dispersant polymers are carboxymethyl celluloses. Still another group of acceptable dispersants are organic dispersant polymers present in Nature, such as polyaspartate.

Polymeric dirt release agent The known polymeric soil release agents, hereinafter "SRA" or "SRAs", can optionally be used in the present tablet compositions. If used, the "SRAs" will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5% preferably from 0.2% to 3.0% by weight of the composition. Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of the hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain adhered thereto during the end of the wash and rinse cycles, serving as This form as an anchor for the hydrophilic segments. The above may allow the spots that appear later in the treatment with SRA to be cleaned more easily in subsequent washing procedures. Alternatively, in automatic dishwashing compositions, said hydrophobically modified polymers act to prevent redeposition on hydrophobic surfaces, such as plastic, and provide the improved additional benefit of spot and film formation on the hydrophobic surfaces. The most suitable polymers for such applications are the hydrophobically modified polyacrylates. The SRAs may include a variety of monomer units with charge, for example anionic or even cationic (see document U.S.A. 4,956,447), as well as uncharged monomer units and the structures may be linear, branched or even star-shaped. The foregoing may include blocking portions that are especially effective in controlling molecular weight or altering the physical or surfactant properties. The structures and distributions of loads can be made to apply them to different types of fiber or textile and for various detergents or detergent additive products. Preferred SRAs include oligomeric terephthalate esters, typically prepared by the process involving at least one transesterification / oligomerization, often with a metal catalyst such as titanium (IV) alkoxide. Said esters can be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without obviously forming a densely interlaced general structure. Suitable SRAs include: a sulfonated product of substantially linear ester oligomer comprised of an oligomeric terephthaloyl ester structure and oxyalkyleneoxy repeat units and sulfonated allyl-derived portions covalently bound to the base structure, for example as described in US Pat. US document 4,968,451, November 6, 1990 to JJ Scheibel and E.P. Gosselink; said ester oligomers can be prepared by (a) ethoxylation of allyl alcohol, (b) reaction of the product of part (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a process of transesterification / two-step oligomerization and (c) reaction to the product of (b) with sodium metabisulfite in water; the propylene / polyoxyethylene 1,2-terephthalate polyesters blocked at their non-ionic ends from US Pat. No. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification / oligomerization of ether (ethylene glycol) methyl. , DMT, PG, and poly (ethylene glycol) ("PEG"); the anionic oligomeric esters completely blocked at their ends from US Pat. No. 4,721, 580, January 26, 1988 to Gosselink, such as the oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8 -hydroxyoctansulfonate; oligomeric non-ionic polyester compounds blocked at their ends from US Pat. No. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, Me-blocked PEG and EG and / or PG, or a combination of DMT, EG and / or PG, PEG blocked from Me and Na-dimethyl-5-sulfoisophthalate; and the anionic esters, especially sulfoaroyl, of blocked terephthalate at their ends of the US document, 4,877,896, October 31, 1989 to Maldonado, Gosselink and others, the latter being typical of the SRAs useful in both laundry and fabric conditioning products. , an example being an ester composition made of monosodium salt of m-sulfobenzoic acid, PEG and DMT optionally but preferably further comprising added PEG, eg, PEG 3.400. SRAs also include simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see document E.U.A. 3,959,230 to Hays, May 25, 1976 and E.U.A. 3,893,929 to Basadur, July 8, 1975; cellulose derivatives such as hydroxyether cellulosic polymers available as METHOCEL from Dow; and C 1 -C 4 alkyl celluloses and C 4 hydroxyalkyl celluloses; see document of E.U.A. 4,000,093, December 28, 1976 to Nicol et al. Suitable SRAs characterized by hydrophobic poly (vinyl ester) segments include poly (vinyl ester) graft copolymers, for example C?-C3 vinyl esters, preferably poly (vinyl acetate), embedded in the base structures of polyalkylene. See European patent application 0 219 048, published on April 22, 1987 by Kud, and others. Commercially available examples include SOKALAN SRAs such as SOKALAN HP-22, available from BASF, Germany. Other SRAs are polyesters with repeating units containing 10-15% by weight of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate, derivatives of a polyoxyethylene glycol of average molecular weight of 300-5,000. Commercial examples include ZELCON 5126 and Dupont and Milease T from ICI. Another preferred SRA is an oligomer having the empirical formula (CAP) 2 (EG / PG) 5 (T) 5 (SIP) 1 comprising terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneneoxy and oxy-1, 2- units propylene (EG / PG) and which are preferably terminated with end blocks, (CAP), preferably modified isethionates, in an oiigomer comprising a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy units and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5: 1 to about 10: 1, and two units blocked at their ends derived from sodium 2- (2-hydroxyethoxy) -ethansulfonate. Said SRA preferably also comprises from 0.5% to 20% by weight of the oligomer, of a crystallinity reduction stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzylsulfonate or a member selected from xylene-, cumen-, and toluene sulfonates or mixtures thereof, said stabilizers or modifiers being introduced into the synthesis vessel, as taught in the US document 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRAs are the oligomeric esters comprising: (1) a base structure comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least trifunctional where the ether bonds are formed resulting in a branched oligomer base structure, and combinations thereof; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy portion; and (2) one or more blocking units selected from the non-ionic block units, anionic block units such as the alkoxylated isethionates, preferably ethoxylated, alkoxylated propansulfonates, alkoxylated propandisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof . The preferred ones of said esters are those of the empirical formula:. { (CAP) x (EG / PG) y, (DEG) and "(PEG) y '" (T) z (SIP) z' (SEG) q (B) m} wherein CAP, EG / PG, PEG, T and SIP are as defined above, (DEG) represents di (oxyethylene) oxy units; (SEG) represents units derived from glycerin sulfoethyl ether and related portion units; (B) represents branching units that are at least trifunctional in which the ester bonds are formed resulting in a branched oligomer base structure; x is from about 1 to about 12; and 'is from about 0.5 to about 25; and "is from 0 to about 12; and '" is from 0 to about 10; and '+ y "+ y'" totals from about 0.5 to about 25; z is from about 1.5 to about 25; z 'is from 0 to about 12; z + z 'totals from about 1.5 to about 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y ', y ", y'", z, z ', q and m represent the average number of moles of the corresponding units per mole of said ester and said ester has a molecular weight ranging from about 500 to about 5000. monomers SEG and CAP preferred for the above esters include Na-2- (2-, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), Na-2-. { 2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologs and mixtures thereof of the ethoxylation and sulfonation products of allyl alcohol. Preferred SRA esters in said class include the transesterification and oligomerization product of 2-. { 2- (2-hydroxyethoxy) ethoxy) ethane sulfonate and / or 2- [2-. { 2- (2-hydroxyethoxy) -ethoxy} ethoxy] ethane sulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using a suitable Ti (IV) catalyst and can be designed as (CAP) 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13 where CAP is (Na + -O3S [CH2CH2O] 3.5) - and B is a glycerin unit and the ratio of EG / PG moles is about 1.7: 1 as measured by chromatography of conventional gas after completing the hydrolysis. Additional classes of SRAs include (I) terephthalates not Ions using diisocyanate coupling agents to bond the polymeric ester structures, see U.S. 4,201, 824, Violland et al., And E.U.A. 4,240,918 Lagasse et al .; (II) SRAs with carboxylate end groups made by the addition of trimellitic anhydride to known SRAs to convert the hydroxyl-terminal groups to trimellitate esters. With an appropriate selection of catalyst, the trimellitic anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimellitic anhydride rather than at the anhydride bond opening. The nonionic or anionic SRAs can be used as starting materials as long as they have hydroxyl end groups that can be esterified. See document of E.U.A. 4,525,524 Tung et al .; (lll) SRAs based on anionic terephthalate of the urethane-bonded variety, see document E.U.A. 4,201, 824 Violland and others; (IV) poly (vinylcaprolactam) and copolymers related to monomers such as vinylpyrrolidone and / or dimethylaminoethylmethacrylate, including both nonionic and cationic polymers, see E.U.A. 4,579,681 Ruppert et al .; (V) graft copolymers, in addition to SOKALAN types made of BASF, by grafting acrylic monomers on the sulfonated polyesters, said SRAs have dirt release and anti-redo activity similar to known cellulose esters: see EP 279,134 A, 1988, to Rhone-Poulene Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinylacetate in proteins such as caseins, see EP 457,205 A to BASF (1991); (VII) Polyester-polyamide SRAs prepared by the condensation of adipic acid, caprolactam, and polyethylene glycol, especially for the treatment of polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever NV, 1974. Other useful SRAs are described in US Pat. US patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay Soil Removal / Antiredeposition Agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-rejection properties. Granular compositions containing said compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01% to about 5%. The most preferred soil release and antiredeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in the U.S.A. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removal-antiredeposition agents are the cationic compounds described in European patent application 1 1, 965, Oh and Gosselink, published on June 27, 1984. Other clay soil removal / antiredeposition agents that can be used include ethoxylated amine polymers described in European Patent Application 1 1, 984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S. Patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and / or antiredeposition agents known in the art can also be used in the compositions herein. See Patent of E.U.A. 4,891, 160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995. Another type of preferred antiredeposition agent includes the carboxymethyl cellulose (CMC) materials. Such materials are well known in the art.

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 compounds of Mn (ll), particularly salts of Mn (ll) of organic ligands. Organic silver coating agents are described in PCT publication No. WO94 / 16047 and co-pending European application No. EP-A-690122. Nitrogen-containing corrosion inhibiting compounds are described in co-pending European application No. EP-A-634,478. The Mn (II) compounds for use in inhibiting corrosion are described in copending European application No. EP-A-672 749.

The organic silver coating agent, when present, may be preferably incorporated at a level of from about 0.05% to about 10%, more preferably from about 0.1% to about 5% by weight of the total composition. The functional role of the silver coating agent is to form "in use" a protective coating layer on any silver component of the wash load to which the compositions of the invention are applied. The silver coating agent must therefore have a high affinity for coupling to the solid silver surface, particularly when they are present as a component of an aqueous wash and bleach solution with which the solid silver surfaces are treated. . Organic silver coating agents include, but are not limited to, fatty esters of mono- or polyhydric alcohols having from about 1 to about 40 carbon atoms in the hydrocarbon chain. The fatty acid portion of the fatty ester can be obtained from mono- or polycarboxylic acids having from about 1 to about 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic fatty acids include behenic acids, 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'-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butyl malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid. The fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from about 1 to about 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleic and lauric alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Preferably, the fatty acid and / or fatty alcohol group of the attached fatty ester material have from about 1 to about 24 carbon atoms in the alkyl chain. The preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters 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 also highly preferred. The foregoing are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above. Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityldilactate, cocoyl isobutyrate, oleylmaleate, oleyldimaleate, and tallowylpropionate. Some fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate and 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 sesbitan diesters of tallow alkyl. Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are preferred glycerol esters herein. Suitable organic silver coating agents include triglycerides, mono or diglycerides, and hydrogenated derivatives thereof, wholly or in part thereof, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rape seed oil, grape seed oil, palm oil and corn oil. The waxes, including the microcrystalline waxes, are organic silver coating agents suitable herein. Preferred waxes have a melting point in the range of about 35 ° C to about 10 ° C and generally comprise about 12 to about 70 carbon atoms. Preferred are petroleum waxes of the paraffin and microcrystalline types which are composed of long chain saturated hydrocarbon compound. Alginates and gelatin are suitable organic silver coating agents that can be used in the compositions herein. Dialkylamine oxides such as methylamine oxide from about C12 to about C2o, and dialkyl quaternary ammonium salts, such as methylammonium halides from about C12 to about C2o are also suitable. Other suitable organic silver coating agents include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of about 12,000 to about 700,000, polyethylene glycols (PEG) with a molecular weight of about 600 to about 10,000 polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose are examples of such polymeric materials. Certain perfume materials, particularly those that demonstrate a high substantivity to metal surfaces, are also useful as organic silver coating agents herein. The polymeric soil release agents can also be used as organic silver coating agents.

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 about 20 to about 50; the paraffin oil selected from predominantly branched C25-45 species with a ratio of cyclic to non-cyclic hydrocarbons from about 1: 10 to about 2: 1, preferably about 1: 5 to about 1: 1. A paraffin oil meeting said characteristics, having a cyclic to non-cyclic hydrocarbon ratio of about 32:68, is sold by Wintershall, Saizbergen, Germany, under the trade name WINOG 70. Nitrogen-containing corrosion inhibiting compounds suitable include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139,279 and British Patent GB-A-1, 137,741, which also describe a method for manufacturing the compounds of imidazole Also suitable as nitrogen-containing corrosion inhibiting compounds are the pyrazole compounds and their derivatives, particularly those wherein the pyrazole is substituted at any of positions 1, 3, 4 or 5 by substituents R1, R3, R4 and R5 wherein Ri is any of H, CH 2 OH, CONH 3, or COCH 3, R 3 and R 5 which are any C 1 -C 20 alkyl or hydroxyalkyl, and R 4 is any of H, NH 2 or NO 2.

Other suitable nitrogen-containing corrosion inhibiting compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mechapto-1, 2,3,4-tetrazole, tionalide, morpholine, melanin, distearylamine, estearoate stearoyl, cyanuric acid, aminotriazole , aminotetrazole and indazole. Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrogen citrate are also suitable. The detergent tablets may contain a corrosion inhibiting compound Mn (ll). The compound Mn (ll) is preferably incorporated at a level from about 0.005% to about 5% by weight, most preferably from about 0.01% to about 1%, more preferably from about 0.02% to about 0.4% by weight of the compositions . Preferably, the compound Mn (ll) is incorporated at a level to provide from about 0.1 ppm to about 250 ppm, more preferably from about 0.5 ppm to about 50 ppm, even more preferably from about 1 ppm to about 20 ppm by weight of Mn ions (ll) in any bleaching solution. The compound Mn (ll) can be an inorganic salt in anhydrous form, or any hydrated form. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride. The compound Mn (ll) can be a salt or complex and an organic fatty acid such as manganese acetate or manganese stearate. The compound Mn (ll) can be a salt or complex of an organic ligand. In a preferred aspect the organic ligand is a heavy metal ion sequestrant. In another preferred aspect the organic ligand is a crystalline growth inhibitor. Other suitable additional corrosion inhibiting compounds include, mercaptans and diols, especially mercaptans, with from about 4 to about 20 carbon atoms including laurylmercaptan, thiophenol, tioneptol, tionalide and trionatranol. Also suitable are saturated or unsaturated C 10 -C 20 fatty acids, or their salts, especially aluminum tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Also suitable are phosphonated octa-decane and other antioxidants such as betahydroxytoluene (BHT). It has been discovered that butadiene and maleic acid copolymers, particularly those provided under commercial reference number 07787 by Polysciences Inc. are of particular utility as corrosion inhibiting compounds. Another preferred detergent active component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of about 20 to about 50.; the preferred hydrocarbons are saturated and / or branched; preferred hydrocarbon oil selected predominantly from branched C25_45 species with a ratio of cyclic to non-cyclic hydrocarbons from about 1: 10 to about 2: 1, preferably from about 1: 5 to about 1: 1. A preferred hydrocarbon oil is paraffin. A paraffin oil meeting the aforementioned characteristics having a cyclic to non-cyclic hydrocarbon ratio of about 32:68 is sold by Wintershall, Saizbergen, Germany, under the trade name WINOG 70. The detergent tablets of the present invention are suitable for use in dishwashing methods they may contain a water-soluble bismuth compound, preferably present at a level of from about 0.005% to about 20%, more preferably from about 0.01% to about 5%, still most preferably from about 0.1% to about 1% by weight of the compositions. The water-soluble bismuth compound can essentially be any bismuth salt or complex with essentially any inorganic or organic counter anion. Preferred inorganic bismuth salts are selected from the bismuth trihalogenides, bismuth nitrate and bismuth phosphate. Bismuth acetate and citrate are preferred salts with organic counter anion.

Colorant The term "colorant", as used herein, refers to any substance that absorbs the specific wavelengths of light from the visible light spectrum. Said colorants, when added to a detergent composition, have the effect of changing the visible color and thus the appearance of the detergent composition. The dyes can be, for example, any dye or pigment. Preferably the dyes are stable in composition e? which are 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 central layer, the first encapsulation layer and / or the second encapsulation layer may contain a dye, a mixture of dyes, colored particles or a mixture of colorful particles such that the compressed portion, the central layer, the first layer of encapsulation and / or the second encapsulation layer have different visual appearances. Preferably one of the core layer, the first encapsulation layer and / or the second encapsulation layer has a colorant. The central layer, the first encapsulation layer and / or the second encapsulation layer can also be of one color and contain particles or specks of another color. For example, the central layer may be white with blue specks, while the first encapsulation layer is blue. Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo, disazo and polyazo dyes. The most preferred dyes include antaquinone, quinoline and monoazo dyes. Preferred dyes include SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (trade name), TURQUOISE ACID BLUE (trade name) and SANDOLAN BRILLIANT GREEN (trade name) all available from Clariant RU, HEXACOL QUINOLINE YELLOW (trade name) ) and HEXACOL BRILLIANT BLUE (trade name both available from Pointings, UK, ULTRA MARINE BLUE (trade names available from Holliday or LEVAFIX TURQUISE BLUE EBA (trade name) available from Bayer, USA) In addition, it is preferred that the colorant does not cause visible spots on the plastic, such as the automatic dishwashing or plastic tableware, after a plurality of cycles, more preferably between 1 and 50 cycles.The dye can be incorporated in the central layer, the first encapsulation layer and / or the second encapsulation layer by any suitable method.The suitable methods include mixing the total detergent active components or selected with a dye in a cylinder or by spraying the active detergent components total or selected with the dye in a rotating cylinder. Alternatively, the dyes can be improved by pre-dissolving the dye in a compatible solvent prior to the addition of the dye to the composition. When the dye is present as a component of the compressed portion, it is present at a level of from about 0.001% to about 1.5%, preferably from about 0.01% to about 1.0%, most preferably from about 0.1% to about 0.3%. When present as a component of the coating layer, the colorant is generally present at a level of from about 0.001% to about 0.5%, more preferably from about 0.02% to about 0.1%, most preferably from about 0.03% to about 0.06% .

Foam suppression systems The detergent tablets of the present invention, when formulated for use in compositions for machine washing, preferably comprise a foam suppression system present at a level of 0.01% to 15%, preferably of 0.05% to 10%, most preferred of 0. 1% to 5% by weight of the composition. The foam suppression systems suitable for use in the present invention may comprise essentially any known antifoam compound, including, for example, silicone anti-foaming compounds and 2-alkyl and alkanol antifoaming compounds. Preferred foam suppression systems and antifoam compounds are disclosed in PCT Application No. WO93 / 08876 and EP-A-705324. The compositions of the invention may optionally contain an alkyl phosphate ester foams suppressant, a silicone foams suppressant, or combinations thereof. The silicone foam suppressor technology and other foaming agents useful herein are documented extensively in "Defoaming, Theory and Industrial Applications," Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-970-6, incorporated herein by reference. See especially the chapters entitled "Foam control in Detergent Products" (Ferch et al.) And "Surfactant Antifoams" (Blease et al.). See also E.U.A. No. 3,933,672 and 4,136,045. Highly preferred silicone foam suppressors are the types of compounds known for use in laundry detergents such as heavy duty granules, although the types hitherto used only in heavy duty liquid detergents may be incorporated into the compositions snapshots For example, polydimethylsiloxanes having trimethylsilyl units or alternating end block can be used just like silicone. The above can be compounds with silica and / or with components that do not have active surface silicon, as illustrated by a foam suppressor comprising 12% silicone / silica, 18% stearyl alcohol and 70% starch in granulated form . An adequate commercial source of the active silicone compounds is Dow Corning Corp.

If it is desired to use a phosphate ester, suitable compounds are described in the patent of E.U.A. No. 3,314,891, issued April 18, 1967, to Schmolka et al., Incorporated herein by reference. Preferred alkyl phosphate esters contain from 16-20 carbon atoms. Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof. It has been found that it is preferred to avoid the use of the simple calcium precipitation soaps as antifoams of the present compositions as they tend to be deposited on the dishes. In fact, the phosphate esters are not totally exempt from such problems and the formulator will generally select to minimize the antifoam content that is potentially deposited in the compositions of the present invention.

Enzyme stabilization system The preferred compositions herein containing enzyme may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6% by weight of a enzyme stabilization system. The enzyme stabilization system can be any stabilization system that is compatible with the detersive enzyme. Said stabilization systems may comprise calcium, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof. Said stabilization systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors. For another suitable stabilizer and enzyme systems see Severson, E.U.A. No. 4,537,706.

Lime soap dispersant compound The compositions of the active detergent components may contain a lime soap dispersant compound, preferably present at a level of from about 0.1% to about 40% by weight, more preferably from about 1% to about 20% by weight, most preferably from about 2% to about 10% by weight of the compositions. A lime soap dispersant is a material that prevents the precipitation of the alkali metal, ammonium salts or amine of fatty acids by the calcium or magnesium atoms. Preferred lime soap dispersant compounds are written in WO93 / 08877.Polymeric Dye Transfer inhibition agents The detergent tablets herein may also comprise from about 0.01% to about 10%, preferably from about 0.05% to about 0.5% by weight of polymeric dye transfer inhibition 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, optionally also contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4'-bis [(4-anilino-6- (N-2- bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular kind of brightener is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino -6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular kind of brightener is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula R- | is aniline, R2 is morphine and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bs [(4-anilino-6-morphino-s-triazin-2-yl) amino] ] 2,2'-isbenedisulfonic. This particular kind of brightener is marketed under the brand name Tinopal AMS-GX by Ciba-Geigy Corporation.

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

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

Attachments The detersive or adjunct ingredients optionally included in the instant compositions may include one or more materials to assist or encourage the development of cleaning, treatment of the substrate to be cleaned, processing aids, or designed to improve the aesthetics of the compositions. Attachments that may be included in the compositions of the present invention, at their established levels of conventional art for use (generally, the adjunct materials comprise, in total, from about 30% to about 99.9%, preferably about 70. % to about 95% by weight of the compositions), include other active ingredients such as color specks, fillers, rinse aids (such as nonionic surfactants, solvents, polymeric dispersants, etc.), germicides, hydrotropes, antioxidants, perfumes, solubilizing agents, vehicles and processing aids. Depending on whether a greater or lesser degree of compaction is required, the filler materials may also be present in the instant compositions. The above include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the composition. The preferred filler material is sodium sulfate, especially in good grades that have mostly low levels of trace impurities.The sodium sulfate used herein is preferably of sufficient purity to ensure that it is not reactive with the bleach; it can also be treated with low levels of sequestrants, such as phosphonates, or EDDS in the form of a magnesium salt. It should be noted that the preferences, in terms of sufficient purity to avoid bleach decomposition, also apply to the pH adjusting component ingredients, specifically including any silicate used herein. The detergent tablets may also contain processing aids that can aid in the production of the detergent tablets. For example, when the center, the first encapsulating layer and / or the second encapsulating layer are compressed it may contain a tacking aid, such as stearic acid, to increase the ease of removal of the compressed layers or center of the dice of a tableting machine Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulphonate, etc., may be present, for example, for the best dispersion of the surfactant. Perfumes stable to bleach (stable in terms of aroma); and bleach-stable dyes such as those described in the U.S.A. 4,714,562, Roselle et al., Issued December 22, 1987 can also be added to the present compositions in suitable amounts.

Because the compositions herein may contain water-sensitive ingredients or ingredients that can co-react upon contacting in an aqueous environment, it is desirable to keep the free moisture content to a minimum, for example, 7% or less, preferably 5% or less. % or less of the compositions; and to provide the package that is substantially impervious to water and carbon dioxide. The coating measures have been described herein to illustrate a form of protecting the ingredients from each other and against air and moisture. Plastic bottles, including re-fill or recyclable types, as well as conventional barrier cartons or boxes are other useful means of ensuring maximum shelf-storage stability. As noted when the ingredients are not highly compatible, it may also be desirable to coat at least one ingredient with a low foaming nonionic surfactant for protection. There are several wax materials that can be easily used to form suitable coated particles of any other incompatible component, however, the formulator prefers those materials that do not have a marked tendency to deposit or deposit films on plates including those of plastic construction.

Form of composition The detergent tablet can be in any conceivable form. The center, the first encapsulating layer and / or the second encapsulating layer may be the same or different in shape. The size of the tablet also remains similarly unrestricted. Preferably, the size is selected to facilitate storage, for ease of use and in such a way that the tablet is coupled to any delivery device used in cleaning, for example, the detergent dispenser in an automatic washing machine. The center, the first encapsulating layer and / or the second encapsulating layer can be regular or irregular. They can be of any regular or irregular geometric shape such as, concave, convex, spherical cubic, trunk of a cone, (a section of a cone), rectangular prism, cylindrical, disc, pyramidal, tetrahedral, dodecahedral, octahedral, conical, ellipsoidal , number 8, or rhombohedral. See CRD Standard Mathematical Tables, 26th Ed, Dr. William H. Beyer Editor, pages 127, 128 and 276 and 278. These may even be signs, symbols, cartoons, trademarks, images, such as corporate logos, characters of carvings, logos or team mascots. The list of possible forms is endless. When any part of the tablet has straight edges it is preferred that either edge be beveled or rounded. Additionally, when a part of the tablet has corners, it is preferred that the corners be round.

Procedure The multi-layer detergent tablet of the present invention can be made by any conventional process that produces an encapsulated multi-layer detergent tablet. These include, but are not limited to, molds, tableting, coating or spraying. For example, a center can be formed in a mold, then surrounded with the first encapsulating layer which is formed by a tablet press around the center, and finally the second encapsulating layer is sprinkled on the first encapsulating layer. The detergent tablets of the present invention are prepared by separately preparing the center, the first encapsulating layer and the second encapsulating layer and then combining them to form the multi-layer detergent tablet. When the center, the first encapsulating layer and / or the second encapsulating layer are a compressed solid, these are prepared by obtaining at least one active detergent component and optionally premixing with vehicle components. Any premix will be carried out in a suitable mixer, for example, a tray mixer, rotating cylinder, vertical mixer, or high cut mixer. Preferably, the dry particulate components are mixed 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 into the dry particulate components.

The resulting composition is then formed into a compressed solid in a compression step using any known suitable equipment. Preferably, the composition is formed as a compressed solid using a tablet press, wherein the tablet is prepared by compressing the composition between an upper and a lower die. In a preferred embodiment of the present invention, the composition is supplied in a die cavity of a tableting machine and compressed to form a compressed portion using a pressure preferably greater than 6.3KN / cm2, more preferably greater than 9KN / cm2, very preferably 14.4KN / cm2. As described in detail above in the present invention, when the center, the first encapsulating layer and / or the second encapsulating layer are not compressed the detergent active agent and any of the other ingredients in the center, the first encapsulating layer and / or The second non-compressed encapsulating layer is premixed using any known suitable mixing equipment. In addition, when the center, the first encapsulating layer and / or the second encapsulating layer are non-compressed, the non-compressed portion may optionally comprise a vehicle with which the active detergent components are combined. The center, the first encapsulating layer and / or the second non-compressed encapsulating layer are uncompressed portions that can be prepared in solid or fluid form. The non-compressed, non-encapsulating portion may be supplied to a mold, which may contain a center or a layer to be encapsulated, by manual delivery or by using a nozzle feed extruder or by any other suitable means. Preferably, the uncompressed material is supplied to the mold using an exact supply equipment, for example a nozzle feeder, such as a weight loss screw feeder available from Optimus Germany or an extruder. When the center, the first encapsulating layer and / or the second encapsulating layer is fluid and non-compressed and is in the form of particles, the method involves supplying a non-compressed, non-encapsulating fluid portion to the portion compressed in the delivery passage and then coating at least a portion of the non-compressed non-encapsulating portion with a coating layer such that the coating layer has the effect of substantially adhering the non-compressed portion to the compressed portion. Where the second encapsulating layer is non-compressible flowable it is fixed to the first encapsulating layer by hardening, the method comprises a delivery step in which the second encapsulating layer is supplied to the first encapsulating portion in such a way that the second encapsulating layer completely surrounds the first encapsulating layer and a subsequent conditioning step, where the second encapsulating is hardened. encapsulating layer not compressed. Said conditioning step may comprise drying, cooling, bonding, polymerization, etc. of the non-compressed, non-encapsulating portion during which the non-compressed, non-encapsulated portion becomes solid, semi-solid or highly viscous. The heat can be used in a drying step. The heat, or exposure to the radiation can be used to effect the polymerization in a polymerization step. This method can also be performed to surround the center when the first encapsulating layer is fluid and not compressed. The detergent tablets can be used in any conventional domestic washing process where detergent tablets are commonly used, including but not limited to automatic dishwashing and fabric washing.

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

Laundry Method The machine washing methods of the present invention typically comprise treating the laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a detergent tablet composition for washing in machine according to the invention. An effective amount of the detergent tablet composition means from 40g to 300g of product dissolved or dispersed in a wash solution with a volume of 5 to 65 liters, which are typical product d and volumes of wash solution commonly employed in conventional methods of washing clothes in machine. In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is loaded with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its volume capacity must be such as to be capable of containing sufficient detergent product as would normally be used in the washing method. Once the washing machine has been loaded with clothes, the dispensing device containing the detergent product is placed inside the drum. At the start of the wash cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the dispensing device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water . To allow the release of the detergent product during washing, the device may possess a number of openings through which the product can pass. Alternatively, the device may be made of a material that is permeable to liquid but impermeable to the solid product, which will allow the dissolved product to be released. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing high localized transient concentrations of the product in the drum of the washing machine at this stage of the wash cycle. Preferred dispensing devices can be reused and are designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Alternatively, the dispensing device may be a flexible container, such as a bag or sack. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it may be formed of a synthetic polymer material insoluble in water provided with an edge or seal seal designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 001 1501, 0011502 and 001 1968. A convenient form of frangible closure in water comprises a water soluble adhesive disp along and sealing an edge of a sack formed from a waterproof polymeric film such as polyethylene or polypropylene.

EXAMPLES The following non-limiting examples further illustrate the present invention. Exemplified compositions include automatic dishwashing and laundry compositions.

Abbreviations used in the examples In the detergent compositions, the abbreviated component identifications have the following meanings: STPP: Sodium tripolyphosphate Zeolite: Zeolite A Citrate: trisodium citrate dihydrate Bicarbonate: sodium hydrogen carbonate Citric acid: Anhydrous citric acid Carbonate : Anhydrous sodium carbonate Silicate: Amorphous sodium silicate (SiO2 ratio: Na2O = 1.6-3.2) Metasilicate: sodium metasilicate (Si? 2 ratio: Na2O = 1.0) PB1: Anhydrous sodium perborate monohydrate. PB4: Sodium perborate tetrahydrate of the nominal formula NaBO23H2O.H2O2.

TAED: Tetraacetyl ethylenediamine Plurafac: ethoxylated / propoxylated fatty alcohol mixed of C? 3-C-t5 with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the trade name Plurafac by BASF Tergitol: Surfactant no. ion available under the trade name Tergitol 15S9 from Union Carbide SLF18: Epoxy blocked poly (oxyalkylated) alcohol of Example III of WO 94/22800 wherein the 1- 2, epoxydodecane is replaced by 1,2-epoxydekane available under the name commercial Politergent SLF18D by OLIN HEDP: Ethan-1-hydroxy-1,1-diphosphonic acid DETPMP: Diethyltriamine penta (methylene) phosphonate, marketed by Monsanto under the trade name Dequest 2060 PAAC: Cobalt salt of pentaamine acetate III BzP: Benzoyl peroxide Paraffin : Paraffin oil sold under the trade name Winog 70 by Wintershall. Protease: Proteolytic enzyme Amylase: 480N amylolytic enzyme: 73 acrylate / methacrylate random copolymer, average molecular weight 3,500 Sulfate: PEG 3000 anhydrous sodium sulfate: Polyethylene glycol with molecular weight of approximately 3000 available from Hoechst PEG 6000: Polyethylene glycol with molecular weight of approximately 6000 Sugar: Domestic sucrose Gelatin: Gelatin type A, fluorescence resistance 65 available from Sigma CMC: Carboxymethylcellulose Acid C12 dodecandioic dicarboxylic acid: Adipic acid: C6 dicarboxylic acid Lauric acid: C12 monocarboxylic acid BTA: Benzotriazole PA30: Acid polyacrylic of average molecular weight of about 4,500 PH: Measured as a 1% solution in distilled water at 20 ° C EXAMPLE 1 A detergent tablet according to the present invention can be prepared in the following manner. A detergent composition as in example 2, formulation A was prepared and passed on a conventional rotary press. This forms the center of the tablet. A gel matrix formulation was then prepared as described in Example 2, formulation A. The appropriate amount of non-aqueous solvent was supplied to a mixer and the cut was applied to the solvent at a moderate speed (2,500-5,000 rpm). The appropriate amount of gelling agent was gradually added to the solvent under cutting conditions until the mixture was homogeneous. The cutting speed of the mixture was gradually increased to the high cut condition of around 10,000 rpm. The temperature of the mixture was increased to 55 ° C and 60 ° C. The cut was then stopped and the mixture could be cooled to temperatures between 35 ° C and 45 ° C. Using a low-cut mixer, the remaining ingredients were then added to the mixture as solids. The final mixture was then dosed into the mold containing the compressed solid center. The center is surrounded by the first encapsulating layer. The tablet is allowed to stand until the gel hardened or was no longer flowable. The second encapsulating layer is then sprinkled on the tablet, encapsulating the first encapsulating layer.

EXAMPLE 2 A detergent tablet according to the present invention can be prepared in the following manner. A gel matrix formulation was prepared as described in Example 2, formulation A. The appropriate amount of non-aqueous solvent was supplied to a mixer and the solvent cut was applied at a moderate speed (2,500-5,000 rpm). The appropriate amount of gelling agent was added gradually to the solvent under cutting conditions until the mixture was homogeneous. The cutting speed of the mixture was gradually increased to the high cut condition of around 10,000 rpm. The temperature of the mixture was increased to 55 ° C and 60 ° C. The cut was then stopped and the mixture could be cooled to temperatures between 35 ° C and 45 ° C. Using a low-cut mixer, the remaining ingredients were then added to the mixture as solids. The final mixture was then dosed into the mold with the desired shape and allowed to stand until the gel hardened or was no longer flowable. 1. Enzyme protease can be Savinase® or as described in the document of E.U.A. 5,677,272. 2. Amylase enzyme as described in the Novo Nordisk PCT / DK96 / 00056 application and was obtained from the alkalophilic Bacillus species having an N-terminal sequence of His-His-Asn-Gly-Thr-Asn-Gly-Thr -Met- Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp, or Termamyl®. 3 PM 4,000-8,000. 4. Water soluble SKS-6 silicate.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A multi-layer detergent tablet containing: a) a center having a first detergent active agent; b) a first encapsulating layer surrounding said center, having a second active detergent agent; c) a second encapsulating layer surrounding said first encapsulating layer, having a third detergent active agent and a disintegration system; characterized in that the disintegration of said second encapsulating layer is such that at least 25% of said third active detergent agent is released before said second detergent active agent is released.

2. A multi-layer detergent tablet containing: a) a center having a first detergent active agent; b) a first encapsulating layer surrounding said center, having a second active detergent agent; c) a second encapsulating layer surrounding said first encapsulating layer, having a third detergent active agent and a disintegration system; characterized in that the disintegration of said second encapsulating layer is such that said third active detergent agent is released at least 2 minutes before said second detergent active agent is released.

3. - A multi-layer detergent tablet containing: a) a center having a first detergent active agent; b) a first encapsulating layer surrounding said center, having a second active detergent agent; c) a second encapsulating layer surrounding said first encapsulating layer, having a third detergent active agent and a disintegration system; characterized in that the disintegration of said second encapsulating layer occurs in an aqueous cleaning environment at a temperature of 25 ° C or less and wherein the release of said second detergent active agent occurs in an aqueous cleaning environment at a temperature of 30 ° C. ° C or greater.

4. A multi-layer detergent tablet according to any of claims 1 to 3, further characterized in that said first detergent active agent is selected from the group consisting of surfactants, bleaching systems, chelators, bleach scrubbers, suppressant system foam, enzymes, detergency builders, polymeric dispersants, silver care agents, silicates, pH regulators, soil release agents, corrosion and glass care inhibitors and mixtures thereof. <

5. A multi-layer detergent tablet according to any of claims 1 to 4, further characterized in that said second detergent active agent is selected from the group consisting of surfactants, bleaching systems, chelators, bleach scrubbers, suppressant system foam, enzymes, detergency builders, polymeric dispersants, silver care agents, silicates, pH regulators, soil release agents, corrosion and glass care inhibitors and mixtures thereof.

6. A multi-layer detergent tablet according to any of claims 1 to 5, further characterized in that said third active detergent agent is selected from the group consisting of surfactants, bleaching systems, chelators, bleach scrubbers, suppressant system foam, enzymes, detergency builders, polymeric dispersants, silver care agents, silicates, pH regulators, soil release agents, corrosion and glass care inhibitors and mixtures thereof.

7. A multi-layer detergent tablet according to any of claims 1 to 6, further characterized in that said third detergent active agent is an enzyme, said second detergent active agent is a bleaching system and said first detergent active agent is a nonionic surfactant and a polymeric dispersant.

8. A multi-layer detergent tablet according to any of claims 1 to 7, further characterized in that said first layer contains a disintegration system and is such that at least 25% of said second detergent active agent is released before said first detergent active agent is released.

9. A multi-layer detergent tablet according to any of claims 1 to 8, further characterized in that said third active agent is a low pH enzyme and said second active agent is a high pH enzyme.

10. A multi-layer detergent tablet according to any of claims 1 to 9, further characterized in that said first active agent is a rinse aid.

11. A method for washing tableware in a domestic washing machine for automatic dishwashing, said method comprising treating the soiled tableware in an automatic dishwasher with said multilayer detergent tablet according to any of claims 1 to 10.

12. A method for washing fabrics comprising said method treating the fabrics with said detergent tablet according to any of claims 1 to 10.