MXPA01007418A - Improved detergent compositions comprising hybrid zeolite builders - Google Patents

Abstract

Built laundry detergent compositions, especially granules, powders, tablets or syndet bars for domestic use, wherein the builder comprises at least in part a hybrid crystalline aluminosilicate having occluded silicate, carbonate, sulfate, phosphate, borate, nitrate, nitrite, Na2O, or mixtures thereof;and wherein the hybrid can further be chemically or physically surface-modified, combined with other builders, or processed in particular ways;and wherein the hybrid is coformulated with detergent adjuncts selected to improve the compositions, especially certain surfactants, particularly mid-chain branched types;certain bleach systems, especially those having bleach catalysts;and certain enzymes or other adjuncts.

Description

IMPROVED DETERGENT COMPOSITIONS COMPRISING ZEOL1TA HYBRID DETERGENT IMPROVERS TECHNICAL FIELD This invention relates to detergents with builder for domestic use, especially having granular form, tablets or synthetic detergent bar. The compositions contain particular aluminosilicate builders, preferably aluminosilicate hybrids and specific occluded matepals such as silicate, carbonate, sulfate, phosphate, borate, nitrate, nitrite, Na2, or mixtures thereof. The builder can be modified on its surface or it can be processed in a particular way. The compositions also contain selected detergent auxiliaries, such as certain surfactants, enzymes, polymers and / or bleaches. Other auxiliaries may also be present, for example, conventional surfactants, enzymes, detergency builders or bleaches.

BACKGROUND OF THE INVENTION The formulation of detergent builders of zeolite in detergents is technically difficult. The zeolites formulated so far in detergents lack an ideal combination of low cost, ease of manufacture, high equilibrium binding of both Ca and Mg, fast binding kinetics for Ca and Mg and ability to contain large amounts of surfactant. Zeolites or aluminosilicates, when added to laundry detergents, may interact adversely with numerous laundry detergent auxiliaries, for example, bleaches, bleach catalysts, enzymes, brighteners and other additives, and / or produce unacceptable effects and / or give other important problems such as redeposition on textiles. Another important technical problem is a strong tendency for low-level auxiliaries or differently charged additives such as cationic surfactants, catalysts or enzymes to adsorb onto relatively large anionically charged surfaces of insoluble inorganic builders. Since such auxiliaries are often expensive and tend to be used at relatively low levels in detergent compositions, their loss by any mechanism, such as interaction with the detergency builder, can have drastic effects on the overall cleaning performance. Therefore, substantial and expensive research and experimentation is needed to integrate a synthetic inorganic builder material with other detergent ingredients for the benefit of their properties and at the same time prevent the cancellation or reduction of the desirable effects of the auxiliaries with which they are used. formula. Such experimentation often produces failures. Therefore, there is a need for fully formulated detergent compositions that accept synthetic inorganic builders in an acceptable manner, especially certain types for which only synthetic methods have been recently described.

TECHNICAL BACKGROUND WO 98/42622 of Englehard Corporation, published on October 1, 1998, provides methods for preparing certain hybrid zeolite-silicate compositions. These materials do not contain hydroxisodalite, in fact a comparison is given to demonstrate the absence of it. Some detergent formulations using hybrid aluminosilicates are also described. The resolution of the problems of formulating these hybrid detergency builders, especially with certain high cost ingredients, low level of potential interaction, are nevertheless not specifically addressed. It seems to be assumed that the zeolite-silicates hydrated detergency builders can be formulated simply as a replacement for the current zeolites, and the teaching of the formulation is for conventional zeolite detergents. However, according to the theory of operation described in WO 98/42622, the hybrid material has a higher load. Either for this reason or due to some other theory of operation, it has now been discovered that the hybrid materials of WO 98/42622 do not have the same properties for detergent formulation purposes as the conventional detergent zeolite, zeolite A.

Although WO 98/42622 provides apparently useful synthetic methods, and the evidence provided in WO 98/42622 strongly suggests that the hybrid material of WO 98/42622 is different from zeolite MAP, whether this hybrid material or occluded by silicate is a novel fact may or may not be the case. There is a substantial amount of prior art about the manufacture of zeolite that is not in computer readable form and as such is relatively difficult to find and / or search. An accessible fraction of this technique includes description of occluded or hybrid type zeolites (using the language of WO 98/42622) or hybrid aluminosilicates having occluded salts of various types, and recommendations that the occlusion is well known to zeolite manufacturers . For example, occluded zeolites are described in "Zeolite Chemistry and Catalysis," Ed, JA Rabo, ACS Monograph Series, Vol. 171, American Chemical Society, Washington DC, 1976. See more particularly Chapter 5, "Salt Occlusion in Zeolite. Crystals ", pages 332-349 and references cited therein, see also chapter 1 of the same reference. In this way, said materials include, for example, zeolite A occluded with sodium nitrate or with another nitrate salt, see the work referenced by Liquornik and Marcus. See also chapter 1, pages 58-63 of the same ACS monograph, which describes, for example, zeolite A occluded with NaAI02; other occluded aluminosilicates, such as sodalite occluded with borate, sodalite occluded with NaOH, cancrinite occluded with Na 2 C 3 -, zeolite Y occluded with halide or nitrate, and other zeolites occluded with salt. In chapter 4 of the ACS monograph, it was indicated "another consequence of the Donnan equilibrium is that electrolytic invasion may occur.In this procedure, the anions of the aqueous phase enter the zeolite phase with a correspondingly equivalent number of additional cations. " See also chapter 4 of the same ACS monograph on pages 310-111, for example, the statement "Modified varieties of many zeolites can be prepared by occlusion of foreign species with the zeolite crystal either during synthesis or after the same". Reference is made to the work of Barrer and others. In chapter 5 on page 338, reference is made to zeolite A occluded with borate. In brief, various occluded aluminosilicate materials are described in the art. Surprisingly, on the other hand, in other citations than WO 98/42622, there seems to be no specific description of the use of occluded or hybrid type zeolites or other occluded aluminosilicates in detergent compositions. Therefore, it is against an antecedent of (a) an apparent plurality of zeolite occlusions coupled with (b) a lack of teaching about how to formulate occluded or hybrid-type aluminosilicate materials in detergents other than a simple substitute for zeolite A or P as taught in WO 98/42622, which is provided in the present invention. In addition, by means of background information about zeolites and occluded zeolites, the expert should refer to D.W. Breck, "Zeolite Molecular Sieves", Wiley, New York, 1974 and Kirk Othmer's Encyclopedia of Chemical Technology, 4a. edition, 1995, Wiley, New York, see Vol. 16, "Molecular Sieves". Builders in general are described in many patents issued to Procter & Gamble, Unilever, Hoechst / Clariant, Kao, Lion, Crosfield, PQ Corp., and others. A recent review in the detergent context is included in the Surfactant Science Series, Marcel Dekker, New York, see Vol. 17, Ed. M.S. Showell, published in 1998. See more particularly chapter 3, "Builders: The Backbone of Powdered Detergents" by Hans-Peter Rieck of Hoechst / Clariant. All percentages herein are by weight of the detergent composition unless otherwise indicated. All references references are incorporated herein by reference in their entirety. The ratios and proportions are by weight unless specifically indicated otherwise.

BRIEF DESCRIPTION OF THE INVENTION In a first aspect or embodiment of the invention, it has now been discovered that improved detergent compositions beyond those described in WO 98/42622 can be formulated by combining zeolite-silicates hybrid builders WO 98/42622 with particular detergent ingredients.

In a second aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with some hybrid zeolite co-builders not specifically described in WO 98/42622. In these materials, the hybrid builder has an occluded material other than silicate, such as sulfate, borate, nitrate, nitrite, phosphate or Na2 ?. In a third aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with combinations of builder zeolite-silicate builders and hybrid zeolite co-builder systems wherein these combinacinoes are not described in WO 98. / 42622. In these systems, the hybrid builder has as much occluded silicate as other material other than the occluded silicate, especially an anion having a charge greater than 1, such as occluded sulfate, occluded borate, occluded phosphate, although occluded nitrate, nitrite is possible occluded or mixtures of any of the aforementioned co-builders. In other variations, alkali metal oxides or hydroxides, such as Na 2? or NaOH, are present with excellent results. In a fourth aspect or embodiment of the invention, improved detergent compositions are formed by combining detergent ingredients with any of said hybrid zeolite-silicate builder or hybrid zeolite co-builder systems, wherein the zeolite-builder The hybrid silicate or the occluded system of hybrid zeolite co-builder is subsequently modified by chemical or physical modification of the external surfaces. Such modification can vary widely, from a chemical approach, such as surface silylation or treatment with reactive aminosilicones, to a physical approach, such as direct contact of the hybrid with PEG, e.g., PEG 4000, nonionic waxy surfactants. , film forming polymers as defined in more detail below or combinations of chemical and physical treatment. The surface treatment aid can improve one or more aspects of cleaning or care of fabrics when the treated hybrid is included in a detergent formulation. For example, the hybrid treated when formulated with low level cationic surfactant co-agents, transition metal bleach catalyst enzymes or the like, can be shown to have a reduced tendency to interfere with the cleaning performance of such desirable auxiliaries. In a fifth aspect or embodiment of the invention, detergent compositions are formed by combining detergent ingredients with any of the hybrid materials in the presence of harmless fillers or common inorganic pigments, including in particular non-zeolitic aluminosilicates such as hydroxisodalite and / or talc and / or bleaches such as titanium dioxide. The hydroxyisodalite or other filler or bleach or mineral may be present in the hybrid, for example, through crystal imperfections, it may be present in the builder, or it may be introduced together with other detergent auxiliaries. Although these filled detergent compositions can be expected to be significantly worse for cleaning than non-filled types of compositions, they are surprisingly effective, for example, in laundry bars. Without being limited by theory, the absolute magnitude of the cation exchange capacity and even the sequestration rate of builder materials are not the only factors to be considered in order to obtain excellent detergent compositions. Dipping and wetting speeds can also be important, and the characteristics of material processing. In this way, although the introduction of materials such as hydroxisodalite and the aforementioned hybrid surface treatments may not be added to the capacity of the technical measurable builder, through these other factors, the filler and / or treatment material of surface can lead to improved detergent compositions. This is particularly true when problems such as redeposition are faced through the co-formulation of the hybrid builder with other selected detergent auxiliaries. Therefore, the present invention has numerous advantages, including improved laundry cleaning and / or antiredeposition performance and / or improved cost effectiveness compared to the cleaning and / or anti-redeposition performance offered by WO 98/42622 alone. Other important advantages are the improved compatibility of the improved ingredients, for example, a reduced tendency of the hybrid detergent builder to interact negatively with co-formulated detergent ingredients.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The present invention includes a detergent composition comprising: (a) from about 0.1% to about 99% of a builder system comprising, in part, a particulate inorganic ion exchange builder material, said enhancer material of detergency comprising a hybrid detergent builder of crystalline zeolitic aluminosilicate and at least one occluded co-builder which is not silicate; and (b) from about 0.1% to about 99% detergent auxiliaries. Preferably, in such embodiment, the hybrid builder comprises from about 0.01 to 1.0, most preferably 0.10 to 1.0, weight fraction of said builder system and said hybrid is characterized by an ability to sequester calcium in excess of the amount of aluminum load inductor in the zeolitic aluminosilicate. Alternatively, said hybrid is characterized by a calcium ion exchange capacity of at least 15% higher, preferably at least 20%, most preferably at least 25% higher than the calcium ion exchange capacity of a reference material selected from zeolite A not hybridized. Said reference zeolite A in fully-exchanged form with Na has a theoretical cation exchange capacity of about 7 meq / g, typically 5-7 meq / g, for example 6 meq / g in practice. Said material for reference purposes suitably has a particle size of from about 1 millimeter to about 10 microns. The occluded non-silicate co-builder can be selected from (i) the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitrite, occluded sulfate, Na2? occluded and mixtures thereof; and (ii) mixtures of said occluded co-builder that is not silicate and occluded silicate; provided that in any of said occluded co-builder mixtures that is not silicate and occluded silicate the weight fraction of occluded silicate is not greater than about 0.99, preferably not more than about 0.80. The invention also comprises a detergent composition containing: (a) from about 0.1% to about 99% of a builder system comprising, in part, a particulate inorganic ion exchange builder material, said enhancer material detergency comprising a crystalline aluminosilicate hybrid and an occluded co-builder, said hybrid builder further comprising at least one adsorbed or chemically bonded co-builder or an auxiliary other than the occluded co-builder; and (b) from about 0.1% to about 99% of detergent auxiliaries other than any auxiliary of said detergency builder system. EJ co-builder adsorbed or chemically bonded externally or auxiliary can be an auxiliary detergency builder or an auxiliary that does not contain builder. When the externally bonded or auxiliary chemically bonded co-builder which is an auxiliary that does not contain builder, preferably reduces the negative surface charge of the hybrid relative to the untreated hybrid, whereby said component (a) has compatibility improved with cationically charged surfactants and / or enzymes. When said hybrid surface treatment is put into practice, the detergent composition of the invention can easily accommodate a detergent auxiliary comprising at least one cationic detersive surfactant. Other detergent auxiliaries may be present, such as at least one anionic detersive surfactant especially the half-chain branched types, in addition to said cationic detersive surfactant. In general, said occluded co-builder is selected from the group consisting of occluded silicate co-builder, co-builder that does not contain occluded silicate, and mixtures thereof. Therefore, there are preferred embodiments wherein said occluded co-builder is an occluded silicate co-builder, said embodiments include those in which the hybrid is completely in accordance with the Engelhard patent publication identified above.

However, the invention also encompasses embodiments wherein said occluded co-builder is selected from the group consisting of occluded co-builder that does not contain silicate and mixtures of occluded co-builder that does not contain silicate and co-builder. silicate occluded detergency builder, and wherein said occluded co-builder that does not contain silicate is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitrite, occluded sulfate, Na2? occluded and mixtures thereof. In this case, some occluded zeolites known in the art, outside the previously identified Engelhard publication, are useful herein. Said occluded zeolites are not known to the inventors to have been used in any laundry detergent, especially granular or modern high density tablet detergents. In another embodiment, the present invention encompasses a detergent composition comprising: (a) from about 0.1% to about 99% of a builder system comprising, in part, a particulate inorganic ion exchange builder material , said builder material comprising a crystalline aluminosilicate hybrid and an occluded co-builder; and (b) from about 0.1% to about 99% of at least one detergent aid selected from the group consisting of: (i) detersive surfactants having at least one biodegradable branched hydrophobe; (ii) organic polymeric materials selected from the group consisting of oligomeric esters blocked at the ends; hydrophobically modified polyacrylates, terpolymers compenising maleate or acrylate, poiimeric dye transfer inhibitors, polyimine derivatives and mixtures thereof; (iii) oxygen bleach promoter materials selected from the group consisting of organic bleach activators, transition metal bleach catalysts, photobleaching agents, bleach promoting enzymes and mixtures thereof; (iv) fabric care promoting agents other than softeners or said organic polymeric materials; and (v) mixtures of (i) - (iv). In this latter embodiment, the hybrid preferably comprises at least about 0.01 weight fraction of said builder system and wherein said occluded co-builder is selected from the group consisting of an occluded silicate co-builder, occluded detergency improver which is not silicate and mixtures of said silicate occluded co-builder and said occluded co-builder which is not silicate; and wherein said occluded non-silicate co-builder, when present, is at a weight ratio to the silicate occluded co-builder of from about 1: 1000 to about 1000: 1 and is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitrite, occluded sulfate, Na2? occluded and mixtures thereof. The builder system itself can be varied. Therefore, a detergent composition as defined above is included wherein said hybrid comprises at least about 0.10 weight fraction of said builder system and wherein from about 0.10 to about 0.90 weight fraction of said improving system of detergency is selected from the group consisting of zeolite A, zeolite B, zeolite P, zeolite MAP, zeolite X, zeolite AX, clays, layered silicates, chain silicates, soluble silicates, citrates, nitrilotriacetates, ether carboxylates (preferably carboxymethyloxysuccinate, tartrate- monosuccinate, tartrate disuccinate, oxydisuccinate or mixtures thereof), carbonates (preferably sodium carbonate and / or sodium bicarbonate), polyacetal carboxylates and mixtures thereof. Amino-functional variants of the ether carboxylates can also be used (desirably for cost reasons at least 80% by weight of the soluble or interchangeable cations inherent in the builder system are sodium, however, other soluble cations, especially potassium, can be include at varying levels and calcium and / or magnesium may also be present Magnesium silicate in particular may be used as a co-builder or as a desirable auxiliary for processing reasons). Other highly desirable detergent compositions comprise the hybrid co-builder along with a builder material specified as described in more detail below. As noted, the invention comprises embodiments wherein the hybrid is in accordance with the previously identified Engelhard patent, and other embodiments wherein the hybrid is not according to Engelhard.

Said modalities include any detergent composition wherein the builder system has measurable hydroxisodalite as evidenced by peaks 14.0, 24.3 and 25.1 degrees 2 teta in the powder pattern of XRD of the builder system taken as a whole; or where the hybrid has measurable hydroxisodalite as evidenced by peaks at 14.0, 24.3 and 25.1 degrees 2 teta in the XRD powder pattern of the hybrid examined as such. In certain especially preferred embodiments, the detergent compositions incorporate biodegradable branched detersive surfactants. These embodiments include detergent compositions wherein said detergency aid comprises at least one detersive agent having at least one biodegradable branched hydrophobe, said surfactant being selected from C8"Ci8 alkyl sulfates branched with C1-C4 at half the chain. , alkoxy alcohols of Cd "Ci8 ethoxylated, propoxylated or butoxylated branched with C-1-C4 in the middle of the chain, C6-C-js alkylethylsulfates branched with C-1-C4 in the middle of the chain, alkylbenzene sulphonates of CQ -C ^ Q branched with C-1-C4 in the middle of the chain and mixtures thereof; and wherein said detersive surfactant is present at a level of from about 0.1% to about 30% by weight of said detergent composition. The invention is very tolerant to variations in quality of the hybrid material. Therefore, the invention includes detergent compositions wherein said hybrid builder material has a capacity to sequester calcium anywhere in excess of the amount of charge inducing aluminum in the crystals of the hybrid builder material. Preferably, however, said builder material is characterized by a calcium ion exchange capacity of at least 25% greater than the calcium ion exchange capacity of a reference material selected from unhybridized zeolite A. Also in the preferred embodiments, the total SIO2 in said hybrid builder material can be 1.02 to 1.50 times the SIO2 of the working frame as determined by comparison of X-ray diffraction, X-ray fluorescence and 29Si NMR analysis. In another preferred embodiment, the invention includes a detergent composition comprising: (a) from about 0.1% to about 99% of a builder system comprising, in part, a particulate inorganic ion exchange builder material comprising a hybrid of crystalline aluminosilicate and occluded silicate having a ratio of SIO2 / AI2O3 below 3 and formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12, said silicate solution having been at least partially depoiimerized by heating prior to the addition of said aluminum source; and (b) from about 0.1% to about 99% of at least one detergent aid selected from the group consisting of: (i) detersive surfactants having at least one biodegradable branched hydrophobe; (ii) organic polymeric materials selected from the group consisting of oligomeric esters blocked at the ends; hydrophobically modified polyacrylates, terpolymers compenising maleate or acrylate, polymeric dye transfer inhibitors, polyimine derivatives and mixtures thereof; (iii) oxygen bleach promoter materials selected from the group consisting of organic bleach builders, transition metal bleach catalysts, photobleaching agents, bleach promoting enzymes and mixtures thereof; (iv) fabric care promoting agents other than softeners or said organic polymeric materials; and (v) mixtures of (i) - (iv). In these modalities, the step of depolymerizing the sodium silicate solution preferably consists of heating at temperatures of 50 ° C to 85 ° C for a period of 10 minutes or more. Said embodiments include those in which the composition comprises soluble silicate as a non-occluded co-builder and wherein the total level of soluble silicate in said composition as a whole is limited, and is preferably not greater than the equivalent of about 3% by weight of the sodium silicate composition 2.0r. Also included are compositions in which the hybrid has measurable hydroxisodalite as evidenced by an XRD powder pattern; the compositions wherein said builder system comprises the particulate hybrid aluminosilicate material together with at least one traditional builder material, at a ratio of hybrid aluminosilicate to tradiiconal builder material from 5: 1 to about 1: 5.; compositions comprising as an auxiliary at a low chelator level (preferably less than about 2% by weight of the composition, most preferably from about 0.1% to about 1.5%; highly preferred chelators include DTPA, EDTA, S, S'- EDDS and mixtures thereof); compositions comprising as an auxiliary a double chelator system having at least one aminofunctional chelator that is not phosphonate and at least one functional phosphonate chelator; and compositions comprising as an auxiliary a low level of polycarboxylate polymer (preferably a Murphy type system, low polymer levels, eg, less than about 2%). The present invention has other embodiments and ramifications, such as a detergent composition comprising: (a) from about 0.1% to about 99% of a builder system comprising, in part, an ion exchange builder material particulate inorganic comprising a hybrid of crystalline aluminosilicate and and occluded co-builder, said hybrid having a ratio of SIO2 / AI2O3 below 3 and formed by a process comprising the step of adding an aluminum source to a solution of concentrated silicate having a pH above 12, said silicate solution having been at least partially depolymerized by heating before the addition of said aluminum source and in addition, optionally but preferably, at least one source of co-builder occludable that is not silicate that has been added in any step and / or in addition, optionally but preferred at least one surface treatment agent that has been applied to the external surfaces of said hybrid after the formation thereof; subject to at least one of the following considerations with respect to the composition of said builder system: - the builder system has measurable hydroxisodalite as evidenced by peaks at 14.0, 24.3 and 25.1 degrees 2 teta in the dust pattern of XRD of the detergency builder system taken as a whole and / or - the hybrid has measurable hydroxyisodalite as evidenced by the peaks at 14.0, 24.3 and 25.1 degrees 2 teta in the XRD powder pattern of the detergency builder system taken as such and / or - the hybrid has occluded co-builder that is not silicate as directly and / or indirectly evidenced by any combination of elemental analysis, XRD powder pattern, 29s / NMR or other known techniques and / or - the hybrid has measurably different surface wetness and / or caraga compared to an untreated hybrid on its surface; and (b) from about 0.1% to about 99% of at least one detergent auxiliary.

In certain preferred examples of said compositions, the hybrid comprises occluded silicate; wherein said hybrid is characterized by peaks of 29 if NMR on the scale of -81 to -85 ppm. In other preferred examples of such compositions, said detergent composition has the form of a laundry bar, tablet, granule or low density powder, granule or high density powder (eg,> 600 g / liter), paste or gel or liquid having dispersed solids, wherein said hybrid has a measurable improvement in the sum of calcium binding and magnesium binding as compared to zeolite A, delta-layered silicates and mixtures thereof. Moreover, the present invention encompasses a detergent composition comprising: (a) from about 0.1% to about 99% of a builder system comprising, in part, a particulate inorganic ion exchange builder material that it comprises a hybrid of crystalline aluminosilicate and and occluded co-builder, said hybrid having a Si? 2 / Al2? 3 ratio below 3 and formed by a process comprising the step of adding an aluminum source to a solution of concentrated silicate having a pH above 12, said silicate solution having been at least partially depolymerized by heating before the addition of said aluminum source and in addition, optionally but preferably, at least one source of co-builder occludable that is not of silicate that has been added in any step and / or in addition, optionally but preferably, at least one agent of surface treatment that has been applied to the external surfaces of said hybrid after the formation thereof; and (b) from about 0.1% to about 99% of at least one detergent auxiliary; provided that said detergent composition has a solid form and the process for preparing the detergent composition comprises at least one step of combining said hybrid material with a film-forming polymer. Also included in the invention are detergent compositions as generally described above wherein the hybrid material has measurably different wetting and / or surface loading as compared to an untreated hybrid on its surface. In a preferred embodiment of said compositions, the detergent composition is included wherein the hybrid material has measurably different wetting and / or surface loading as compared to the untreated hybrid on its surface; and wherein said measurable difference is achieved by the step of treating the hybrid material with PEG or a film-forming polymer.

Detergency metering system In more detail, the present invention includes detergent compositions having a builder system. A "builder system", as defined herein, comprises one or more detergent ingredients known in the art as "builders", provided that at least one "hybrid" or "occluded" aluminosilicate builder is included. as defined in more detail later. In certain embodiments, the builder system differs from the builder systems described in WO98 / 42622 in that the hybrid builder material is different from the hybrids in W098 / 42622. In other embodiments, the builder system may be identical to those described in WO98 / 42622. However, in this circumstance, the detergent compositions of the present invention have additional enhancer characteristics that derive from the selection of auxiliarand / or the processing method. To a minimum, a "detergency builder system" as defined herein, must have at least one ingredient that helps control the hardness of the water. "Water hardness" includes calcium without forming complex that is generated from water and / or dirt in dirty fabrics; very generally and typically, "water hardness" also includes other non-complex cations that have the potential to precipitate under alkaline conditions, especially the alkaline earths, most particularly magnesium. Well known conventional detergency builders include sodium tripolyphosphate, a "soluble complexing builder" which has a range of functions and benefits beyond the formation of calcium complex, such functions include, for example, peptization of diseases inorganic Another well-known detergency builder is zeolite A, especially zeolite A of 0.01-10 microns in the sodium form. This builder is a relatively insoluble crystalline material, which functions by ion exchange and is sometimes referred to as an "ion exchange builder." Another well-known detergency builder is sodium carbonate. Sodium carbonate functions as a "precipitant builder" - it reduces the hardness of water by forming one or more types of insoluble complex, such as calcium carbonate. The builder systems herein can generally include one or more water-soluble complexing builders and / or one or more ion exchange builders and / or one or more precipitator builders, provided that an essential hybrid component is present as defined below. The builder systems described in the art often also include transition metal binding materials known as chelators, and / or organic polymers, such as sodium polyacrylate, which have a builder function, however for the purposes of unambiguous consideration for materials in the present formulations, the convention of considering separately chelators and those organic polymers that have a detergency builder function-will be added with auxiliary detergents added separately. This is for purposes of formula consideration and does not exclude that said materials, in practice, are coprocessed with the "builder system", for example in high density agglomerated particles.

Typical builder systems of the present are further illustrated by: a builder system comprising a hybrid as defined below, together with a layered silicate and sodium carbonate; - a builder system comprising a hybrid as defined below, together with sodium tripolyphosphate - a builder system comprising a hybrid as defined below, together with sodium carbonate and a member selected from the group consisting of of sodium oxydisuccinate, sodium carboxymethyloxysuccinate, sodium nitrilotriacetate, sodium citrate and mixtures thereof; - a builder system comprising a hybrid as defined below, together with zeolite A and sodium carbonate; and - a builder system comprising a hybrid as defined below, having a film-forming polymeric coating, optionally together with one or more of zeolite A, sodium carbonate and sodium citrate (recall that in such case, the level of polymer for purposes of formula consideration is considered in the detergent auxiliary outside the builder system). In terms of essential component, the detergent compositions and builder systems herein are required to include at least one inorganic ion exchange builder material in crystalline particles and at least one occluded co-builder. The term "hybrid" indicates that the aluminosilicate and co-builder are integrated in the same crystal, other than a simple mixture of crystals separated from the components. The term "occluded" furthermore characterizes the location of one material in relation to the other by specifying that the builder builder is included instead of simply externally on the aluminosilicate crystals. The term "hybrid" can be used here as an abbreviated term; when disqualified, it comprises all crystalline aluminosilicates in suitable particles, which have any type of occluded mateial that helps the performance of the detergent. In alternative terms, the detergency builder materials "hybrids" or "occluded" herein also encompass all those zeolite compositions composed of a builder co-detergent and a zeolite useful as a builder, provided that the composition is the product of a process comprising the step of adding a source of aluminum to a solution of concentrated silicate or silicate builder solution having a pH above 12, said silicate solution or silicate builder solution having been at least partially depolymerized, preferably heating, before of the addition of said aluminum source. In such compositions, the builder co-builder may vary widely and includes phosphate, carbonate, borate, nitrate, nitrite, sulfate, Na2, NaOH and mixtures thereof. This alternative definition emphasizes that the present invention is not limited to a particular theory of operation. In general, the hybrid builder materials herein can be categorized into a number of different classes, depending on the material that is occluded in the aluminosilicate crystals. (a) hybrids comprising occluded silicate; (b) hybrids comprising occluded occluded detergency builder that is not silicate; (c) hybrids comprising occluded silicate and occluded builder which is not silicate. The hybrid builder materials may vary depending on the type of crystal, whereby the hybrids of the present may generally be hybrids based on type of zeolite A crystal, a type of zeolite P crystal or gismondin, type AX, or any other known type of crystal that is associated with ion exchange aluminosilicate materials. Hybrids comprising occluded silicate include those of WO 98/42622, Engelhard, which are described in detail later. Hybrids comprising occluded non-silicate co-builder include particulate crystalline aluminosilicates having occluded material selected from the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitrite, occluded sulfate, Na2 ? occluded, occluded NaOH and mixtures thereof. The adjective "occluded" is used to emphasize that not only the selected material will be present but it must be located in the aluminosilicate crystals. The precise location may vary, although in most cases, it is believed that at least a portion of occluded material lies outside the smaller zeolite cages while it is at least partly within the larger zeolite cages. Hybrid mixtures can generally be used in any proportion. Such mixtures include mixtures of a hybrid according to WO 98/42622 with mixtures of a hybrid varying from WO 98/42622 through the possession of at least one of (i) an occluded co-builder which is not silicate, different, or (ii) a different type of crystal compared to WO 98/42622. The hybrid materials of the present may have a range of particle sizes; primary crystals in the size range of about 0.01 to about 20 microns being suitable, from about 1 miera to about 10 microns and having good ability to diffract X-rays being preferred. These primary crystals can be agglomerated in larger aggregates to minimize dust and / or segregation in fully formulated laundry detergents. All hybrids in the present generally can vary in size of primary crystallites and the degree of perfection of the crystal. The hybrid materials herein can have a range of occluded detergency builder content, for example, from about 0.001 to about 1.0 fraction in number of available occlusion sites can be occupied by occluded co-builder. Hybrids that have combinations of occluded and adsorbed builder are possible. The hybrid materials herein may have a variable cation composition, for example including hydrogen or ammonium or even in part calcium or magnesium, although typically the preferred cation is sodium. Potassium or lithium, if present, will be in a rather limited proportion, for example, less than about 0.01% of available interchangeable sites. The charge equilibrium amounts of said cations may be present, or amounts of undercharge equilibrium, for example when the hybrid material is extensively washed in pure water. The hybrid materials herein may optionally have adsorbed or occluded organic auxiliaries, such as perfumes. Provided they are located in a manufactured formulation, perfumes, like organic poiimeric builders or chelators, are added for purposes of consideration of the formula, outside the builder system. The hybrid materials herein may have a variable degree of hydration, for example, if used in detergent compositions which are aqueous suspensions, they may be completely hydrated. In other non-limiting examples, if the hybrid material is incorporated in a non-aqueous liquid detergent, a bleach comprising high density granular detergent or bleach precursor, or a composition comprising a hydrolytically labile or pro-perfume perfume precursor, the Hybrid material can be anhydrous or only partially hydrated. Preferred hybrid builders that have occluded non-silicate occluded co-builder herein have occluded materials that are typically relatively small inorganic anions, for example, occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitrite , occluded sulfate and mixtures thereof. A preferred group of hybrid detergency builders having occluded non-silicate co-builder have occluded materials that contain an anionic charge greater than one, eg, occluded phosphate, occluded carbonate, occluded sulfate, and mixtures thereof. A preferred group of hybrid builders having occluded non-silicate builder has occluded materials that are free of phosphorus and free of boron, for example, occluded carbonate, occluded nitrate, occluded nitrite, occluded sulfate and mixtures of the same. A preferred group of hybrid detergency builders having occluded non-silicate occluded builder have occluded materials that are free of nitrite, for example, occluded carbonate, occluded nitrate, occluded sulfate, and mixtures thereof. Another group of hybrid detergency builders having occluded non-silicate occluded co-builder have occluded materials that are nitrite-free, nitrite-free, boron-free and phosphorus-free, eg, occluded carbonate, occluded sulfate, Na2 ? occluded, occluded NaOH and mixtures thereof. Unless otherwise indicated, the hybrid detergent builder herein is characterized by at least one of: (i) a calcium sequestration rate for 5 minutes of at least 15%, preferably at least 20% , most preferably at least 5% higher than zeolite A having comparable crystal size; and / or (i) a 15 minute capacity or equilibrium to sequester calcium in excess of the loading amount by inducing aluminum in the zeolitic aluminosilicate. Alternatively, said hybrid is characterized by a 15-minute calcium ion exchange or equilibrium capacity of at least 15% greater, preferably at least 20%, most preferably at least 25% greater than the capacity of calcium ion exchange of a reference material selected from an unhybridized zeolite A. Said reference zeolite A in fully-exchanged form in Na has a theoretical cation exchange capacity of approximately 7 meq / g, typically 5-7 meq / g, for example 6 meq / g in practice where the abbreviation "meq / g "refers to milliequivalents per gram. Said material for reference purposes suitably has a particle size of about 1 miera to about 10 microns. See, for example, the methods described in WO 98/42622 and which are described in more detail below, especially Table 1 and the percentage improvement discussion given below that illustrates how the previously identified percentages are calculated. Levels of detergency builder system in laundry detergent powder completed, synthetic bar, gei, tablet or bag can vary widely, for example, from 0.1% to about 99% of a builder system comprising the essential hybrid material . The portion of the hybrid aluminosilicate builder material may also vary, ranging from about 0.01 to 1.0, most preferably from 0.10 to 1.0 weight fraction in the builder system.

Hybrid aluminosilicate which is not in accordance with WO 98/42622 It should be emphasized that the present invention includes embodiments in which, by means of hybrid material, only hybrid aluminosilicates that are not in accordance with WO 98/42622 are used as an essential component. These hybrids can generally be selected in any proportion from: (i) silicate-containing hybrids of zeolites having crystal type that differs by X-ray diffraction from those described in WO 98/42622 and (ii) hybrids of a crystalline ajuminosilicate and at least one occluded detergency builder which is not silica or is not silicate.

Preferably, this builder builder is selected from the group consisting of phosphate, carbonate, borate, nitrate, nitrite, sulfate, Na2, NaOH and mixtures thereof. Of course, combinations of silicate-type hybrids such as WO 98/42622 and hybrids having a non-silicate co-builder selected from the group consisting of phosphate, carbonate, borate, nitrate, nitrite, sulfate, Na 2? and mixtures thereof in all proportions. Hybrids that are not in accordance with WO 98/42622 herein generally include those known in the art of manufacturing zeolite, see, eg, "Zeolite Chemistry and Catalysis," Ed, JA Rabo, ACS Monograph Series, Vol. 171 , American Chemical Society, Washington DC, 1976, incorporated herein by reference. See very particularly the same volume, chapter 5, "Salt Occlusion in Zeolite Crystals", pages 332-349 and references cited therein. Such materials include, for example, zeolite A occluded with borate, occluded with hydroxide, occluded with nitrate or occluded with another nitrate salt. See, for example, the work of Barrer or of Liquornik and Marcus referred to in the cited standard texts. The occluded salt molecules may or may not penetrate the sodalite cages of the zeolite, and may be disposed in the large cages. In general, the occlusion may be of the so-called reversible type or may be non-reversible. The occlusion of the present purposes is best conducted with sodium as a cation and without a transition metal such as the cation, although more generally, occlusion variations with transition metal or with silver cation are possible and may have beneficial effects, such as increase in antimicrobial activity of a detergent composition. In addition to the occlusion of carbonate, nitrate, nitrite, sulfate, phosphate, borate, mixtures thereof and mixtures thereof with silicate in any proportion, the present invention also includes the occlusion of Na2 = in zeolites, such as zeolite A occluded with Na2 ?. It is known that certain zeolites tend to decompose nitrate catalytically to NaN 2 (chabazite and mordenite) and even to produce Na 2 ?. The hybrid aluminosilicates herein can be prepared by any known method, see, for example, above-cited ACS monograph and references thereto, said methods can be based on aqueous solutions, for example, using the above-identified anions in a method of another way similar to the Engelhard method WO 98/42622 or variations thereof, or it may be non-aqueous or melt-based methods. Preferred hybrids and combinations include those wherein the zeolite is zeolite A, B, P, X, AX or MAO; sodium is the only cation; and the occluded detergency builder is selected from carbonate, hydroxide and Na2O. Suitable levels are from about 0.1% to about 80%, preferably from about 0.5% to about 30% by weight of the hybrid aluminosilicate when used alone. Suitable levels of a builder system in the present detergent compositions are from about 0.1% to about 85%, preferably from about 1% to about 40% by weight. Detergency builders other than hybrid aluminosilicate are conventional and can, for example, be selected from water-soluble organic builders such as sodium 1,2-oxidisuccinate salts, sodium salts of citric acid, sodium salts of carboxymethyloxysuccinate, salts sodium nitrilotriacetic acid and the like; water insoluble inorganic builders such as zeolites A, P, B, X or any of its modifications, water-soluble organic builders such as various cellulosic polymers and inorganic builders such as sodium carbonates, sodium phosphates, sodium tripolyphosphates and the like, including a wide range of capacity and velocity of calcium and / or magnesium ion. The builder system can be supplemented by one or more materials known as chelators (chelators such as organic polymers, being added separately in the formula and being materials that generally have the ability to strongly pass transition metal ions or metal precipitates from colloidal transition in aqueous alkaline media).

Chelators suitable for use herein include sodium salts of ethylenediamine disuccinate, ADTA, HEDP, DTPA and mixtures thereof; Typical levels are in the range of about 1 ppm to about 2% by weight of the detergent composition.

Hybrid aluminosilicate component according to WO 98/42622 The present invention includes embodiments in which a particular hybrid aluminosilicate according to WO 98/42622 is used as an essential component. This hybrid material can be obtained from Engelhard Corp. It is a crystalline zeolitic aluminosilicate having occluded silicate, and in WO 98/42622 it is referred to as a "zeolite / silica hybrid composition" (HZSC). The terms "aluminosilicate having occluded silica", "aluminosilicate having occluded silicate", "hybrid zeolite / silica composition" and the acronym "HZSC" are used interchangeably. According to WO 98/42622, HZSC materials can be prepared by crystallization of high aluminum content zeolites in environments with high content of alkaline material / high silica content. Chemical analyzes idican an excess of silica in HZSC beyond the inherent to its crystalline structures. Said materials, at least in certain cases, demonstrate sequestration capabilities for cations such as calcium which exceed the amount of zeolitic aluminum available for ion exchange and which have even exceeded the theoretical limit possible for a zeolite. Therefore, the HZSC materials and their properties are potentially different both in degree and type from those of a conventional zeolite. According to the inventors of WO 98/42622, the "key mechanism in the effectiveness of HZSC materials is derived from the ability of zeolite cages to isolate and stabilize small highly charged silicate units". The inventors of the present invention emphasize that alternative theories can be advanced, for example it is known that small polyanions of co-builder (in this case silicate) can reduce electrostatic repulsions between cations in aluminosilicates. This can stabilize occluded aiuminosilicates with sodium exchange and with calcium exchange in relation to non-occluded aluminosilicates. Such a theory would be broadly consistent with the composition description of HZSC. Although less likely in view of the data of WO 98/42622, sodium metasilicate, if mixed closely with zeolite, could alternatively provide compositions, effectively made by the process of WO 98/42622, which act more effectively than the builder compositions hitherto available, for example, by means of an improved concerted action as a precipitating builder co-together with the zeolite. Therefore, the present invention should not be limited to theory. Rather, the value of WO 98/42622 as a source of builder for the present invention may lie to a greater degree in the product of the methods described than in the precise mode of the description of the compositions. Notwithstanding the forng precautions, WO 98/42622 discloses that silicate units are introduced during HZSC synthesis by providing an environment wherein the silica in the reaction mixture is depolymerized to predominantly highly charged monomer units before crystallization begins. . The occluded silicate units of HZSC are visible in the 29 Si NMR spectrum. The HZSC as a whole is established as the "most potent" in the formation of multivalent cation complexes that are existing zeolites, silicates or mixtures thereof. The structure of the zeoite and the occluded silicate units are set to "act together, as shown by a new type of hybrid composition that shows properties that are not zeolites or silicates or physical mixtures of the two." In addition to the high ion exchange capacity, HZSC materials demonstrate unusually fast sequestration rates, important in applications such as detergency improvement. By means of technical background, without wishing to be limited to theory, the sequestration properties of zeolites arise from their ability to exchange ions. The ability to exchange ions derives from the isomorphic substitution of Al (III) for Si (IV) in classical zeolite structures resulting in a net excess of negative charge in the aluminosilicate structure. This requires a counterbalance by the inclusion of interchangeable cations. The excess load and therefore the exchange capacity is a function of aluminum content. The "detergent" zeolites, according to WO 98/42622, up to ahota have been restricted to the relatively short list of "high aluminum" zeolites. By Lowenstein's rule, the Si / Al ratio of a zeolite may not be equal to 1.0 and concomitantly the aluminum content may not exceed 7.0 meq per gram for an anhydrous material in the sodium form. This capacity can alternatively be expressed as 197 mg of CaO per gram of zeolite (anhydrous) when the water softening is the desired exchange reaction. The zeolites demonstrate that this maximum aluminum content includes zeolite A, high aluminum analogs of zeolite X and analogs of high aluminum content of gismondin (often referred to as zeolite B, P or MAP). Also according to WO 98/42622, although zeolite A has been the "detergent zeolite" of choice for years, the possibility of employing a high aluminum version of gordonin-like materials in calcium sequestration has been known for more. of a generation (USP 3,112,176 Haden et al) and recently a renewed interest has been found (for example, USP 5,512,266 Brown, et al). In addition to zeolites, the ability of silicates to form ion complexes such as calcium and especially magnesium has been known for a long time and sodium silicate has long been used as a cheap, low yield builder. Very recently, complex silicates such as Hoechst SKS-6 have been developed which are claimed to be competitive with higher yield zeolites. Moreover, according to WO 98/42622, the ability for the silicates to form ion complexes such as calcium and magnesium is inversely proportional to the silicate chain length and directly proportional to the electronic charge on this chain fragment. The silicates depolymerize upon increasing alkalinity (see FIG. 1 of WO 98/42622). At a moderate pH (where washing cycles are conducted) the silicates are polymeric. However, at much higher pHs, silica not only becomes predominantly monomeric, but also that monomer can possess multiple charges. If such highly charged small fragments could be exposed to solutions having multivalent cations, very powerful high capacity sequestering agents would be obtained. The inventors of WO 98/42622 assert that they have created such a situation by isolating and stabilizing substantial concentrations of those species within zeolite cages where ions such as calcium and magnesium can freely enter from an aqueous environment (such as wash water). and react with these powerful sequestering agents. WO 98/42622 also discloses that the HZSC compositions can be prepared by reacting a source of finely divided aluminum such as a dry aluminosilicate gel or powdered gibbsite and most preferably finely divided metacaolin with concentrated silicate solutions at above pH values. from 12 to temperatures that vary from room temperature to approximately 100 ° C and at atmospheric pressure. It is crucial for the preparation of the HZSC compositions that the aluminum source be added to the final reaction mixture. In this way, if all the ingredients of the reaction mixture are added together and heated to crystallization temperature, a conventional zeolite of the prior art will be formed and the HZSC materials of WO 98/42622 will not be formed. According to WO 98/42622, it is even more convenient to prepare HZSC compositions by heating the reaction mixture at temperatures of 50 ° C to 85 ° C before the addition of the aluminum source for a period of about 30 minutes or more. Although it is not desired to limit any theory of operation, it appears that heating the reaction mixture for about 30 minutes prior to the addition of aluminum allows the silicate to depolymerize and predominantly form the occluded silicate units described above. According to WO 98/42622, HZSC materials can also be prepared by reacting finely-divided metacaoline with concentrated solutions of sodium silicate at pH values above 12 at temperatures ranging from room temperature to about 100 ° C and under pressure. atmospheric WO 98/42622 also establishes a preference for using high purity metakaolines, especially those having low iron content and titania, when color is a consideration. For example, the metacaoline having a Fβ2 ?3 content of less than 1%, preferably less than 0.5% by weight and a TiO2 content of less than 2% by weight preferably less than 1% by weight are useful. The metacaoline must be in powder form. These powders can be prepared by stirring grains and coarse impurities of kaolin ores, generally by fractionating the degranulated crude, drying the resulting suspension of fractionated hydrocarbon, spraying the dried material, calcining in a conventional manner to produce metacaoline (see, for example, US 3,112,176 (Haden et al)), and pulverizing the metacaoline by means of a hammer mill or the like. E.U.A. 3,014,836 Proctor et al., Is cross-referenced here for description with respect to the production of calcined kaolin pigments from an acid (bleached) kaolin filter cake by the steps including drying, spraying, calcination and repulping; in the practice of this invention, the procedures of Proctor et al., should be modified using lower calcination temperature to produce the desired metacaolin form of calcined clay. The kaolin mineral can be improved by means such as foam flotation, magnetic purification, selective flocculation, mechanical delamination, trituration or combination thereof before drying, spraying, calcination and repulping. In many commercial operations, a chemically dispersed strip of kaolin is dried in a spray dryer, forming microspheres. See, for example, US patent. No. 3,586,523 Fanselow et al. The resulting microspheres of water caolin (not calcined) are then pulverized, calcined and repulped as taught in the patent of Fanselow et al. According to WO 98/42622, the particle sizes of the water kaolinite precursor of the metacaoline starting material affect the size of the HZSC product. Since HZSC products having a fine particle size are generally preferred, fine particle size metakaolins obtained from fine-particle size water-based kaolins are recommended. These particle sizes are very often measured by kaolin producers as values obtained by sedimentation, typically using a Sedigraph® 5100 analyzer (provided by Micromeretics Corporation) and the values reported as "equivalent spherical diameter" (e.s.d.). The use of other measuring instruments may give slightly different values. In Example 3 of WO 98/42622, reproduced below as "HZSC synthesis example 1", illustrative of the procedure of WO 98/42622, typical samples of the hydrocarbon precursor of metacaoline are approximately 90% by weight finer what is esd of 1 miera, as measured using the Sedigraph ^ 5100 instrument. The high-brilliance water caolin used in this example can be prepared from a thick white Georgian caolinate oil by the steps of compressing, degranulating, foam flotation remove color impurities, mechanical delamination and fractionation. The fractionated product, approximately 90% by weight finer than e.s.d. of 1 miera, can be recovered as a dispersed fluid aqueous strip that can be spray dried, pulverized, calcined on the condition of metacaoline and repulverized. The particle size of the repulped metacaoline is thicker than that of the hydrocarbon. The HZSC compositions of WO 98/42622 can be further prepared by synthesizing those zeolitic molecular sieves having a molar ratio of high Al 2 O 3 / SiO 2, for example molar ratios of Si 2 Al 2+ 3 in the range of 2 to 3 according to the teachings of the prior art, with the crucial exception that the aluminum source is added to the latter to the reaction mixture. Species include type P (also known as type B), zeolite A, types X with high alumina content and chabazite analogues. After crystallization, the zeolite crystals are washed uniformly with water, preferably deionized water, to remove sodium and spurious silica from the glass surfaces. In some cases, some replacement of sodium by hydrogen may take place during washing. The crystals can be washed with solutions other than those of pure water. Approximately 5 to 40% silica content of the washed crystals is due to the occluded silicate species, usually up to 20%. Thus, the analysis of Si? 2 total as determined by conventional chemical analytical means will exceed that of SiO2 that would be expected based on the silica content of the structure as indicated by x-ray powder patterns and 29s analysis. NMR of the composition of HZSC. The silicate portion occluded from this silica is easily achieved from the NMR peaks at about -81 to -85 ppm. 29 If NMR has become a standard technique in the analysis of zeolites. The utility of this technique is based on the fact that different frequencies correspond to different electronic environments around the silicon, typically affected in zeolites by the chemistry of neighboring atoms and / or bond angles of Si-O. 29If NMR detects all Si, not only that which is associated with long-range crystallinity. This makes it sensitive to species that may not be detected by XRD.

EXAMPLE OF SYNTHESIS OF HZSC 1 SEE EXAMPLE 3 of WO 98/42622) To prepare an improved detergency builder, termed a zeolite-silica hybrid composition (HZSC), based on a gismondin-type aluminosilicate, the following procedure was applied: 1000 grams of fine particle size metacaolin obtained by calcining an ultrafine hydrophobic kaolin , ground, mechanically delaminated (90% by weight finer than 1 miera of e.s.d.) followed by pulverization is used. The powdered metacaoline is mixed in an alkaline silicate solution containing 702 grams of N-Brand ^ sodium silicate solution and 1064 grams of NaOH in 4800 grams of deionized water that has been mixed and preheated to 72 ° C. The mixture is then reacted with vigorous stirring at 72 ° C for eight hours at ambient pressure in an open stainless steel vessel. The crystalline product of the reaction is filtered and washed three times with batches of 2000 ml of deionized water at 72 ° C. The crystalline product is dried in a forced air oven at 100 ° C overnight. The crystalline product is analyzed and found to have a Si / Al molar ratio of about 1.15 (SÍO2 / AI2O3 = 2.30). An XRD epolvo pattern essentially identical to that of WO 98/42622 of Example 1 and 2 (characteristic of gismondin-type zeolites) is obtained. This material is a HZSC (hybrid composition of zeolite-silica) according to WO 98/42622.

In addition, the sodium content of this material as synthesized is found to be essentially equal to that of silica (Na / Si = 1.01), and which is substantially above the aluminum content on a molar basis (Na / Al = 1.16). ). In general, the aluminum content of a zeolite is expected to be equal to its cationic content insofar as each aluminum of the structure induces a charge of net negative structure which is counterbalanced by cations to maintain electroneutrality. Additional sodium is a characteristic of HZSC and is believed to result in sodium in association with occluded silicate species. The average particle size (50% by weight finer than) of the crystalline product is 5.5 microns as determined by Sedigraph ^ 5100.

EXAMPLE OF SYNTHESIS OF HZSC 2 (SEE EXAMPLE 10 of WO 98/42622) In order to synthesize an improved detergency builder called hybrid zeolite-silica composition, in this example based on a structure of zeolite A, a HZSC material is prepared by the following procedure. An alkali silicate solution is prepared by dissolving 175.0 grams of NaOH and 99.0 grams of N-Brand® sodium silicate in 522.8 grams of deionized water. After mixing and preheating the mixture to 80 ° C, 109.5 grams of metamaline Metamax ^ are added and the mixture is reacted by stirring for one hour at 80 ° C in a constant temperature bath. The resulting product is filtered and washed three times with batches of 1000 ml of deionized water. The sample is then dried overnight in a forced air oven at 100 ° C. The product of this example demonstrates a clean, strong XRD powder pattern characteristic of zeolite A. The material is then subjected to the hardness sequestration test of WO 98/42622, example 7. The hardness removal readings at 15 seconds and 15 minutes are 43% and 51% respectively, showing that the hardness sequestration is remarkably faster and substantially more than that of the unmodified zeolite A. The hybrid composition offers substantial advantages over comparable zeolites in both the speed and the amount of hardness removal.

EXAMPLE OF SYNTHESIS OF HZSC 3 (SEE EXAMPLE 13 of WO 98/42622) To prepare an improved builder, called HZSC, based on a gismondin type structure, the following procedure is followed. A synthesis mixture identical to that of WO Example 12 98/42622 is prepared but in a different order of addition / reaction. In this way, 34.03 kg of deionized water, 19.38 kg of 50% NaOH solution and 6.41 kg of N-brand sodium silicate are combined and heated under stirring at 72 ° C in a stainless steel reactor. After an equilibrium period of 30 minutes to allow silicate depolymerization, 9.08 kg of Luminex brand metacaolin are added and the mixture is reacted with vigorous stirring for 8 hours at 72 ° C. After the reaction period, the product is washed and filtered over several filters in a large tray including multiple resuspensions and multiple rinses with substantial excess of deionized water. The XRD powder pattern for this product is of a highly crystalline material of a gismondin type structure, consistent with that of Example 12 of WO 98/42622. However, unlike example 12 of WO 98/42622, 9 If NMR shows a clear step to the main peak at -81 to -85 ppm which is characteristic of a HZSC. In addition, the elemental analysis indicates the high Si / Al ratio (Si / Al = 1.20) and the sodium levels approaching molar silicon contents (Na / Si - 1.01) and the characteristic excess of sodium to aluminum over a molar base (Na / Al 1.21). With the indication of occluded silicate NMR, a thorough calcium exchange is conducted as in example 12 of WO 98/42622. The analysis of the exhaustively exchanged sample gives 23.8% of CaO, 43.2% of SÍO2 and 31.4% of AI2O3 on a dry weight basis. In this way, the material contains approximately 7.20 meq / g of Si, 6.16 meq / g of Al and 8.49 meq / g of Ca. The ratio of Ca / AI meq / g approaching 1.4 is consistent with that of HZSC and not consistent with that of a zeolite that is limited to 1.0. The calcium capacity approaching 8.5 meq / g is consistent with a HZSC and inconsistent with the theoretical limit of 7.0 meq / g indicated for the zeolites. The product of this example is a HZSC and not simply a high aluminum version of zeolite P as prepared in Example 12 of WO 98/42622, despite the fact that both can be prepared using identical reagents, times of reaction and tratures and identical crystallization / washing equipment. Therefore, it is evident that the order of addition of reagents and probably the complete depolymerization of the silicate are imperative in the formation of HZSC.

EXAMPLE OF SYNTHESIS OF HZSC 4 (SEE EXAMPLE 14 of WO 98/42622) To prepare an improved detergency builder, called HZSC, based on a gismondin-like structure, and to demonstrate aluminum sources other than metacaoline can be used in the formation of HZSC, the following procedure is followed: An aluminosilicate gel with a thick composition that approaches 1: 1 Si / Al is prepared by dissolving 2.95 kg of NaAl? 2, in 14.0 kg of deionized water. To this is added 7.45 kg of N-Brand ^ sodium silicate. The resulting gel is beaten with a blade of high shear stress to a seemingly homogeneous consistency. The homogenized gel is ied on stainless steel trays and dried overnight in an oven at 100 ° C. A portion of this dry gel is pulverized and used as a dry aluminosilicate reagent. In this way, 89 grams of NaOH and 88 grams of N-Brand ^ sodium silicate are dissolved in 600 grams of deionized water and brought to a trature of 72 ° C under agitation. After equilibration, 160 grams of the dry gel aluminosilicate reagent is added to the mixture under stirring and crystallization at 72 ° C for 5.5 hours. The sample is washed and filtered under vacuum with an excess of deionized water and dried at 100 ° C overnight. The XRD powder pattern for this material is that of a highly crystalline gismondine type structure. The 9Si NMR spectrum shows a clear step to the main peak at -81 to -85 ppm, characteristic of HZSC. The HZSC material produced according to this example is tested according to the procedure set forth in Example 7 of WO 98/42622. The obtained result indicates that the material obtained by this example possesses the same rapid cation exchange removal, that is, 48% in 15 seconds and 82% in 15 minutes than that possessed by the novel material of Example 3 of WO 98/42622 (Synthesis example of HZSC 1 above). From this, this example establishes that other sources of aluminum other than metacaoline can be used in the synthesis of HZSC materials.

EXCHANGE CAPACITY OF BALANCING IONS OF A HZSC (SEE EXAMPLE 5 of WO 98/42622) The complete sequestration capacity of the crystalline product of HZSC 1 synthesis example (example 3 of WO 98/42622) at a pH of 10 (typical of wash water) is established by exchanging 3.0 grams of the material twice with 6.0 grams of CaCl2 2H2O dissolved in 400 ml of deionized water. The exchanges are each conducted for approximately 45 minutes at a trature of 100 ° C. The sample is filtered and washed six times with approximately 100 cp.3 of deionized water to remove any spurious CaCl2. The sample is then dried at 100 ° C for about 12 hours. The sample is then subjected to conventional X-ray fluorescence chemical analysis techniques. The analysis reveals 23.5% by weight of CaO, 42.0% by weight of SÍO2, 31.9% by weight of AI2O3 and approximately 1.0% of other materials on a dry weight basis. Thus, the material contains 7.0 meq / g of Si, 6.26 meq / g of Al and 8.37 meq / g of Ca. This not only indicates 34% more claice than that which can be considered by exchange with the available aluminum, it is almost 20% greater than the capacity of 7.0 meq theoretically possible for ion exchange in a maximum aluminum zeolite. In terms of mg CaO / g of anhydrous zeolite (as in the Henkel test) this is a capacity of 236, well above the theoretical zeolite maximum of 197. Clearly, the exchange of zeolite ions is not the only mechanism of kidnapping that operates for HZSC.

The above synthesis examples demonstrate the preparation of the WO 98/42622 materials denoted "HZSC" for hybrid zeolite-silica compositions demonstrating remarkable speed and multivalent cation complex uniformity. This is especially useful in smoothing / buffing enhancement applications. These properties are confirmed in WO 98/42622 which are derived from the ability of zeolite cages to occlude small highly charged silicate species. Whatever the theory regarding the structure of these compositions, the zeolite and the occluded or introduced silicate appears to act collectively as a hybrid composition showing properties that are not zeolites, specifically tested silicates, or physical mixtures of the two. In order to demonstrate that HZSC NMR peaks at approximately -81 to -85 ppm are due to occluded silicate in HZSC compositions, samples of 2 MAP products manufactured by Crosfield under the trade names Zeocros 180 and Doucil A-24 are they get and they are tested as they are received. XRD powder patterns for both samples indicate mediatable hydroxisodalite as evidenced by the peaks at 14.0, 24.3 and 25.1 degrees 2 teta, WO 98/42622, figures 4a, b. A sample of high aluminum content zeolite P made according to the Haden method (US patent 3,112,176) is found to contain no discernible sodalite as determined by XRD. Representative samples of HZSC, including those of Examples 3 and 13 of WO 98/42622 are examined by XRD and in no case is measurable sodalite present.

Pure MAP zeolite as prepared by the Haden method is subjected to 2 Si NMR analysis. It is free of the H81C-81 to -85 ppm characteristic step, Figure 5a of WÓ 98/42622. In a publication of Carr, S. W., Gore, B. and Anderson, M. W., Chem Mater. 1997, Vol. 9, pages 1927-1932, it has been noted that Crosfield's zeolite MAP, such as received, contains an NMR step close to the characteristic of HZSC. Without said step present in Haden's pure MAP zeolite, an alternative explanation to what Carr et al. Claims, of the step that is due to surface hydroxyl groups was sought by the inventors of WO 98/42622. In this way, they obtained a hydroxisodalite sample and found that it had a large NMR peak centered at approximately -85.0 ppm. The published values for sodalite vary from approximately -83.5 to -85 ppm, the variation being largely due to the exact degree of hydration (see High Resolution Solid State NMR of Silicates and Zeolites, G. Enqelhardt and D. Michel, John Wiley & Sons, Chichester, 1987). this hydroxisodalite was added by the inventors of WO 98/42622 at a level of 1% to the pure MAP and resulted in an XRD pattern, Figure 4c of WO 98/42622, essentially identical to that of the MAP contaminates with sodalite of the Crosfield commercial products, figures 4a, b, of WO 98/42622. The inventors of WO 98/42622 subjected this mixture to 29 NMR analysis and contrasted it with the pure MAP of Haden, Crosfield MAP contaminated with sodalite and HZSC of example 3 of WO 98/42622. Pure MAP did not have a step in the region of -83 ppm, indicated by Carr et al., (Figure 5a of WO 98/42622). In addition to 1%, sodalite produced a spectrum, Figure 5c of WO 98/42622, with the step essentially identical (although weaker) to that of the Crosfield product contaminated with sodalite, Figure 5d WO 98/42622. In this way, the most reasonable explanation for the observations of Carr et al., Is contamination by sodalite in the Crosfield MAPs as received. HZSC is free of these contaminations and nevertheless contains the characteristic NMR step. It is more reasonable to assign to this step occluded silicates that are also expected in this regime in which sodalite is not present.

SPEED OF HARDNESS SEQUESTRATION (SEE EXAMPLE 7 of WO 98/42622) To evaluate the relative performance of HZSC-type materials against zeolite as water softening agents in mixtures that resemble wash water, sequestration tests were conducted in mixed calcium / magnesium solutions at 35 ° C, and pH of 10. 1.5 liter loads of calcium solutions plus 1.03 molar magnesium are regulated in their pH with glycine solutions at a pH of 10. The molar ratio of Ca: Mg is set to 3: 1. The test hardness solutions are heated to 35 ° C in a constant temperature bath in which 0.45 grams of HZSC equilibrated in air or reference builders are added and the test mixtures are agitated by means of an agitator higher at a speed of 200 rpm. The hardness concentration is monitored by a Orion model 9332BN total hardness electrode connected to a Orion model 720A pH meter. Both the "instantaneous" and "equilibrium" removal of a detergency builder can be critical parameters depending on the particular environment in which they are used. The removal of hardness at 15 seconds is taken as indicative of "instantaneous" hardness removal and the 15 minute readings are taken as a measure of "equilibrium" properties. HZSC materials as well as reference materials are subjected to this test and the results are summarized in Table 1.

TABLE 1 Hardness removal recorded in time by HZSC type builders and some reference materials. * hybrid of type gismondin with occluded silicate ** hybrid of zeolite A type with occluded silicate Reference materials (see WO 98/42622) Note with respect to percentage improvement levels described above. HZSC1 and HZSC3 have a hardness removal improvement at 15 seconds, compared to zeolite A of ((48-10) / 10) x 100 = 380.0%. HZSC1 and HZSC3 have an improvement in hardness removal at 15 minutes, compared to zeolite A, of ((82-41) / 41) x 100 = 100.0%. This test indicates that the materials of HZSC at 15 seconds are faster than the reference materials (conventional zeolites) and at least in the case of HZSC that has structure of type gismondina, have data of removal at 15 minutes improved that the reference materials. However, note that if the HZSC materials have a reduced crystal size in relation to the reference materials, an improvement in the removal of hardness is expected after 15 seconds. Since, for the HZSC of zeolite A type, the removal data at 15 minutes are not substantially improved over the reference materials, this leaves some doubt as to the value of the overall water softening improvement offered by HZSC type zeolite A. Such overall value, however, is not a function of water softening in a simple test as given above, but also depends on the effective cleaning performance in a fully formulated laundry detergent. This subsequent performance is affected by the presence of laundry detergent auxiliaries. In short, the manufacturer of builders is in a position to suggest that builders materials be evaluated by the detergent formulator, but is not well placed to accurately predict through simple tests which materials are the most effective in practice.

DETERGENT COMPOSITIONS The detergent compositions of the present invention include a builder system comprising, at least in part, the hybrid aluminosilicate described above, together with specified detergent auxiliaries. When the builder system does not differ from WO 98/42622, the detergent compositions of the present invention are required to constitute a combination of a hybrid material of WO 98/42622 and at least one selected detergent auxiliary not described or suggested in WO. 98/42622. These selected auxiliaries, especially advantageous together with hybrid builders, are described in detail below as "Class I detergent auxiliaries". When the builder system differs from that described in WO 98/42622, very particularly, when the hybrid builder material is not specifically described in WO 98/42622, the detergent compositions of the present invention comprise at least the builder material. Hybrid detergency and one or more broadly defined detergent auxiliaries. These more broadly defined detergent auxiliaries may include any detergent auxiliary or detergent auxiliary class described in WO 98/42622 and the associated literature preferences, as well as any class I detergent auxiliary. Of course, the preferred class I auxiliaries are included in all preferred embodiments of all detergent compositions herein at levels of from about 0.0001% to about 99% of the detergent composition. Moreover, the preferred detergent compositions preferably include at least two detergent auxiliaries of class I, most preferably at least three of said auxiliaries. Preferred detergent compositions according to the invention may contain: (a) from 2 to 6% by weight of one or more detergent surfactants, (b) from 10 to 80% by weight of one or more detergency builders, including the hybrid aluminosilicate, (c) from 5 to 40% by weight of a bleach system, (d) from 0.05 to 10% enzyme or mixtures thereof, and (e) optionally other detergent ingredients up to 100% by weight. Of course, bleach-free modalities are also contemplated. The highly preferred detergent compositions herein comprise, in addition to (a) the hybrid builder, (b) from about 0.1% to about 99% of at least one detersive auxiliary selected from the group consisting of: (i) detersive surfactants having at least one branched hydrophobe, preferably branched at half the chain; (I) organic polymeric materials selected from polyacetal carboxylates, hydrophobically modified polyacrylates, terpolymers that compensate acrylate or maleate, polymeric soil release agents, polymeric dye transfer inhibitors, polyamines, polyimines, polymeric rheology modifiers and mixtures thereof; (Ii) oxygen bleach promoter materials selected from bleach activators; organic bleach builders; transition metal bleach catalysts; photobleaches and mixtures thereof; (V) textile care promoting agents other than said organic polymeric materials; and (v) mixtures of (i) - (iv). Sources and examples of said materials have been given in the previous summary.

Class I detergent auxiliaries Biodegradable branched surfactants The present invention includes important embodiments comprising at least one surfactant or mixture of biodegradable branched surfactants and / or altered crystallinity and / or branched to the middle of the chain. The terms "biodegradablely branched" and / or "with altered crystallinity" and / or "branched to the middle of the chain" (acronym "MCB" used hereafter) indicate that said surfactants or mixtures of surfactants are characterized by the presence of surfactant molecules having a moderately non-linear hydrophobe; very particularly, wherein the hydrophobe of the surfactant is not completely linear, on the one hand, it is not branched to a degree that would result in unacceptable biodegradation. The preferred biodegradable branched surfactants are different from LAS, ABS, Exxal, Lial, etc. commercially known, whether branched or unbranched. The biodegradable branched materials comprise light branching particularly located, for example, from about one to about three methyl, and / or ethyl and / or propyl and / or butyl branches in the hydrophobe, where the branch is located distantly from the head group. of surfactant, preferably towards the middle of the hydrophobe. Typically, one to three branches may be present in a single hydrophobe, preferably only one. Such biodegradable branched surfactants may have exclusively linear aliphatic hydrophobes, or the hydrophobes may include cycloaliphatic or aromatic substitution. Highly preferred are the linear MCB analogue surfactant analogues, linear alkylpoly (alkoxylates) and linear alkylbenzenesulfonate, said surfactant being suitably selected from Cs-Cis alkyl sulfates branched with C 1 -C 4 at half the chain, alkyl ethoxylated alcohols, Propoxylated or butoxylated CQ-C ^ Q branched with C 1 -C 4 at the half chain, C 1 -C 4 branched C 1 -C 4 alkylethylsulphates at the half chain, branched C 1 -C 6 alkylbenzenesulfonates with C1-C4 in the middle of the chain and mixtures thereof.

When they are anionic, the surfactants in general may be in acid or salt form, for example sodium, potassium, ammonium or substituted ammonium. The biodegradable branched surfactants offer substantial improvements in cleaning performance and / or utility in cold water and / or resistance to water hardness and / or economy of use. Such surfactants, in general, can belong to any known class of surfactants, for example, anionic, nonionic, cationic or zwitterionic. The biodegradable branched surfactants are synthesized through Procter & amp; Gamble, Shell and Sasol. These surfactants are described more fully in WO98 / 23712 A published on June 4, 1998; WO97 / 38957 A published October 23, 1997; WO97 / 38956 A published October 23, 1997; WO97 / 39091 A published October 23, 1997; WO97 / 39089 A published October 23, 1997; WO97 / 39088 A published October 23, 1997; WO97 / 39087 A published October 23, 1997; WO97 / 38972 A published October 23, 1997; WO98 / 23566 to Shell, published June 4, 1998; Sasol's technical bulletins; and the following pending patent applications assigned to Procter & Gamble: Preferred biodegradable branched surfactants include MCB surfactants as described in the following references: WO98 / 23712 A published June 4, 1998 includes descriptions of non-ionic MCB surfactants including primary alkyl polyoxyalkylenes of MCB of the formula (1): CH3CH2 (CH2) wC (R) H (CH_2)? C (RI) H (CH2) and C (R2) H (CH2) z (EO / PO) mOH (1), where the total number of carbon atoms in the branched primary alkyl portion of this formula including the branches R, R ^ and R2, but not including the carbon atoms in the alkoxy portion of EO / PO, is preferably from 14 to 20, and wherein in addition to this agent mixture surfactant, the total average number of carbon atoms in the hydrophobic primary alkyl portion of MCB is preferably 14.5-17.5, most preferably 15-17; R, Rl and R2 are each independently selected from hydrogen and C-j_3 alkyl, preferably methyl, provided that R, R1 and R2 are not all hydrogen and, when z is 1, at least R or R "! is not hydrogen, w is an integer from 0 to 13, x is an integer from 0 to 13, and is an integer from 0 to 13; whole of at least 1; w + x + y + z is 8-14; and EO / PO are alkoxy portions preferably selected from ethoxy, propoxy groups and mixed ethoxy / propoxy groups, wherein m is at least 1, preferably 3-30, most preferably 5-20, most preferably 5-15.Non-ionic MCBs may alternatively include portions derived from butylene oxide, and the -OH portion may be replaced by any of the end-blocking portions either known for conventional nonionic surfactants WO97 / 38957 A published on October 23, 1997 includes the description of branched alcohols about half the chain of the formulas R-CH2CH2CH (Me) CH-R1-CH2? H ( I) and HOCH2-R-CH2-CH2-CH (Me) -R1 (II) comprising: (A) dimerization of alpha-olefins of the formulas RCH = CH2 and R1CH = CH2 to form r olefins of the formulas R (CH2) 2- C (R1) = CH2 and R1 (CH2) 2-C (R) = CH2; (B) (i) atomization of olefins and then reaction thereof with carbon monoxide / hydrogen under Oxo conditions or (ii) direct reaction of the olefins of step (A) with CO / H2 under Oxo conditions. In the above formulas, R, R1 = linear alkyl of 03.7.

W097 / 38957 A describes (i) the production of MCB alkyl sulfate surfactants by sulfating (I) or (II); (I) MCB alkylethyloxylate preparation consisting of ethoxylating and then sulfatar (I) or (II); (iii) preparation of MCB alkylcarboxylate surfactants consisting of oxidizing (I) or (II) or their aldehyde intermediates and (iv) preparing surfactants of MCB acyltaurate, MCB acyl isethionate, MCB acyl sarcosinate or N-acyl acrylate. MCB methylglucamide using the branched alkylcarboxylates as a supply material. WO97 / 38956 A published on October 23, 1997 describes the preparation of branched alpha olefins in the middle half or near the middle half of the chain that is made: (a) preparing a mixture of carbon monoxide and hydrogen; (b) reacting the mixture in the presence of a catalyst under Fischer-Tropsch conditions to prepare a hydrocarbon mixture comprising the olefins described; and (c) separating the olefins from the hydrocarbon mixture. WO97 / 38956 A also describes the preparation of branched alcohols in the middle half or near the middle half of the chain by reacting the described olefins with CO / H2 under Oxo conditions.

These alcohols can be used to prepare (1) MCB sulfate surfactants by sulfating the alcohols; (2) MCB alkyl ethoxy sulfates ethoxylating, then sulfating, the alcohols; or (3) branched alkylcarboxylate surfactants by oxidizing the alcohols or their aldehyde intermediates. The branched carboxylates formed can be used as a supply material for preparing branched acyltaurate surfactants, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide, etc. WO97 / 39091 A published October 23, 1997 includes the description of a detergent surfactant composition comprising at least 0.5 (especially 5, most especially 10, most especially still 20) percent by weight of longest alkyl chain , MCB surfactant of the formula (I). A-X-B (I) wherein A is 9-22 (especially 12-18) alkyl hydrophobe of C MCB having: (i) a longer linear C chain attached to the X-B portion of 8-21 carbon atoms; (ii) alkyl portion of C -) _ 3 branching from this longer linear chain; (iii) by at least one of the branching alkyl portions attached directly to a C of the longest linear C chain at a position within the range of the 2 C position, counting from C 1 is attached to the CH 2 B portion, carbon 2 omega (the C terminal minus 2C); and (iv) the surfactant composition has an average total number of carbon atoms in the A-X portion of 14.5-17.5 (especially 15-17); and B is a hydrophilic portion (surfactant head group) preferably selected from sulfates, sulfonates, polyoxyalkylene (especially polyoxyethylene or polyoxypropylene), alkoxylated sulfates, polyhydroxy portions, phosphate ester, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, carboxylates polyalkoxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, mono- / di-alkanolamides, monoalkanolamide sulfates, diglycolamide and its sulfates, glyceryl esters and their sulfates, glycerol ethers and their sulfates, polyglycerol ether and sulphates thereof, sorbitan esters, esters of polyalkoxylated sorbitan, ammonioalkanosulfonates, amidopropylbetaines, quat, alkylated, alkylated / polyhydroxyalkylated / oxypropyl quat, imidazolines, 2-ylsuccinates, sulphonated alkyl esters and sulfonated fatty acids; and X is -CH2- or -C (O) -.

WO97 / 39091 A also describes a laundry detergent or other cleaning composition comprising: (a) 0.001-99% detergent surfactant (I); and (b) 1-99.999% auxiliary ingredients. WO97 / 39089 A published on October 23, 1997 includes the description of liquid cleaning compositions comprising: (a) as part of the surfactant system 0.1-50 (especially 1-40) percent by weight a branched surfactant to the half the chain of the formula (I); (b) as the other part of the surfactant system, 0.1-50% by weight co-surfactants; (c) 1-99.7% by weight of a solvent; and (d) 0.1-75% by weight of auxiliary ingredients. The formula (I) is A-CH2-B where A = 9-22 (especially 12-18) alkyl hydrophobe of C-MCB having: (i) a longer linear carbon chain attached to the X-B portion of 8-21 carbon atoms; (ii) alkyl portions of C- | _3 branching off from this longer linear chain; (iii) at least one of the branching alkyl moieties directly attached to a carbon of the longest linear carbon chain at the position within the 2 C position range, counting from carbon No. 1 which is attached to the CH2B portion, to the omega-2 carbon (the C terminal carbon minus 2C); and (iv) the surfactant composition has an average total number of carbon atoms in the A-X portion of 14.5-17.5 (especially 15-17); and B is a hydrophilic portion selected from sulfates, polyoxyalkylene (especially polyoxyethylene and polyoxypropylene) and alkoxylated sulfates. WO97 / 39088 A published on October 23, 1997 includes the description of a surfactant composition comprising 0.001-100% of primary slcoxylated alkyl sulphates of MCB of the formula (I): CH3CH2 (CH) wCHR (CH2)? CHR1 (CH2) and CHR2 (CH2) zOSO3M (I) wherein the total number of carbon atoms in the compound (I) including R, R1 and R2 is preferably 14 to 20 and the total number of carbon atoms in the branched alkyl portions preferably averages 14.5-17.5 (especially 15-17; R, R1 and R2 are selected from H and alkyl from C-j_3 (especially Me) as long as R, R1 and R2 are not all H; when z = 1 at least R or R1 is not H; M are especially selected cations of Na, K, Ca, Mg, quaternary alkylammonium of the formula N + R3R4R5R6 (II); M is especially Na and / or K; R3, R4, R5, R6 are selected from H, alkylene of C- | _22 > branched alkylene of C4..22. alkanol from C < | 6, alkenylene of C? _22, / or branched alkenylene of 04.22; w. x > y = 0-13; z is at least 1; w + x + y + z = 8- 14. WO97 / 39088 A also describes (1) a surfactant composition comprising a mixture of branched primary alkyl sulphates of the formula (I) as before. M is a cation soluble in water; when R2 is C-3 alkyl, the ratio of surfactants having z = 1 to surfactants having z = 2 or greater is preferably at least 1: 1 (most especially 1: 100); (2) a detergent composition comprising: (a) 0.001-99% primary alkoxylated alkylsulphate of MCB of the formula (III) and / or (IV): CH3 (CH2) aCH (CH3) (CH2) bCH2OS? 3M (III), CH3 (CH2) dCH (CH3) (CH2) eCH (CH3) CH2OS? 3M (IV), where a, b, d and e are integers, preferably a + b = 10-16, d + e = 8-14 and when a + b = 10, a = 2-9 and b = 1-8; when a + b = 11, a = 2-10 and b = 1-9; when a + b = 12, a = 2-11 and b = 1-10; when a + b = 13, a = 2-12 and b = 1-11; when a + b = 14, a = 2-13 and b = 1-12; when a + b = 15, a = 2-14 and b = 1-13; when a + b = 16, a = 2-14 and b = 1-14; when d + e = 8, d = 2-7 and e = 1-6; when d + e = 9, d = 2-8 and e = 1-7; when d + e = 10, d = 2-9 and e = 1-8; when d + e = 11, d = 2-10 and e = 1-9; when d + e = 12, d = 2-11 and e = 1-10; when d + e = 13, d = 2-12 and e = 1-11; when d + e = 14, d = 2-13 and e = 1-12; and (b) 1-99.99% by weight of detergent auxiliaries; (3) a primary alkyl sulfate surfactant, branched to half the chain of formula (V): CH3CH2 (CH2)? CHR1 (CH2) and CHR2 (CH2) zOSO3M (V) where x, y = 0-12; z is at least 2; x + y + z = 11-14; Rl and R2 are not both H; when one of R ^ or R2 is H and the other is Me, x + y + z is not 12 or 13; and when R ^ is H and R2 is Me, x + y is not 11 when z = 3 and x + y is not 9 when z = 5; (4) alkyl sulfates of the formula (III) wherein a and b are integers and A = b = 12 or 13, a = 2-11, b = 1-10 and M is Na, K and optionally substituted ammonium; (5) alkyl sulfates of the formula (IV) in which d and e are integers and d = e is 10 or 11 and when d = e is 10, d = 2-9 and e = 1-8; when d = e = 11, d = 2-10 and e = 1-9 and m is Na, K, optionally substituted ammonium (especially Na); (6) Methyl-branched primary alkyl sulphates selected from methyl pentadecanolsulfate of 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, or 13-; methylhexadecanolsulfate of 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- or 14-; methyltetradecanolsulfate of 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12 -; methylpentadecanolsulfate of 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12 -, or 2.13 - and / or mixtures of these compounds. WO97 / 39087 A published on October 23, 1997 includes the description of a surfactant composition comprising 0.001-100% of an alkoxylated alkyl sulphates branched to half the chain of the formula (I) wherein the total number of atoms of carbon of compound (I) including R, R1 and R3, but not including carbon atoms of alkoxy portions of EO / PO is from 14 to 20 and the total number of carbon atoms in branched alkyl portions averages 14.5- 17.5 (especially 15-17); R, R ^ and R2 = H or C ^ .3 alkyl (especially Me) and R, R1 and R2 are not all H; when z = 1 at least R or R1 is not H; M = specially selected cations of Na, K, Ca, Mg quaternary alkylamines (II) (M is especially Na and / or K) R3, R4, R5, R6 = H, alkylene of C- | _22. branched alkylene of 04.22. alkanol from C ^ .Q, alkenylene from C < | 22 and / or branched alkenylene of C4..22; w. x, y = 0-13; z is at least 1; w + x + y + z = 8-14; EO / PO are alkoxy portions, especially ethoxy and / or propoxy; m is at least 0.01, especially 0.1-30, very especially 0.5-10, very especially 1-5.

Also described are: (1) a surfactant composition comprising a mixture of branched primary alkoxylated alkyl sulphates of the formula (I). When R2 = C alquilo _3 alkyl, the ratio of surfactants having z = 2 or greater to surfactant having z = 1 is at least 1: 1, especially 1.5: 1, most especially 3: 1, very especially 4: 1; (2) a detergent composition comprising: (a) 0.001-99% primary alkoxylated alkylsulfate branched to half the chain of formula (III) and / or (IV) M is as above; a, b, d and e are integers, a + b = 10-16, d + e = 8-14 and when a + b = 10, a = 2-9 and b = 1-8; when a + b = 11, a = 2-10 and b = 1-9; when a + b = 12, a = 2-11 and b = 1-10; when a + b = 13, a = 2-12 and b = 1-11; when a + b = 14, a = 2-13 and b = 1-12; when a + b = 15, a = 2-14 and b = 1-13; when a + b = 16, a = 2-14 and b = 1-14; when d + e = 8, d = 2-7 and e = 1-6; when d + e = 9, d = 2-8 and e = 1-7; when d + e = 10, d = 2-9 and e = 1-8; when d + e = 11, d = 2-10 and e = 1-9; when d + e = 12, d = 2-11 and e = 1-10; when d + e = 13, d = 2-12 and e-1-11; when d + e = 14, d = 2-13 and e = 1-12; and (b) 1-99.99% by weight of detergent auxiliaries; (3) a primary alkoxylated alkylsulphate surfactant of MCB of the formula (V), R 1, R 2, M, EO / PO, m is the same as before; x, y = 0-12; z is at least 2; x + y + z = 11-14; (4) alkoxylated alkylsulfate branched to half the chain of the formula (Ili) in which: a = 2-11; b = 1-10; a + b = 12 or 13; M, EO / PO and m are the same as before; (5) an alkoxylated alkylsulphite compound branched to half the chain of the formula (IV) in which: d + e = 10 or 11; when d + e = 10, d = 2-9 and e = 1-8 and when d + e = 11, d = 2-10 and e = 1-9; M is the same as before (especially Na); EO / PO and m are the same as before; and (6) methyl branched primary ethoxylated alkyl sulfates selected from ethoxylated methylpentadecanolsulfate of 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, or 13-; Ethoxylated methylhexadecanolsulfate of 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- or 14-; ethoxylated methyltetradecanolsulphate of 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2, 12-; ethoxylated methylpentadecanolsulphate 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2, 12-, or 2.13- and / or mixtures of these compounds. The compounds are ethoxylated with an average degree of ethoxylation of 0.1-10. WO97 / 38972 A published on October 23, 1997 includes a description of a method for making longer chain alkyl sulfate surfactant mixture compositions consisting of (a) sulfating with SO3, preferably in a falling film reactor, a mixture of long chain aliphatic alcohol having an average carbon chain length of at least 14.5-17.5, the me < The alcohol mixture comprising at least 10%, preferably at least 25%, most preferably at least 50%, most preferably still at least 75%, most preferably even 95% aliphatic alcohol of MCB having the formula ( I); wherein R, R "1, R2 = H or C ^ _3 alkyl, preferably methyl, provided that R, R * and R2 are not all H, and when z = 1, at least R or R 'is not H; w, x, y = integers 0-13, z = integer of at least 1, and w + x + y + z = 8-14, where the total number of carbon atoms in the primary branched alkyl portion of the formula (I), including the branching R, Rl and R2 is 14-20, and wherein also for the alcohol mixture the total average number of carbon atoms in the primary branched alkyl portions having the formula (I) is >; 14.5-17.5, preferably > 15-17; and (b) neutralizing the acid alkyl sulfate produced by step (a), preferably using a base selected from KOH, NaOH, ammonia, monoethanolamine, triethanolamine and mixtures thereof. Also disclosed is a method for making longer chain alkoxylated alkyl sulfate surfactant mixture compositions, which consists of alkoxylating the specified long chain aliphatic alcohol mixture; sulfating the resulting polyoxyalkylene alcohol with SO3; and neutralizing the resulting acidic alkoxylated alkylsulfate. Alternatively, the alkoxylated alkyl sulphates can be produced directly from the polyoxyalkylene alcohol by sulfating with SO 3 and neutralizing. WO98 / 23566 A Shell, published June 4, 1998 discloses branched primary alcohol compositions having from 8 to 36 carbon atoms and an average number of branches per mole of 0.7-3 and comprising ethyl and methyl branches. Also described are: (1) a preparable branched primary alkoxylate composition by reacting a branched primary alcohol composition as above with an oxirane compound; (2) a preparable branched primary sulfate alcohol sulfating a primary alcohol composition as before; (3) a branched alkoxylated primary alcohol sulfate preparable by alkoxylating and sulfating a branched alcohol composition as before; (4) a branched primary alcohol carboxylate preparable by oxidizing a branched primary alcohol composition as before; (5) a detergent composition comprising: (a) surfactants selected from branched primary alcohol alkoxylates as in (1), branched primary alcohol sulphates as in (2), and branched alkoxylated primary alcohol sulphates, as in (3); (b) a detergency builder; and (c) optionally additives selected from foam control agents, enzymes, bleaching agents, bleach activators, optical brighteners, co-surfactants, hydrotropes and stabilizers. The primary alcohol composition, and the sulfates, alkoxylates, alkoxysulfates and carboxylates prepared therefrom, exhibit good cold water detergency and biodegradability. The biodegradable branched surfactants useful herein also include the modified alkyl aromatics, especially modified alkyl benzene sulphonate surfactants disclosed in co-assigned, commonly assigned patent applications, (P & G Case Nos. 7303P, 7304P). In more detail, these surfactants include alkylarylsulfonate surfactant systems (P &G Case 6766P) comprising from about 10% to about 100% by weight of said surfactant system of two or more alkylarylsulfonate surfactants with altered crystallinity of the formula (B-Ar-D) a (Mcl +) b where D is SO3-, M is a cation or mixture of cations, q is the valence d said cation, a and b are numbers selected such that the composition is electroneutra; Ar is selected from benzene, toluene and combinations thereof; and B comprises the sum of at least a primary hydrocarbyl portion containing from 5 to 20 carbon atoms and one or more portions with altered crystallinity wherein said portions with altered crystallinity interrupt or branch out from said hydrocarbyl portion and wherein said system of alkylarylsulfonate surfactant has alteration in crystallinity to the extent that its critical sodium solubility temperature, as measured by the CST test, is not greater than about 40 ° C and wherein said alkylarylsulfonate surfactant system furthermore has a at least one of the following properties: percentage of biodegradation, as measured by the modified SCAS test, which exceeds tetrapropylenebenzene sulfonate; and weight ratio of non-quaternary carbon atoms to quaternary carbon atoms in B of at least about 5: 1. Said compositions also include mixtures of surfactants (P &; G case 7303P) comprising (preferably, consisting essentially of): (a) from about 60% to about 95% by weight (preferably from about 65% to about 90%, most preferably from about 70% by weight) about 85%) of a mixture of branched alkylbenzene sulphonates having the formula (I): (I) wherein L is an acyclic aliphatic portion consisting of carbon and hydrogen and having two methyl terminals, and wherein said mixture of branched alkylbenzene sulfonates contains two or more (preferably at least three, optionally more) of said compounds differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulfonates is characterized by an average carbon content of from about 10.0 to about 14.0 carbon atoms (preferably from about 11.0 to about 13.0, most preferably from about 11.5 to about 12.5) wherein said said average carbon content is based on the sum of carbon atoms in R "!, L and R2 (preferably said sum of carbon atoms in R ^ L and R2, is 9). to 15, most preferably 10 to 14) and further, wherein L has no substituents other than A, R "and R2; M is a cation or mixture of cations (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, most preferably selected from H, Na, K and mixtures thereof, most preferably still selected from H, Na and mixtures thereof) having a q valence (typically a 1 2, preferably 1); a and b are selected integers such that said compounds are electroneutral (a is typically 1 to 2, preferably 1, b is 1); R "! Is C1-C3 alkyl (preferably C 1 -C 2 alkyl, most preferably methyl); R2 is selected from H and C 1 -C 3 alkyl (preferably H and C 1 -C 2 alkyl, most preferably H and methylated, most preferably H and methyl provided that at least about 0.5, most preferably 0.7, most preferably still 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonate R2 is H); A is a benzene moiety (typically A is the -C6H4- moiety, with the SO3 of the formula (I) in the para- position with respect to the portion L, although in a certain proportion, generally not more than about 5%, preferably 0 to 5% by weight, the SO3 portion is ortho- With respect to); Y (b) from about 5% to about 60% by weight (preferably from about 10% to about 35%, most preferably from about 15% to about 30%) of a mixture of unbranched alkylbenzene sulphonates having the formula ( II): (II) wherein a, b, M, A and q are as defined above and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terminals, and wherein Y has an average carbon content of about 10.0 to about 14.0 (preferably from about 1.0 to about 13.0, most preferably 11.5 to 12.5 carbon atoms); (preferably said mixture of unbranched alkylbenzenesulfonates is further characterized by a sum of carbon atoms in Y, from 9 to 15, most preferably 10 to 14); and wherein said composition is further characterized by a 2/3-phenyl index of from about 350 to about 10,000 (preferably from about 400 to about 1200, most preferably from about 500 to about 700) (and preferably wherein said mixture of surfactants has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, most preferably less than about = .1, most preferably still from 0 to 0.05). Also included by the branched-chain surfactants of the alkylbenzene derivative types are mixtures of surfactants comprising the product of a process comprising the steps of: alkylating benzene with an alkylation mixture; sulfonate the product of (I); and neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from about 1% to about 99.9% by weight of branched C7-C20 monoolefins, said branched monoolefins having structures identical to those of the branched monoolefins formed by dehydrogenation of branched paraffins from the formula R ^ LR2 wherein L is an acyclic aliphatic portion consisting of carbon and hydrogen and containing two terminal methyls; R ^ is C-alkyl! to C3; and R2 is selected from H and C- alkyl; to C3; and (b) from about 0.1% to about 85%, by weight of linear C7-C20 aliphatic olefins; wherein said alkylation mixture contains the branched C7-C20 monoolefins having at least two different numbers of carbon in the range of C7-C2o, and has an average carbon content of about 9. 5 to about 14.5 carbon atoms; and wherein said components (a) and (b) are in a weight ratio of at least about 15:85.

Selected Cationic Surfactants Preferred detergent compositions herein also include those in which the hybrid builder material of WO 98/42622, or a different hybrid builder as described herein, are combined with cationic surfactants. These selected cationic surfactants include: (i) cationic surfactants having a long chain and three relatively short chains in which one or more substituents attached to the nitrogen atom contain oxygen, such as, for example, hydroxyethyl and / or in which the relatively long chain is branched. Such surfactants include, for example, compounds having the formula R "! N_R2R3R4 X" wherein R1 is straight or branched alkyl of Cs-C-is (optionally including one or more aryl moieties, ether or ester) and wherein R2-R4 can vary independently and, for example, can comprise methyl, ethyl, propyl, butyl, hydroxyethyl, hydroxypropyl and mixtures thereof provided that at least one of R2-R4 is hydroxyalkyl, preferably hydroxyethyl. X "is any compatible anion, for example one selected from halogen (eg chlorine, bromine), acetate, citrate, lactate, glycolate, phosphate, nitrite, sulfate and alkyl sulfate, mixtures of these compounds and the corresponding anions can be used; and / or (ii) cationic surfactants having the formula: [R2 (OR3) y] [R4 (OR3) and] 2R5N +? - wherein R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 atoms of carbon in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, - CH2CH (CH2? H) -, -CH2CH2CH2-, and mixtures thereof; selected from the group consisting of C 1 -C 4 alkyl, hydroxyalkyl of CJ-C 4, benzyl ring structures formed by linking the two groups R 4, -CH 2 CHOH-, -CHOHCOR 6 CHOHCH 2 HH, wherein R 6 is any hexose or polymer of hexose having a molecular weight less than about 1000, and hydrogen when y is not 0; R ^ is the same as R4 or is a chain of in which the total number of carbon atoms of R2 plus R§ is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values of y is from 0 to approximately 15; and X is any compatible anion, for example, chloride and / or cationic surfactants other than the conventional alkyltrimethylammonium salts corresponding to the general formula: wherein R-j, R2, R3, and R4 are independently selected from an aliphatic group of 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate and alkyl sulfate radicals; wherein in said compounds the aliphatic groups contain, in addition to carbon and hydrogen atoms, other bonds such as ether linkages, and / or other groups such as amino groups. Longer chain aliphatic groups, for example those of about 12 carbon atoms, or greater, may be saturated or unsaturated. It is preferred where R < R2, R3 and R4 are independently selected from Cj alkyl to about C22. Especially preferred for some purposes are cationic materials containing two long alkyl chains and two short alkyl chains or those containing one long and three alkyl chain. short alkyl chains other than methyl. The long alkyl chains in the compounds described in the previous sentence have from about 8 to about 22 carbon atoms, preferably from about 10 to about 14 carbon atoms.

Also useful herein are the bis-alkoxylated quaternary ammonium surfactants (bis-AQA) and combinations including the ones described in WO9744433 A1 W09744431 A1, WO9744432 A1, WO9743394 A, WO9743393 A, WO9743391 A, WO9743390 A, WO9743389 A, WO9743371 A, WO9744420 A, WO9744419 A, WO9744418 A, WO9743388 A, WO9743387 A, WO9743365 A, WO9743364 A. See also WO9738968 A1. The selected cationic surfactants can be used herein for one or more purposes, including the net contribution to cleaning, especially of greasy soils, or for other purposes, such as softening through washing and / or antimicrobial purposes. Suitable levels of these cationic surfactants herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although much higher levels, for example, up to about 30% or more, can be useful especially in nonionic formulations: cationic (ie, limited or free of anionic). However, the highly preferred compositions combine the cationic surfactant at a very low level, for example, from about 0.1% to about 5%, preferably not more than about 2%, with the HZSC materials. The selected cationic surfactants, even at low levels, are surprisingly effective with the HZSC builder materials.

Conventional cationic surfactants, especially alkyltrimethylammonium, can be used in conjunction with the types of cationic surfactant selected if desired.

Selected sugar-derived surfactants Preferred detergent compositions herein also include those wherein the hybrid builder material of WO 98/42622 or a different hybrid builder as described herein is combined with selected sugar-derived surfactants. These selected sugar-derived surfactants include in particular the C 1 J-C-J S alkyl-N-met.Iglucamides, for example as described in WO 92/06070 A or WO 92/05071 A published on April 16, 1992; any of the known lactobionamide surfactants and combinations of the glucosamides and / or lactobionamides with alkyl polyglycosides (APG).

Cationic-anionic ion pair surfactants The U.S.A. 5,472,455 discloses water-soluble complexes of anionic and cationic surfactants. These are useful in conjunction with hybrid builders.

Bleach The preferred detergent compositions of the invention include those that combine HZSC builders or hybrids with selected bleach or bleach-forming materials.

Transition metal bleacher catalysts These selected materials include one or more bleach catalysts containing transition metal such as the materials described in WO 98/39406 A, WO 98/39405 A, WO 98/39335 A, for example those illustrated more specifically below - see also WO 97/00937, WO 96/06155, EP 718398 A, USA 5,720,897 and WO 97/48787. Particularly preferred are bleach catalysts containing iron or manganese. Even more preferred are the transition metal bleach catalysts based on any rigid cyclic macropol ligand, for example any truncacyclononane-based mnonuclear or dinuclear transition metal complex, most preferably monometallic catalysts where the rigid macropolyclic ligand is cross-linked. , as in Bcyclam or any of its homologs, for example those in which the terminal alkyl portions connected to the nitrogen are selected from methyl, ethyl and mixtures thereof. A particularly useful transition metal bleach catalyst wherein the terminal alkyl portions connected to the nitrogen are methyl is [Mn (Bcyclam) C12]: "Bcyclam" (5,12-dimetiI-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane) is prepared according to J. Amer. Chem. Soc, (1990), 112, 8604. Bcyclam (1.00 g., 3.93 mmol) is dissolved in dry CH3CN (35 mL, distilled from CaH2). The solution at 15 ml until the CH3CH starts to boil. Then, the flask is brought to atmospheric pressure with Ar. The degassing process is repeated 4 times. Mn (pyridine) 2Cl2 (1.12 g, 3.93 mmol), synthesized according to the procedure of the J. Inorg literature. Nucí Chem., (1974), 36, 1535, is added under Ar and the mixture is stirred overnight at room temperature. The reaction solution is filtered with a 0.2μ filter. The filtered material evaporates. 1.35 g of product is collected, 90% yield. The amount of transition metal bleach catalyst, when present in the detergent compositions of the invention, is suitably from 0.0001% to 1% by weight, very typically from 0.001% to approximately 0.1%.

Organic bleach catalysts The selected bleach promoting materials also include organic bleach catalysts or organic bleach enhancers or so-called oxygen transfer agents, for example the N-acylimine types described in WO98 / 07825 A or the phosphinoylimine types described in US patent 5,652,207. Such materials also include sulfonimines. These materials on organic bleach catalysts, unlike the activators of so-called bleach activators or bleach precursors such as TAED, which are stoichiometric and non-catalytic. The bleach catalysts include the compounds themselves and / or any of their precursors, for example any ketone suitable for the production of dioxiranes and / or any of the heteroatoms containing heteroatoms of dioxirane precursors or dioxiranes, such as sulfonimines and / or imines described in the US patent 5,576,282 and references described therein. In general, organic bleach catalysts include the anionic, cationic, nonionic or zwitterionic types. Zwitterionic types are among the most preferred. Particularly preferred organic bleach catalysts include omega- (3,4-dihydroisoquinolinio) alcansulfonates as in U.S. Patent 5,576,282 and oxaziridines as described in U.S. Patent 5,710,116.The levels may be, for example, from about 0.01% to approximately 5%.

Hydrophobic bleach activators and other activators v / o selected bleach precursors Preferred detergent compositions herein include, in addition to a hybrid builder material, a hydrophobic peracid or an activator capable of releasing said peracid. Hydrophobic types include those containing a chain of 6 or more carbon atoms, preferred hydrophobic types having a linear aliphatic C8-C-14 chain optionally substituted by one or more ether oxygen atoms and / or one or more portions aromatic, preferably located in such a way that the peracid is an aliphatic peracid. Very generally, said optional substitution by ether oxygen atoms and / or aromatic portions can be applied to any of the peracids or bleach activators herein. Branched chain peracid types and aromatic peracids having one or more linear or branched long chain substituents of C3-C-16 may also be useful. The peracids can be used in the acid form or as any soluble salt with a stable cation to the bleach. Especially useful herein are the organic peroxycarboxylic acids of the formula: O O O O II II R 11-C "-N-R 22-C" -OOH R 1 -N-C-R2-C-OOH R- R- or mixtures thereof wherein R 1 is alkyl, aryl alkylaryl containing from about 1 to about 14 carbon atoms, R2 is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms and R5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms. When these peracids have a sum of carbon atoms in R1 and R2 together of about 6 or greater, preferably from about 8 to about 14, they are particularly suitable as hydrophobic peracids for bleaching a variety of relatively hydrophobic or "lipophilic" spots including the of the types of "percudido". Calcium, magnesium or substituted ammonium salts may also be useful. With respect to any of these peracids, a bleach activator that produces the corresponding peracid under perhydrolysis conditions can be conveniently used. The bleach activator will generally have a residual group having any suitable pKa for hydrolysis during use. The conjugated acid pKa of the residual group is a measure of adequacy and is typically from about 4 to about 16 or greater, preferably from about 6 to about 12, most preferably from about 8 to about 11. The common residual groups include oxybenzenesulfonate. Most commonly, when the peracetic acid is the desired peracid, the bleach activator or bleach precursor is an acetylated diamine, such as tetracetylethylenediamine (TAED). Other useful hydrophobic bleach activators of the corresponding peracids useful herein are acetylenic materials such as undec-10-ynyl-oxy-benzenesulfonic acid or related activators as described in DE19616782 A1. Another useful bleaching material, whether in the form of peracid, bleach activator or diacyl peroxide is derived from phthalimido-substituted materials such as phthalimido-percaproic acid or 6-phthalimidohexaneperoxoic acid (CAS Registry Number 128275-31-0), for example as described in the USA 5,487,818, E.U.A. 5,415,796, EP 852,259 A and WO 98/39405 A, although other substituted phthalimido bleach promoting materials, for example those of EP 780,374 A or EP 325,288 A, may also be used. Another useful hydrophobic bleach activator and / or the corresponding peracid are described in E.U.A. 5,061, 807, DE 3823172 A, and the patent application open to the Japanese public (Kokai) No. 4-28799. The peracid is preferably 3-dodecyl-2,5-dioxo-1-pyrrolidinohexaneperoxoic acid. Analogs varying in length of the longest chain of CS-C-J S, as well as branched analogs, other related imidoperoxycarboxylic acids as described in E.U.A. 5,061, 807 and any of the corresponding activators with any known residual group are equally applicable herein. Particularly preferred hydrophobic bleach activators include sodium nonanoyloxybenzenesulfonate (NOBS or SNOBS), substituted amide types and the previously identified activators related to certain myoperaperacid bleach, for example as described in E.U.A. 5,061, 807. Also useful are acyl lactam activators, especially acylcaprolactams (e.g., WO 94-28102 A), acylvalerolactams. (e.g., E.U.A. 5,503,639) and certain N (alkanoyl) aminoalkanoyloxybenzenesulfonates as described in WO 98/27056 A. The diacyl peroxides corresponding to any of the previously identified peracids and / or activators are also included herein.

Also useful herein as activators are compounds which, under perhydrolysis conditions, release (i) percarboxylic acids and (ii) leaving groups which can act as a substrate for enzymes, especially reductive-active oxide enzymes. See DE19713852 A. Combinations of the previously identified peracids and / or bleach activators are also especially useful. In addition, combinations of the previously identified peracids and / or activators with conventional bleach activators, especially TAED, can give very good combinations of percussion removal and hydrophilic spots. The bleach activators are suitably used in amounts of 1 to 8% by weight, preferably 2 to 5% by weight.

Photobleaching agents The present invention encompasses combinations of the hybrid detergent builder materials defined above with photobleaching agents. In general, any photobleach can be used, such as fully or partially sulfonated zinc and / or aluminum phthalocyanines. See for example BE-865371 A, GB 14 08144 A, E.U.A. 4,497,741, RD 182041 or EP 119,746. Other photobleaching agents suitable for use herein are any that are commercially available from CIBA. However, the preferred photobleaching agents useful in the present invention include Si phthalocyanines as described in WO 97/05202 A, the low matrix photobleaching agents as described in WO 98/32832 A and E.U.A. 5,679,661, superoxide-generating photobleaches as described in WO 98/32829 A, singlet oxygen-generating photobleaches as described in WO 98/32828 A, and other photobleaching agents as described in WO 98/32827 A, WO 9832826 A, WO 98/32825 A and WO 98/32824 A. The photobleaches can be used individually or in combination. The type and amount of hue can be adjusted according to what the formulator wants.

Bleach Promoter Enzymes The present invention includes combinations of the hybrid detergent builder materials defined above with bleach promoting enzymes. Bleach-promoting enzymes in general include those enzymes that have bleach-promoting action through oxidation or reduction of soils and / or color spots. The term "bleach promoting enzymes" includes natural enzymes or those obtained by genetic engineering having a bleach promoting function with or without there being a requirement for the addition of any other active oxide reduction or bleaching material. In addition, the term "bleach promoting enzymes" encompasses enzymes as such and any related polypeptides having a similar effect. Suitable bleach promoting enzymes herein include oxide reductases. Very particular bleaching promoter enzymes include oxidases or combing systems including the same (DE19523389 A1), mutant blue copper oxidases (WO9709431 A1), peroxidases (see for example EUA 5,605,832, WO97 / 31090 A1), mannanases (WO9711164 A1 ); laccases, see WO9838287 A1 or WO 9838286 A1 or for example those laccase variants having amino acid changes in myceliophthora or scytalidium laccases as described in WO9827197 A1 or laccase systems mediated as described in DE19612193 A1, or those derived from strains of coprinus (see, for example WO9810060 A1 or WO9827198 A1), phenol oxidase and polyphenol oxidase (JP10174583 A) or phenol oxidase-mediated systems (WO9711217 A); increased phenoloxidase systems (WO 9725468 A WO 9725469 A); phenol oxidases fused to an amino acid sequence having a cellulose binding domain (WO9740127 A1, WO9740229 A1) or other phenol oxidases (WO 9708325 A, WO9728257 A1) or superoxide dismutases. The oxide reductases and / or their associated antibodies can be used, for example, with H 2 O 2, as taught in WO 98/07816 A. Depending on the type of detergent composition, other active reduction oxide enzymes can be used, including for example catalases (see, for example JP09316490 A). The bleach promoting enzymes may be coated (see for example WO9731088 A1) or uncoated. Also useful herein are combinations of the hybrid detergent builder with any oxygenase of extracellular origin, especially fungal oxygenase such as dioxygenase of extracellular origin. the latter is very especially keracetinase, catecholase or an anthocyanase, optionally in combination with another suitable oxidase, peroxidase or hydrolytic enzymes, as taught in WO9828400 A2.

The enzyme compositions herein may be solid or liquid, aqueous or non-aqueous and include a liquid composition substantially free of water comprising (A) an enzyme; (B) a substance selected from (i) substances that in aqueous medium are precursors for substrates for the enzyme; and (ii) substances that are cofactors for the enzyme; and (C) a non-aqueous liquid phase as described in WO9741215 A1. Bleach-promoting enzyme systems include those that generate hydrogen peroxide in situ, for example glucose oxidases or glucose oxidase-like polypeptides as taught in WO9820136 A1; or an enzyme having an aminoalcohol- or D-amino acid oxidase activity and a substrate for the enzyme as described in DE19545729 A1. Other bleach promoter enzyme systems useful herein incorporate lipoxygenase enzyme, unsaturated acid and a transition metal ion as described in DK9800352 A. In a preferred mode, lipoxygenase or other suitable bleach promoter enzyme is combined with the catalysts of transition metal bleach that are taught elsewhere in the present invention. Additional useful detergent compositions herein are those one-part or multi-part compositions or washing means comprising the hybrid builder materials together with bleach-promoting enzyme systems comprising chloroperoxidase, a source of hydrogen peroxide, chloride and adhesion agent, preferably formed at or near the site of use, as described in WO 98/42370 A. Other systems related to bleach promoter enzyme useful herein include those of WO 9807824 A and WO9807816 A1, which describe a composition detergent comprising a source of hydrogen peroxide and an antibody directed to a donor-hydrogen peroxide oxide reductase.

Detergency Meter The present invention also encompasses combinations of the above-defined hybrid builder materials with specific inorganic builders, most particularly one or more of the following materials.

Crystalline Silicates Specific crystalline silicates especially useful herein include a crystalline sodium silicate foliated with a high delta phase fraction as described in EP-860398 A1; DE19707449 C1; layered silicates or particular sheet silicates as described in JP09025116; JP10007416 A; WO9703018 A1; DE19613060 A1; EP-753568 A; EP-745559 A1; E.U.A.5567404 A; EP-731058 A1; crystalline sodium silicate having delta, alpha, beta and / or NS phase as described in WO9719156 A1; other crystalline silicates as described in WO9716525 A1; JP08311494 A; JP08311493 A; JP08268708 A; crystalline silicates made by amorphous silicate concretion as described in JP09183611 A; crystalline disilicals as described in DE4439083 A1; crystalline silicate powders with RUB-18 structure and X-ray diffraction pattern specified as described in EP-775670 A1; anhydrous crystalline silicates, especially containing potassium as described in WO98 / 31631 A1, JP09302384 A; and metasilicate pentahydrate as described in CN1131125 A.

Amorphous Silicates Specific amorphous sodium silicates useful herein include mixed sodium silicate-sulfate metal powders containing the metal sulfate as a solid solution as described in EP-728837 A1; Ammonium silicate and alkali amorphous granules as described in IT1265262 B; X-ray amorphous sodium silicate with low crystallization temperatures prepared from amorphous silicate with higher water content which can be converted to beta and alpha modifications by sequential microwave drying, as described in DE19710383 A1; other specific amorphous silicates as described in DE19541755 A1; DE 19525378 A1; WO96 / 28382 A; DE4446363 A1; DE4435632 A1; JP10007417 A; JP09309719 A; and crystalline / amorphous silicate combinations as described in JP09087690 A, JP09067592 A.

Amorphous aluminosilicates Amorphous aluminosilicates useful herein include those of JP09202613 A; JP 08333113 A.

Crystalline aluminosilicates v / o zeolites The specific zeolite compositions useful herein in conjunction with the hybrid builder materials include P-type zeolites as described in EP 758,626 A1; WO96 / 34828 A1; WO96 / 14270 A1; alkali metal silicates deposited on P-type zeolites as described in WO9734980 A1; zeolites irradiated with gamma rays as described in CN1113263 A, or the equivalent material made without irradiation; aluminosilicates having mainly tetrahedrally coordinated aluminum, formed by the 2: 1 chemical modification of stratified clay minerals as described in WO9618576 A1; zeolites prepared from aluminosilicate gels under pulsation as described in RU2083493 C1; microporous A-LSX zeolite as described in EP-816291 A1; zeolites that have grown with the aid of microwave energy as described in DE19548742 C1; and mechanically ground zeolite A having a particle size less than one miera as described in JP09067117 A.

Magnesium silicate Magnesium silicates may be used in conjunction with the hybrid builders herein. These include the magnesium silicate materials of WO 97/10179. In greater detail, a highly preferred illustrative magnesium silicate compound for use as a builder component with the hybrid builder materials herein is one that has a calcium binding capacity (CBC) of at least 10 mg. of CaO per gram at room temperature, a magnesium binding capacity (MBC) of at least 10 mg of MgO per gram at room temperature and a calcium binding rate (CBR) of not more than 300 seconds at room temperature, being the time taken to remove half of Ca2 + from a solution of -100 ppm of Ca2 + at a charge of 3 grams per liter, and having either a polymorph-related structure of silica or a stratified structure with a diffraction peak of Wide characteristic X-ray powder that occurs at a spacing of between 11 and 17 A.

Planting detergency systems planted Several seed detergency builders can be used in conjunction with the hybrid builder materials herein.

These include sodium carbonate in combination with a crystallization seed for calcium carbonate, see GB 1 437 950; tabular calcium carbonates as described in WO9840458 A1; rhombohedral calcium carbonates as described in WO9840457 A1; WO9840456 A1; WO9840455 A1; see also detergency builders with crystalline microstructure comprising carbonate WO9638526 A1; WO9733966 A1; WO9638525 A1; WO9638524 A1.

Other Inorganic Detergent Meters The inorganic builders especially useful in conjunction with the hybrid builders herein are non-cake-forming silicates treated with organic compounds as described in JP09208218 A; other novel silicates as described in JP10081509 A; Sodium silicates compacted as described in WO9717286 A1; hydrated trisodium phosphate as described in WO9715527 A1; and an ion capturing agent for toric alkaline metal ions containing a precipitating agent for the ions within pores of a porous support. Preferably the support is silica gel. The pore diameter of the support is 0.3-15 nm. The precipitating agents comprise carbonates, bicarbonates, silicates, sulfates and salts of organic acid of alkali metal. This last detergency builder is disclosed in JP09241680 A. Another useful inorganic builder improves alkaline delay particles, surfactant and an ion-blocking agent to raise the pH of the wash water after reducing its hardness, as described in WO9709414 A1.

Non-bleaching enzymes Enzymes other than generic proteases and amylases as described in WO98 / 42622 can be used in conjunction with hybrid builders for an unexpectedly large advantage. Said enzymes include non-generic proteases, non-generic amylases, non-bleaching enzymes other than proteases and / or amylases, bleaching enzymes, combinations thereof, combinations of these with any suitable antibodies, inhibitors, stabilizers or promoters; and combinations of any of the non-generic enzymes and / or enzyme-specific adjuvants with generic proteases and / or amylases. Specific bleaching and auxiliary enzymes for use therewith, for purposes of formula consideration, are considered with the bleaching system, as described elsewhere herein. Preferred non-bleaching enzymes useful in conjunction with hybrid builder materials herein include enzymes derived from extremophiles, as well as hydrolases other than protease and / or amylase. Preferred non-bleaching enzymes other than the protease and / or amylase in particular may have low or even very high activity (EP 839.05 A), may include combinations of plant cell wall degrading enzymes and non-cell wall degrading enzymes (WO 98/39403 A) and very specifically can include pectinase (WO 98/06808 A, JP10088472 A, JP10088485 A), pectolyase (WO98 / 06805 A1); pectin lyases free of other pectic enzymes (WO9806807 A1); chondriotinase (EP 747,469 A); xylanase (EP 709,452 A, WO98 / 39404 A, WO98 / 39402 A) including those derived from flexed microtetraspora (E.U.A. 5683911); isopeptidase (WO 98/16604 A); keratinase (EP 747,470 A, WO 98/40473 A); lipase (GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154 A); cellulase or endoglucanase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A; WO98 / 03640 A; see also neutral or alkaline cellulases derived from strain VKM F-3500D from chrysosporium lucknowense as described in WO9815633 A); polygalacturonase (WO 98/06809 A); mycodextranase (WO 98/13457 A); termitase (WO 96/28558 A); cholesterol esterase (WO 98 28394 A); or any combination thereof. Preferred proteases useful herein include certain variants (WO 96/28566 A, WO 96/28557 A, WO 96/28556 A, WO 96/25489 A). Other particularly useful proteases are the sutituted multiple protease variants comprising a substitution of an amino acid residue with another amino acid residue occurring naturally at a position of amino acid residue corresponding to position 103 of the subtilisin of Bacillus amyloliquefaciens with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19 , 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87 , 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140 , 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205 , 206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 2 28, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefaciens subtilisin; wherein said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than the amino acid residue positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisna and / or multiply substituted protease variants comprising a substitution of one amino acid residue with another naturally occurring amino acid residue. in one or more positions of amino acid residues corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amylollquefaciens subtilisin as described in PCT applications Nos. PCT / US98 / 22588, PCT / US98 / 22482 and PCT / US98 / 22486 all filed on October 23, 1998 from The Procter & amp;; Gamble Company (cases of P &G 7280 & , 7281 &7282L, respectively). Bleach / amylase / protease combinations are also useful (EP 755,999 A, EP 756,001 A, EP 756,000 A). Also in relation to the enzymes herein, enzymes and their directly linked inhibitors, for example, protease and their inhibitors linked by a peptide chain as described in WO 98/13483 A, are useful in conjunction with hybrid builders. of the present invention. Enzymes and their unbound inhibitors used in combinations selected herein include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A. Amylases can be used with horny amylase antibodies and taught in WO 98/07818 A and WO 98/07822 A, lipases can be used together with lipase antibodies as taught in WO 98/07817 A and WO 98/06810 A, the proteases can be used together with protease antibodies as taught in WO 98/07819 A and WO 98/06811 A, the cellulase can be combined with cellulase antibody as taught in WO 98/07823 A and WO 98/07821 A. In general, the enzymes may be combined with similar or different enzyme-directed antibodies, for example as taught in WO 98/07820 A or WO 98/06812 A. Preferred enzymes herein may be of any suitable origin, such as vegetable, animal, bacterium no, hongps and yeast. Preferred selections are influenced by factors such as pH activity and / or optimum pH stability, thermostability and stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes, such as bacterial amylases and bacterial proteases, as well as fungal cellulases are preferred.

Pro-perfume v / o lasting perfume The present detergent compositions include those in which the hybrid detergent builder is combined with a pro-perfume, proessence and / or a particular durable perfume system. Said selected ingredients are described more fully in EP 864,642 A1; EP 864,642 A1; WO98 / 07809 A or WO98 / 07814 A or WO98 / 07812 A or WO98 / 07683 A or WO98 / 07407 A or WO98 / 27192 A or WO98 / 07811 A (beta keto esters; WO97 / 34986 A or WO97 / 34989 A or WO97 / 34578 A1 or WO98 / 27190 A or WO98 / 06803 A (acetals and ketals pro-fragrance), WO9731094 A1 or EUA 5,500,138 (durable perfume system) W096 / 29281 A (schiff bases and / or esters); EUA 5,668,102 (esters of non-allylic perfume alcohols) and ZA9610649 A (sulfonates of perfume alcohols).

End blocked soil release agents End blocked polymeric soil release agents (see, eg, US 5,415,807, WO96 / 18715 A2, WO97 / 23542 A1 and many other Gosselink et al patents) are especially useful in conjunction with hybrid builder materials of the present invention. Suitable SRAs may have an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and allyl sulfonated terminal portions covalently derived from the base structure as described in E.U.A. 4,968,451; 1, 2-propylene / polyoxyethylene terephthalate polyesters blocked at the non-ionic ends as in E.U.A. 4,711, 730; oligomeric esters completely and partially blocked at the anionic ends of E.U.A. 4,721, 580; the oligomeric blocked block non-ionic polyester compounds of E.U.A. 4,702,857; and the esters of terephthalate blocked at the anionic ends, especially sulfoaroyl of E.U.A. 4,877,896, the latter being typical of SRA useful in both fabric conditioning and laundry products, an example being an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and DMT optionally but preferably further comprising PEG added, example PEG 3400. Another preferred SRA is an oligomer that has the empirical formula (CAP) 2 (EG / PG) 5 (T) 5 (SIP)? comprising units of terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) and which preferably terminate with end blocks (CAP), preferably modified isethionates, horns and teachings in E.U.A. 5,415,807. Still other preferred groups of SRAs are oligomeric esters of the empirical formula:. { (CAP) x (EG / PG) y- (DEG) and »(PEG) and -» (T) z (SIP) .Z '(SEG) q (B) m} .

The preferred SEG and CAP monomers for these esters include Na 2- (2-, 3-dihydroxypropoxy) ethane sulfonate ("SEG"), 2-. { 2- (2-hydroxyethoxy) ethoxy} Na ethanesulfonate ("SEG3") and its homologs and mixtures thereof and the products of ethoxylation and allyl alcohol sulfolation. Preferred SA esters in this class include the transesterification and oligomerization product of 2-. { 2- (2-hydroxyethoxy) ethoxy} Ethansulphonate and / or 2- [2-. { 2- (2-hydroxyethoxy) -ethoxy} sodium ethoxy] ethane sulfonate. The DMT 2- (2,3- dihydroxypropoxy) ethane sulfonate, EG and PG using an appropriate Ti (lV) catalyst and can be designated as (CAP) 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13 where CAP is (Na + _? 3S [CH2CH2?] 3.5) - and B is a glycerin unit and the EG / PG molar ratio is about 1.7: 1 as measured by conventional gas chromatography after of complete hydrolysis.

Processing of Hybrid Detergency Meter with Film Forming Polymers Some embodiments of builder systems and detergent compositions of the present invention, especially those in granular or powdered form, may also contain from about 0.1% to about 10%, typically from about 0.3% to about 7%, preferably from about 0.3% to about 4%, most preferably from 0.5% to about 2.5% by weight of soluble film-forming polymer in an aqueous suspension comprising the organic surfactants, aluminosilicate materials and neutral or alkaline salts herein. The polymer must be at least partially soluble in suspension so that it dries to a film capable of cementing the walls of the granules together as the suspension dries. For optimum granulated physical properties, the polymer must be substantially soluble in the suspension and is preferably completely soluble in the suspension. The suspension will typically comprise a surfactant phase and the insoluble aluminosilicate material suspended in a (often saturated) solution of the neutral or alkaline salt, which preferably comprises sodium sulfate. The suspension will generally be alkaline in nature due to the presence of the aluminosilicate material and either anionic surfactants or alkaline salts. Since the suspension will generally be a strong electrolyte solution, the optimum solubility of the polymer is obtained when it is in the form of an alkali metal, ammonium or substituted ammonium salt (eg, mono, di or triethanolammonium) at least partially neutralized or replaced. Alkali metal salts, especially sodium, are most preferred. Although the molecular weight of the polymer can vary over a wide range, it is preferably from about 1000 to about 500,000, most preferably from about 2000 to about 250,000 and most preferably from about 3000 to about 100,000. Film-forming polymers suitable herein include homopolymers and copolymers of unsaturated aliphatic mono or polycarboxylic acids. Preferred carboxylic acids are acrylic acid, hydroxyacrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, crotonic acid and citraconic acid. The polycarboxylic acids (for example maleic acid) can be polymerized in the form of their anhydrides and subsequently hydrolyzed. The copolymers can be formed from mixtures of unsaturated carboxylic acids with or without other copolymerizable monomers, or they can be formed from individual unsaturated carboxylic acids with other copolymerizable monomers. In this case, the weight percentage of the polymer units derived from non-carboxylic acids is preferably less than about 50%. The copolymerizable monomers include, for example, vinyl chloride, vinyl alcohol, furan, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and -butenoic Preferred polymers of the above group are the homopolymers and copolymers of acrylic acid, hydroxyacrylic acid or methacrylic acid, which in the case of the copolymers contain at least about 50%, and preferably at least about 80%, by weight of derived units of the acid. Particularly preferred polymers are sodium polyacrylate and sodium polyhydroxyacrylate. Other specific preferred polymers are homopolymers and copolymers of maleic anhydride, especially copolymers with ethylene, styrene and vinyl methyl ether. These polymers are commercially available under the trade names Versicol and Gantrez. Polymerization of homopolymers and copolymers of acrylic acid can be achieved using free radical initiators, such as alkali metal persulfates, acyl and aryl peroxides, acyl and aryl pertersols and aliphatic azo compounds. The reaction can be carried out in situ or in aqueous or non-aqueous solutions or suspensions. The chain terminating agents can be added to control the molecular weight. The maleic anhydride copolymers can be synthesized using any of the above-mentioned types of free radical initiators in suitable solvents such as benzene or acetone, or in the absence of a solvent, under an inert atmosphere. These polymerization techniques are well known in the art. It will be appreciated that instead of using a single polymeric aliphatic carboxylic acid, mixtures of two or more polymeric aliphatic carboxylic acids can be used to prepare the above polymers. Other film-forming polymers useful herein include the cellulose sulfate esters 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 in this group. Other suitable film-forming polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates described in the U.S.A. No. 3,723,322, Diehl, issued March 27, 1973; the dextrin esters of polycarboxylic acids described in the U.S.A. No. 3,919,107, Thompson, issued November 11, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and hydrolyzed starches described in the U.S.A. No. 3,803,285, Jensen, issued April 9, 1974; and the craboxylated starches described in the U.S.A. No. 3,629,121, Eldib, issued December 21, 1971; all incorporated here by reference. Preferred polymers of the above group are the carboxymethyl celluloses. Particularly preferred polymers for use herein are copolymers of acrylamide and acrylate 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 of about 20% of the polymer. Most preferably, the polymer has a molecular weight of from about 4,000 to about 10,000 and an acriiamide content of from about 5% to about 15%. Said polymer acts to increase the percentage of a mixture that is in the aqueous phase (lye). This improves the rate at which the droplets of the mixture will dry in a spray tower and can conveniently increase the density of the resulting detergent granules when, for example, large amounts of sodium sulfate or other high density inorganic salt is present. the lye phase. The patent of E.U.A. 4,379,080, issued April 5, 1983, provides additional details; in particular, the description of useful spray-drying processes that can be used to combine the present hybrid builders with film-forming polymers.

Organic detergency builders The detergent compositions of the present invention also include those in which a hybrid builder is combined with organic builders selected from polycarboxylates, most particularly those of JP10147640 A catalytic oxidation derivatives of (a) compounds containing OH selected from glycerin, glyceric acid (GA), glycerates, tartronic acid (TA) and tartronates in the presence of (b) metal salts selected from Fe salts and Zn salts as catalysts and polymerizing (c) ketomalonic acid or its salts; - compositions comprising alkali metal or ammonium borates and compounds having at least two OH groups in vicinal configuration as described in W096 / 38523 A; - succinic acid derivatives of mono, di or tri pentaerythritol as described in WO96 / 22961 A; - improved types of polyacetal polycarboxylates as described in EP 803,521 A; - tartronic acid prepared by catalytic oxidation of, for example, glycerin as described in JP08151345 A, JP08092156 A; - di or oligotartaric acids as described in DE19523116 A1; Succinates of sugar acid as described in DE19515899 A1; - dextrin, optionally oxidized as described in DE19613880 A1; WO97 / 20905 A; DE19545727 A1; DE19545723 A1; - oxidized starch and / or polysaccharides and / or maltodextrins as described in WO96 / 29351 A; WO96 / 27618 A; DE4426443 A; WO9827118 A; JP09249892 A; WO97 / 32903 A; JP09188704 A; EP 755,944 A; WO9638484 A; - cysteic monosuccinates as described in WO97 / 23450 A; - soluble amino ether carboxylic acids as described in JP10204045 A; JP10204044 A; JP10088189 A; and - mixtures thereof.

Functional polymers other than soil release agents and / or film-forming polymers The present detergent compositions also include those in which a hybrid builder is combined with a functional polymer other than a soil release agent or film-forming polymer as defined above. defined previously. Preferred among said polymers are one or more members selected from the group consisting of: hydrophobically modified polyacrylates (see, eg, EP 812,905 A2, EP 786,516 A2, such materials are available from Rohm &Haas, National Starch and others); terpolymers comprising acrylate or maleate (see, for example, US Pat. No. 4,647,396, US Pat. No. 4,698,174, EP 608,845, said materials are available from Rohm &Haas et al.); - polymeric dye transfer inhibitors (e.g.

PVPNO, see for example EP-704523 A1 or WO96 / 20996 A1 or polymers of DE19621509 A1 or WO96 / 37598 A1 available from BASF; - polyamines (see, for example WO97 / 00936 A1, WO97 / 23546 A1, WO97 / 28207 A1, WO97 / 42285 A1 and WO 97/35950 A1); - polyimine derivatives such as ethoxylated / propoxylated polyalkyleneamine polymers (see for example E.U.A. 5,565,145) or functionalized base structure polyamines (see WO97 / 42286 A1); - polymeric rheology modifiers (see, for example, modified polysaccharides, known "deflocculating polymers" - see, for example, E.U.A. 5,147,576 and mixtures thereof); and - mixtures of any of the above polymers.

Softeners The hybrid builders of the present invention can be used with certain specific softeners with excellent results. For example, detergents with softener through washing additives can be prepared by combining the hybrid builders with cationic biodegradable softeners as described in EP 831, 144 A, ZA9702461 A, WO97 / 34976 A, WO 97/36976 A; biodegradable diester quaternary ammonium compounds as described in WO 98/03619 A; softeners having hydrolysable portions as described in WO97 / 34975 A; quats with mono-long chain softeners as described in WO97 / 34972 A; unsaturated softeners as described in WO98 / 17757 A; combinations of chelator / softener as described in WO97 / 13828 A; esterquats and unsaturated fatty acids as described in WO 97/11142 A; low odor softeners as described in WO 98/47991 A; softeners activated in the dryer as described in E.U.A. 5,830,835; transparent softeners as described in WO98 / 17756 A, WO 97/03169 A; EP-839899 A1; fabric softeners of carboxylic quaternary amnion plus cationic nitrogen containing combinations of charge increasers as described in WO 98/12292 A; E.U.A. 5,733,855 A; WO 98/12293 A; WO 98/08924 A; or dispersible polyolefins as described in WO97746654 A.

Fillers and Bars, Especially Synthetic Detergent Bars The hybrid builder materials of the present invention are usefully incorporated into laundry detergent bars or sticks that can be made by any known technique.

In such combinations, some preferred combinations with the hybrid detergent builder are with fillers such as magnesium or calcium sulfates, kaolin, clays, hydroxisodalite or the like; the sulfates of divalent metals as described in WO98 / 20103 A; soap / synthetic detergent / starch combinations as described in WO98 / 18896 A; in bars of increased firmness as described in AU 9656053 A; with enzymes as described in WO98 / 18897 A; with dihydric alcohols as described in WO98 / 16611 A; cast molding with soap-based network structures as described in WO98 / 11864 A; with anionic detergents, soaps, polyphosphates and polyhydroxy fatty acid amides specified as described in WO98 / 05752 A; with absorbent gelling materials as described in E.U.A. 5,703,026; as molded bars by casting by alcohol-free processes as described in E.U.A. 5,703,025 or on paraffin wax, WO 97/22684 A; in bars with anionic synthetic detergent surfactant, bleaching agent and non-liquid thixotropic binding agents as described in W097 / 44434 A; in bars with soil release agents as described in WO97 / 42283 A, BR 9502489 A; in bars with cellulose as described in WO 97/36985 A; in bars with chelator as described in CN 1107884 A; or in bars with bleach and enzyme as described in WO 97/08283 A.

Detergent auxiliaries other than Class I auxiliaries Detergent surfactants The detergent compositions of the invention may contain one or more conventional detergent surfactants selected from anionic, cationic, nonionic, amphoteric and zwitterionic soap detergent active compounds which are not soap and mixtures thereof. Many suitable surfactants are available and described in the literature, for example in "Surface-Active Agents and Detergents", Volumes I and II, by Schwarts, Perry and Berch, in the well-known texts of Me Cuteheon and in the "Series of Surfactants Sciences "from texts published by Marcel Dekker, New York. Preferred surfactants include synthetic nonionic anionic and nonionic types, although soaps, including those derived from plant sources, can also be used, in bars. Anionic surfactants are well known and include alkylbenzene sulfonates, for example, "linear" types having an alkyl chain length of C8-C15 or non-biodegradable "hard branched" types although the latter types are relatively undesirable, especially where It is not allowed by legislation or where environmental considerations are a priority. Primary and secondary alkyl sulphates, particularly C12-C15 primary alkylsulphates, can be used; alkyl ether sulfates; olefinsulfonates; alkylxylene sulphonates; dialkylsulfosuccinates; and fatty acid ester sulfonates, such as methyl ester sulfonates. Sodium salts are typically preferred. The nonionic surfactants that can be used include ethoxylated primary and secondary alcohols, especially C8-C20 primary and secondary aliphatic alcohols ethoxylated from 1 to 20 moles of ethylene oxide per mole of alcohol, and most especially C9 primary aliphatic alcohols. -C15 ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. The corresponding derivatives of Guerbet alcohols, Exxal ^, Isofol® or Lial® may also be useful. Also of interest are non-ethoxylated nonionic surfactants, for example polyhydroxyamides. The choice of detergent active compound (surfactant), and the quantity, will depend on the intended use of the composition: different surfactant systems can be chosen for manual washing products and for products intended for use in different types of washing machines. The surfactant system may optionally be complemented by one or more cationic surfactants, such as alkyltrimethylammonium salts, fats or variants thereof.

Examples of other suitable cationic surfactants are described in the following documents, all of which are hereby incorporated by reference in their entirety: M.C. Publishing Co., McCutcheon's Detergents &; Emulsifiers, (North American edition, 1997); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; patent of E.U.A. 3,155,591; patent of E.U.A. 3,929,678; patent of SHE. 3,959,461, patent of E.U.A. 4,387,090 and patent of E.U.A. 4,228,044. In addition, special-purpose surfactants, for example linear or branched C8-C20 fatty acid alkyl dimethylamine N-oxides can be added for fat cleaning. Amine oxide or cationic surfactants, when present, are typically used at levels below about 5%, very generally at levels in the range of about 0.1% to about 2%. The total amount of surfactant system present will depend on the intended end use, but suitably varies from about 2% to about 60% by weight, preferably about 5% by weight 40% by weight. Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.

Detergency Meter As indicated, the detergent compositions of the invention contain a hybrid aluminosilicate as described in more detail below as a builder. This material can be supplemented by one or more of the aforementioned class I auxiliaries or any of the following detergency builders. The total amount of builder in the compositions, including the hybrid aluminosilicate and other builders, if present, will suitably vary from 10 to 85% by weight. A suitable complementary builder is selected from zeolite A, zeolite P, zeolite X, zeolite AX (or any other co-crystallized zeolite having equivalent effect), zeolite P with maximum aluminum content and mixtures thereof. The amount of zeolite present can suitably vary from 5 to 60% by weight, most preferably from 15 to 40% by weight, calculated on an anhydrous basis (equivalent to from 6 to 75% by weight, preferably from 19 to 50% by weight calculated on a hydrated basis). If desired, the zeolite can be used in conjunction with other inorganic or organic builders. Inorganic builders that may be present include sodium carbonate. Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, mono, di and trisuccinates of glycerol, carboxymethyloxysuccinates, carboxymethyloxy alonates, dipicolinates, hydroxyethyliminodiacetates, alkyl and alkenylmalonates and succinates; and salts of sulfonated fatty acid, although this list does not intend to be exhaustive. Other organic builders useful herein include polyacetal carboxylates, for example polymers and copolymers having polyglyoxylate structural units; see, for example, E.U.A. 4,146,495; E.U.A. 4,140,676; EP 803,521 A; These materials are available from Monsanto, Nippon Shokubai, BASF and others. Preferred complementary builders for use in conjunction with the hybrid aluminosilicate include salts of citric acid, most especially sodium citrate, suitably used in amounts of 3 to 20% by weight, most preferably 5 to 15% by weight. Other complementary detergency builders are water-soluble or partially water-soluble silicates, either crystalline or amorphous. These include the so-called layered silicates such as SKS-6 from Hoechst / Clariant and / or soluble silicates of ratio 2 or ratio 3. Such materials, when present, are typically used at levels on the scale of about 0.1% to about 20. % of the composition; very commonly, the level is below approximately 10%. In more detail, suitable silicate builders include the water-soluble and water-soluble types, and include those having a chain, layer or three-dimensional structure, as well as the amorphous-solid or unstructured-liquid types. Alkali metal silicates are preferred, particularly those liquids and solids having a Si 2: Na 2+ ratio. in the range from 1.6: 1 to 3.2: 1, including, particularly for the purposes of automatic dishwashing, 2-ratio solid aqueous silicates marketed by PQ Corp. under the trademark BRITESIL ^, e.g., BRITESIL H2O; and stratified sodium silicates, e.g., those described in the U.S.A. 4 patent., 664,839, issued on May 2, 1987 to H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is silicate of morphology * -Na2Si? 5 crystalline and aluminum-free laminated sold by Hoechst, and is especially preferred in granular laundry compositions. See preparation methods in German Application DE-A-3,417,649 and DE-A-3,742,043 and technical publications by Hoexhst / Clariant, eg, Surfactanta Sciences Series, Marcel Dekker, New York, see Vol. 71, Ed. M.S. Showell, published in 1998. See more particularly chapter 3, "Builders: The Backbone of Powdered Detergent" by Hans-Peter Rieck of Hoechst / Clariant. Other layered silicates, such as those having the general formula NaMSix02x + - | and H20 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 also be used herein. Stratified silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 as the stratified silicate forms alpha, beta and gamma. Other silicates, e.g., magnesium silicate, for example for stabilization of oxygen bleach for purposes of processing aid, may also be useful.

Also suitable for use herein are crystalline ion exchange materials synthesized or hydrates having chain structure and a composition represented by: xM2? And Si? 2.zM'O wherein M is Na and / or K, M ' is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in E.U. 5,427,711. Conventional aluminosilicate builders or conventional zeolites are useful in certain embodiments. These include materials that have the formula: [Mz (Al? 2) z (Si? 2) v_xH2 ?, where z and v are integers of at least 6, the molar ratio of zav is in the range of 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, occurring naturally or synthetically derived. An aluminosilicate production method is described in E.U. 3,985,669, Krummel et al., October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, as far as is different from Zeolite P, so-called Zeoite MAP. Natural types can be used, including clinoptilolite. Zeolite A has the formula: a- | 2 [(Al? 2) i2 (Si? 2) i2]? H2? wherein x is from about 20 to about 30, especially about 27. Dehydrated zeolites can also be used (x = 0-10). Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Suitable carbonate builders include alkali metal and alkaline earth metal carbonates such as those described in German Patent Application No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate , sodium sesquicarbonate and other carbonate minerals such as trona. Other useful carbonate builders are those of E.U.A. 5,658,867, issued August 19, 1997, to Pancheri et al., Incorporated herein by reference or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2C? 3.CaC? 3 when they are anhydrous , and even calcium carbonates including calcite, aragonite and valerite, especially shapes having areas of high surfaces relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars. Also preferred to complement the builder in some embodiments are polycarboxylate polymers, most especially acrylic / maleic copolymers suitably used in amounts of 0.5 to 15% by weight, especially 1 to 10% by weight of the detergent composition. However, the invention includes embodiments of which such conventional polycarboxylate polymers are substantially absent. The term "substantially absent" means that no amount is added deliberately although adventitious quantities may be present, for example as a result of the presence in a preformulated additive, such as a particulate enzyme additive.

Bleach The detergent compositions of the invention may also include one or more components of a conventional bleaching system. Said bleaching system may generally comprise any source of oxidative or reductive bleach, for example chlorine bleach such as hyopalite, especially hypochlorite; any hypoalite precursor, such as sodium dichloroisocyanurate; or any reductive bleach, for example sodium hydrosulfite or sodium bisulfite. Preferred bleach systems include those that are oxidative and comprise at least one source of bleach oxygen. Very generally, for example, when a transition metal bleach catalyst is used, there is no need for any source of bleach oxygen other than oxygen from the air. However, very typically a source of oxygen bleach is added to the formulation. These sources of bleaching oxygen include hydrogen peroxide, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and any other salt or adduct capable of releasing hydrogen peroxide in water and mixtures thereof. Conventional bleaching systems also often include hydrophilic bleach activators (bleach precursors) or corresponding peracids, for example TAED (tetraacetylethylenediamine) or percathetic acid. Bleach stabilizers, for example heavy metal sequestrants and / or free radical inhibitors may also be present. In some cases, for example low levels of tin compound are used to stabilize the bleach. In detergent compositions herein, sodium percarbonate or other persalts may be present in an amount of 5 to 30% by weight, preferably 10 to 25% by weight. The bleach activators are suitably used in amounts of 1 to 8% by weight, preferably 2 to 5% by weight. Organic or inorganic peroxyacids can also be used. These are usually in an amount within the range of 2 to 10% by weight, preferably 4 to 8% by weight.

Enzymes Conventional proteases and / or amylases can be used in the present compositions, for example, Savinase®, Termamyl® available from Novo or enzymes as taught in WO 98/42622, Engelhard.

Polymeric soil release agents Polymeric soil release agents, hereinafter "SRA" or "SRP" can be used herein. The levels include from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0%. Preferred SRAs can have hydrophilic segments and hydrophobic segments and can include anionic or even cationic monomeric units (see E.U.A. 4,956,447), as well as uncharged. The structures can be linear, branched or even star-shaped. Preferred SRAs include oligomeric terephthalate esters, for example, made by transesterification / oligomerization with a suitable catalyst. Said esters may incorporate additional monomer linkage through u, two, three, four or more positions, generally without heavy entanglement. SRAs also include those with segments of ethylene terephthalate or propylene terephthalate with ethylene oxide or propylene oxide, see E.U.A. 3,959,230 and E.U.A. 3,893,929; cellulose derivatives such as hydroxyether cellulosic polymers available from METHOCEL of Dow; and C-1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses; see E.U.A. 4,000,093. Suitable SRAs characterized by hydrophobic poly (vinyl ester) segments include poly (vinyl ester) graft copolymers, for example, vinyl esters of Cj-Cß, preferably poly (viyl) acetate, grafted onto oxide base structures. polyalkylene. See European patent application 0 219 048, published April 22, 1987, by Kud, et al. Commercially available SRAs include SOKALAN SRA 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, derived from a polyoxyethylene glycol of average molecular weight of 300-5,000. Commercial examples include ZELCON 5126 from duPont and MILEASE from ICI. Additional classes of SRA include (I) non-ionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see E.U.A. 4,201,824 and E.U.A. 4,240,918; (II) SRA with carboxylate end groups made by adding trimellitic anhydride to known SRAs to convert terminal hydroxyl groups to trimethoitate esters. See also E.U.A. 4,525,524; (lll) SRA based on anionic terephthalate of the urethane-bound variety, see E.U.A. 4,201, 824; (IV) poly (vinylcaprolactam) and copolymers related to monomers such as vinylpyrrolidone and / or dimethylaminoethylmethacrylate, including nonionic and cationic polymers, see E.U.A. 4,579,681; (V) graft copolymers, in addition to the SOKALAN types of BASF made by grafting acrylic monomers onto sulfonated polyesters; these SRAs have dirt release and anti-redeposition activity for known cellulose ethers; see EP 279,134 A, 1988; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on proteins such as caseins, see EP 457,205 A, 1991; (VII) SRA of polyester-polyamide prepared by condensing adipic acid, caprolactam and polyethylene glycol, especially treating polyamide fabrics, see DE 2,335,044 1974. Other useful SRAs are described in E.U.A. 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated or acylated amines or polyamines having clay dirt removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines.; Liquid detergent compositions typically contain about 0.01% to about 5%. A preferred etchant and anti-redeposition agent is ethoxylated tetraethylenepentamine. See the patent of E.U.A. 4,597,898. See also European patent application 111, 965, published June 27, 1984. Other clay soil removers / anti-redeposition agents that may be used include the ethoxylated amine polymers described in European Patent Application 111, 984, published on June 27, 1984; the zwitterionic polymers described in European patent application 112,592, published on July 4, 1984; and the amine oxides described in the U.S.A. 4,548,744. Other known clay soil removers and / or anti-redeposition agents are described in US Pat. 4,891, 160 and in WO 95/32272, published on November 30, 1995. Another type of preferred anti-redeposition agent includes the known materials such as carboxylmethylcellulose (CMC).

Polymeric dispersion agents Polymeric dispersion agents can be used here at levels of from about 0.1% to about 7%, by weight, especially in the presence of hybrid builders of aluminosilicate, zeolite and / or layered silicate. Said di-agents include polymeric polycarboxylates and polyethylene glycols. It is believed that polymeric dispersing agents increase the performance of the detergency builder by mechanisms such as inhibition of crystal growth, particulate soil release, peptization and anti-redeposition. The polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic. The presence of the polymeric polycarboxylates in the present or polymeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid, as in water-soluble salts of polymerized acrylic acid. The average molecular weight of said polymers perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably still from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. See the patent of E.U.A. 3,308,067. Copolymers based on acrylic / maleic acid can also be used. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers preferably ranges from about 2,000 to 100,000, most preferably about 5,000 to 75,000 and most preferably still about 7,000 to 65,000. The ratio of acrylate segments to those of maleate will generally vary from about 30: 1 to about 1: 1, most preferably about 10: 1 to 2: 1. Alkali metal, ammonium and substituted ammonium salts can be used. See European patent application No. 66915, published December 15, 1982, as well as EP 193,360, published September 3, 1986, which also discloses polymers comprising hydroxypropylacrylate. Other useful dispersing agents include the terpolymers of maleic / acrylic / vinyl alcohol. Such materials are also described in EP 193,360, including, for example, terpolymer 45/45/10 maleic / acrylic / vinyl alcohol. Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance and can act as a clay dirt removal and anti-redeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably about 1,000 to about 50,000 and most preferably about 1,500 to about 10,000. The dispersing agents of polyaspartate and polyglutamate can also be used. A preferred average molecular weight is about 10,000.

Other types of polymer that may be used include various terpolymers and hydrophobically modified copolymers, including those marketed by Rhom & Haas, BASF Corp., Nippon Sokubai and others for all forms of water treatment, textile treatment, or detergent applications.

Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.01% to 1.2% by weight, in the detergent compositions herein. Suitable brighteners include those identified in the US patent. 4,790,856. These include Verana PHORWHITE brighteners. Other brighteners described in '856 include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Arctic White CWD, the 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazole; and 2- (stilbene-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015.

Dye transfer inhibiting agents The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Typically, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and materials considered for the bleaching system such as zinc, manganese and phthalocyanines. silicon, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%.

Guelaator Agents The detergent compositions herein may also optionally contain one or more chelating agents for metals such as iron and / or manganese in water soluble, colloidal or particulate form or associated as oxides or hydroxides, or found in association with such soils. as humic substances. Preferred chelators effectively control said transition metals, especially limit the deposition of said transition metals or their compounds on the fabrics and / or control undesirable reduction oxide reactions in the washing medium and / or in the fabrics or in faces of hard surfaces. Such chelating agents include those having low molecular weights as well as polymeric types, typically having at least one, preferably two or more donor heteroatoms such as O or N, capable of coordination with a transition metal. Common chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Preferred chelating agents (chelators) include EDTA, S, S'-EDDS, DTPA, phosphonate types such as HEDP and mixtures thereof. If used, the chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent composition. Most preferably, the chelating agents will comprise from about 0.01% to about 3.0% by weight of the composition. Foam suppressors - Foam suppressors useful herein may be individual materials or may be mixed or combined in known ways, see Kirk Othmer Encyclopedia of Chemical Technology, 3a. Ed., Vol. 7, p. 430-447 (John Wiley &Sons, Inc., 1979). Common foam suppressors include C-J0-C24 monocarboxylic fatty acids, preferably C-jβ-C-is and salts thereof. See the patent of E.U.A. 2,954,347. Suitable salts include the salts of Na, K, Li, Ca, Mg, Al, Zn, ammonium and alkanolammonium. Stearic acid and aluminum tristearate are common examples. Alternative foam suppressors include linear, cyclic or mixed high molecular weight liquid or waxy C-12-C70 hydrocarbons (see E.U.A. 4,265,779) such as paraffins or halogenoparaffins; fatty acid esters such as fatty acid triglycerides; fatty acid esters of monovalent alcohols; C-18-C40 ketones. aliphatics such as stearone; N-alkylated aminotriacines as well as tri to hexa-alkylmelamines or di to tetra-alkyldiaminoclortriazines; and hydrocarbyl, especially stearyl, preferably monostearyl, phosphate esters such as monostearyl acid phosphate. Another preferred category of foam suppressors comprises silicone foam suppressors including polyorganosiloxane oils, such as polydimethisiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes with silica particles wherein the polyorganosiloxane is chemisorbed or fused to the silica. See E.U.A. 4, 265,779, EP 89307851.9, E.U.A. 3,455,839, and German patent application DOS 2,124,526. Silicone scavengers and foam controlling agents in granular detergent compositions are further described in E.U.A. 3,933,672 and E.U.A. 4,652,392. In certain preferred silicone foam suppressants useful herein, a solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The suppressor of primary silicone foams is branched / interlaced. Certain liquid laundry detergent compositions with controlled foams will comprise from about 0.001 to about 1, most preferably from about 0.05 to about 0.5, weight percent of silicone foam suppressors comprising (1) a non-aqueous emulsion of an agent primary antifoam which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound that produces silicone resin, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of Mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of not more than about 2% by weight; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S.A. 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994, and US patents. 4,639,489 and 4,749,740, Aizawa et al in column 1, line 46 to column 4, line 35. Other foam suppressors useful herein comprise secondary alcohols (eg, 2-alkylalkanols) and mixtures of said alcohols with silicone, such as the silicones described in the USA 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the Cg-C-ig alkyl alcohols having a C-i-C-jg chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the trade name ISALCHEM 123 from Enichem. Mixed foam suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1: 5 to 5: 1. The foam suppressors, when used, are preferably present in a suppressive amount of foams. By "foam suppressing amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foams to result in a low foaming laundry detergent for use in automatic laundry washing machines.

Other ingredients A wide variety of other ingredients useful in detergent compositions can be included in compositions herein, including perfumes, foam stabilizers, softening clays such as bentonite, montmorillonite, hectorites, other clays such as laponite or kaolin, chlorine scavengers such as ammonium sulfate; other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, fillers, especially for stick compositions, etc. If desired, magnesium and / or calcium salts such as MgCl 2, MgS 4, CaCl 2, CaS 4, magnesium silicates or the like may be added, for example, as fillers for stick forms of the compositions. Various detersive ingredients employed in the present compositions can optionally be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said phosphate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash solution, where it performs its intended detersive function. The detergent compositions herein will preferably be formulated so that, during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between 7.0 and 10.5, most preferably between about 7.0 and approximately 9.5. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Form of the Compositions The compositions herein may vary in physical form, as illustrated in non-limiting manner by granular, tablet, bar and pouch forms. The compositions include the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of an assortment device placed in the tub of the machine with the dirty fabric charge. The average particle size of the components of granular detergent compositions herein is preferably such that no more than 5% of the particles are greater than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15 mm in diameter . "Average particle size" herein may be determined by screening a sample of material that will be sized in a number of fractions (typically 5) in a series of Tyler sieves. The weights of the fractions are plotted against the opening size of the sieves. The average particle size is the aperture size through which 50% by weight of the sample would pass. Some preferred granular detergent compositions according to the present invention are high density types, now known in the market; typically these have a bulk density of at least 600 g / liter, most preferably from 650 g / liter to 1200 g / liter.

Laundry Method The methods for machine washing typically comprise the treatment of laundry with an aqueous wash solution in a washing machine having dissolved or dispersed therein an effective amount of a detergent composition of the invention. By "effective amount" is meant here from 40 g to 300 g of product dissolved or dispersed in a volume washing solution of 5 to 65 liters. In the context of laundry, the "levels of use" of the product can vary widely, depending not only on the type and severity of soils and stains, but also on the washing water temperatures and volumes and type of washing machine. In a preferred use aspect, an assortment device is employed in the washing method. The assortment device is loaded with the detergent product and used to introduce the product directly into the tub of the washing machine before starting the washing cycle. Its capacity must be such that it can contain sufficient detergent product as would normally be used in the washing method. Once the washing machine has been loaded with clothes, the assortment device containing the detergent product is placed inside the tub. At the beginning of the wash cycle of the washing machine, the water is introduced into the tub and the tub rotates periodically. The design of the assortment device will be such as to allow the containment of the dry detergent product but then allow the release of this product during the wash cycle in response to its agitation as the tub rotates and also as a result of its contact with the water of washing. Alternatively, the dispensing device may be a flexible container, such as a bag or sack. The bag can be of a fibrous construction coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it can be formed of a synthetic polymeric material insoluble in water provided with an edge or seal seal designed to be broken in aqueous medium as described in published European patent application Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of brittle water closure comprises a water soluble adhesive disposed along and sealing an edge of a sack formed of a water-impermeable polymeric film such as polyethylene or polypropylene.

Abbreviations used in the examples Sodium 011-13 Alkylbenzenesulfonate (linear, branched or mixed). Alkylsulfate CxyAs: Alkylsulfate, typically sodium salt form, derived from fatty alcohol containing x a and carbon atoms. Examples include sodium tallow alkyl sulfate (TAS) and branched alkyl halves of the chain, from Guerbet (WO 97/39088) containing from 10 to 20 carbon atoms (very typically from 14 to 16 or from 16 to 18) omezclas of the same. Alkylalkoxysulfate Sodium salt of linear or branched fatty alcohol (WO / 39087) condensed with one or more moles of ethylene oxide, propylene oxide, especially C1x-1 alkyl sulphate and sodium condensed with z moles of ethylene oxide, v.gr ., C15Q1S.

Nonionic Linear or branched nonionic surfactant (WO / 39091), typically CxyEz derived from fatty alcohol with chain length of x a and condensed with an average of z moles of ethylene oxide. Suitable examples include C25E3, C24E5, C24E7.

Glucamide (Coco) ALKYL-n-METILGLUCAMIDE OF c16-c18 or alkyl-N-methylglucamide of C16-18. Amine oxide N-oxide of linear or branched C12-C18 alkyldimethylamine (WO97 / 39091). QAS Quaternary ammonium surfactant, eg, dodecyltrimethylammonium chloride, or R2.N + (CH3) 2 (C2H40H) X- with R2 = C12-C14 X- = C Fatty acid Sodium linear alkylcarboxylate derived from a mixture of 80/20 fatty acids of tallow and coconut (longer chain soaps can be double-acting and contribute to the suppression of foams); whole cut fatty acids in the upper part of c12-C14; mixtures Material Improver described in the examples of hybrid detergency synthesis mentioned above. Zeolite system; one or more of; Zeolite A Hydrated sodium aluminosilicate of the formula Na12 (AI02SiOa) 12.27H20 having a particle size in the range of 0.1 to 10 microns (weight expressed on an anhydrous basis). Zeolite P Zeolite P (may be of the maximum aluminum type).

Zeolite X Zeolite X. Zeolite AX co-crystallized AX Zeolites (Condea, EP 816291 A1).

Sodium silicate system 2r or 3r; crystalline layered silicate of the formula d-Na2-Si205 (Hoechst / Clariant); amorphous sodium silicate (SiO2: Na2O = 2.0: 1); mixtures thereof. (the hydration of any zeolite may vary) Phosphates: one or more of STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Polycarboxylate that is not polymeric; one or more of: Citrate Anhydrous citric acid; trisodium citrate dihydrate activity of 86.4% with a particle size distribution between 425 μm and 850 μm; and mixtures thereof.

TMS / TDS Monosuccinate-tartrate / Disiccinate-tartrate, sodium salts. ODS 2,2'oxidisuccinate, sodium salts. CMOS Carboxymethyloxysuccinate, sodium salts. NTA Nitriloacetic acid, sodium salts. Carbonate Carbonate of sodium or potassium anhydrous, e.g., with particle size between 200 μm and 900 μm for mixing; or less than 100 μm, if there is no agglomerate.

Polycarboxylate of any polycarboxylate of molecular weight above polymer type of 1000, especially sodium salt of copolymer of 1: 4 maleic / acrylic acid, average molecular weight of 70,000, sodium salt; sodium polyacrylate of average molecular weight of 4,500; mixtures thereof; or mixtures of said polymers with any PEG. A polycarboxylate of the preferred polymer type has polyglyoxylate structural units (see, for example, US Pat. No. 4,146,495, US Pat. No. 4,140,676, EP 803,521 A) Anti-rejection agents, sodium carboxymethylcellulose; methyl cellulose methyl cellulose ether with a high degree of polymerization of 650 available from ShimEtsu Chemicals; starch derivative, sugar derivative, sorbitol derivative or any other antiredeposition agent derived from carbohydrate or ash accumulation prevention agent, or mixtures thereof. Enzyme system: one or more than: Protease Enzyme activity protease 4KNPU / g sold by NOVO Industries A / S under the trade name Savinase. Alcalase Proteolytic enzyme activity 3AU / g sold by NOVO Industries A / S. Cellulose Enzyme cellulolytic activity 1000 CEVU / g sold by NOVO Industries A / S under the trade name Carezyme. Amylase Activity amylolytic enzyme 120KNU / g sold by NOVO Industries A / S under the trade name Termamyl 120T Lipase Lipolytic activity enzyme 100KLU / g sold by NOVO Industries A / S under the trade name Lipolase Endolase Enzyme activity endoglucanase 3000 CEVU / g sold by NOVO Industries A / S Sodium perborate bleach tetrahydrate of nominal formula primary oxygen NaB02.3H20.H202 (abbreviated: PB4); sodium hydrogen peroxide perborate of nominal formula NaB02.H202 (abbreviated: PB1); sodium percarbonate of nominal formula 2Na2C03.3H2O2 (abbreviated: PC); any of these in coated or uncoated form; or mixt thereof. Activator of blanCualquier di- or poli. lower acylated soluble amine hydrophilic quencher in water, especially tetraacetylethylenediamine. Activator of blanNOBS, that is, nonanoyloxybenzenesulfonate in hydrophobic chelator form of the sodium salt; NAC-OBS, that is, (6- nonamidocaproyl) oxybenzenesulfonate; mixt thereof; or the like, Peroxyacid preforv.gr., EP 778342 A1. hydrophobic molding agent, eg, omega- (3,4-dihydroisoquin-organic bleach, linolamine, US 5,576,282). Catalyst for blanv.gr., as described in WO 97/00937, metal chelator. WO 96/06155, EP 718,398 A transition Photoblanker Sulfonated zinc phthalocyanine encapsulated in bleachable dextrin-soluble polymer, or low-tint photobleaner - see, for example, phthalocyanine derivatives of Si from WO 97/05202. or more than: DTPA Diethylenetriaminepentaacetic acid. DTPMP Diethylenetriaminepenta (methylenephosphonate), manufactured by Monsanto under the trade name Dequest 2060.

EDDS Ethylenediamine-N-N'-disuccinic acid, isomer (S, S) in the form of its sodium salt, HEDP 1, 1-hydroxyethanediphosphonic acid. 4,4'-bis (2-sulphotryl) biphenyl disodium brightener; 4,4'-bis (4-anilino-6-morpholino-1, 3,5-triazin-2-yl) amino) stilbene-2,2'-disulfonate disodium; mixtures thereof. Dirt releasing agent; one or more of: SRP 1 End blocked esters with sulfobenzoyl, with base structure of oxyethyleneoxy and terephthaloyl SRP 2 Short block polymer of poly (1, 2-propyleneterephthalate) diethoxylated Release agent of v.gr., as described in WO 97/42285 TEPAE dirt ethoxylated tetraethylenepentamine. PVP Polyvinylpyrrolidine polymer, with an average molecular weight of 60,000.

PVPNO Polymer of N-oxide of polyvinylpyrrolidone, with an average molecular weight of 50,000. PVPV1 Copolymer of polyvinylpyrrolidinone and vinylimidazole, with an average molecular weight of 20,000. Anti-foaming system eg, controller of polydimethylsiloxane foams with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1; It can be complemented by fatty acid (s). Other materials Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm. Sulfate Anhydrous sodium sulfate. Stabilizers, processing aids and other minor components; e.g., one or more of: Sodium Borate Borate. Wax Paraffin wax PEGx Polyethylene glycol, with a molecular weight of x. PEO Polyethylene oxide, with an average molecular weight of 50,000.

Perfume Any perfume or pro-perfume, see, for example, "floral perfume" in WO 97/34987. In the following examples, all levels are given in% by weight of the composition.

EXAMPLE 1 Granular laundry detergents for use in household appliances or manual laundry at a concentration of 100 to 10,000 ppm, depending on the apparatus and / or water and / or conditions, are prepared according to the invention.

Sulphate, stabilizers, 100% 100% 100% 100% 100% 100% processing aids, minor components up Density in g / liter 200- 200- 200- 200- 200- 200- (interval) 900 900 900 900 900 900 EXAMPLE 2 Granular laundry detergents for use in household appliances or manual laundry at a concentration of 100 to 10,000 ppm, depending on the apparatus and / or water and / or conditions, are prepared according to the invention.

Sulphate, stabilizers, 100% 100% 100% 100% 100% 100% processing aids, minor components up to Density in g / liter 200-900 200- 200- 200- 200- 200-900 (range) 900 900 900 900 EXAMPLE 3 Bar compositions for laundry are prepared according to the present invention.

High Density Detergent Composition Process Spray drying towers can be used to make granular laundry detergents from base powders. These often have a density less than about 500 g / l. Typically. An aqueous suspension of ingredients is passed through a spray-drying tower at a temperature of about 175 ° C to about 225 ° C. Additional steps of the procedure should be used to obtain low density, high density detergents. "High density" means greater than about 550, typically greater than about 650, grams / liter or "g / l"). In this way, spray-dried pellets can be densified by charging a liquid surfactant, often a non-ionic surfactant, into the pores of the granules and / or by passing them through one or more high-speed mixers / densifiers, such as a device sold as "Lódige CB 30" or Lódige CB 30 Recycler. "This comprises a static cylindrical mixing drum having a central rotating shaft on which mixing / cutting vanes are mounted. are introduced into the drum and the arrow / vane assembly is rotated at speeds in the range of 100-2500 rpm to provide uniform mixing / densification, see US 5,149,455 and 5,565,422.Another suitable commercial apparatus includes the granulator "Shugi Granulator" and the "Drais K-TTP 80". Spray-dried granules can also be densified by treating them in a moderate speed mixer / densifier to obtain particles, for which the Lambda KM "(Series 300 or 600) or" Lódige Ploughshare "mixers / densifiers are suitable and are typically operated at 40-160 rpm Other useful equipment includes the "Drais KT 160." This step of the process using a mixer / densifier (eg, Lodige KM) can be used alone or sequentially with the mixer / densifier (v. ., Lódige CB) mentioned above to achieve the desired density Other types of granule manufacturing apparatus useful herein include the density described in US Patent 2,306,898 to GL Heller, December 2, 1942. Although it may be more suitable Using the high speed mixer / densifier followed by the low speed mixer / densifier, the sequential, inverse mixer / densifier configuration can also be used One or a combination of various parameters including residence times in the mixers / densifiers, equipment operating temperatures, temperature and / or composition of the granules, the use of auxiliary ingredients such as liquid binders and flow aids, can be used to optimize the densification of the granules spray dried. By way of example, see the procedures in E.U.A. 5,133,924; E.U.A. 4,637,891 (granulation of spray-dried granules with a liquid binder and aluminosilicate); E.U.A. 4,726,908 (granulation of spray-dried granules with a liquid binder and aluminosilicate); and E..U.A. 5,160,657 (coating of granules with aluminosilicate). The heat sensitive or highly volatile detergent ingredients are preferably incorporated into the detergent composition without redistributing spray drying, for example, by feeding thermally sensitive ingredients or volatile ingredients continuously or intermittently to a mixing / densifying equipment. A preferred embodiment involves charging a paste of surfactant and anhydrous material into a high speed mixer / densifier (e.g., Lódige CB) followed by a moderate speed mixer / densifier (v, gr., Lódige KM) to form high density agglomerates. See E.U.A. and use. 5,486,303. The liquid / solids ratio of the ingredients can be selected to obtain high density agglomerates that are freer and crisp. See E.U.A. 5,565,137. Optionally, the method may include one or more streams of non-dimensioned particles. These can be recycled to mixers / densifiers for subsequent agglomeration or accumulation. Oversized particles can be sent to a grinding apparatus, the product of which is fed back to the mixer / densifier equipment. Said recycling facilitates the control of the general particle size giving finished compositions having a relatively uniform particle size distribution (400-700 microns) and a density (> 550 g / l). See E.U.A. 5,526,448 and E.U.A. 5,489,392. Other suitable methods that do not require spray drying are described in E.U.A. 4,828,721, E.U.A. 5,108,646 and E.U.A. 5,178,798. In another embodiment, high density detergent compositions can be produced using a fluidized bed mixer in which the ingredients are combined as an aqueous suspension (typically 80% solids content) and sprayed in a fluidized bed to provide finished granules. Optionally before mixing in fluid bed the suspension can be treated using the aforementioned Lódige CB mixer / densifier or a "Flexomix 160" mixer / densifier, available from Shugi. You can also use the fluidized bed or moving beds of the type available under the trade name? Scher Wyss. "Another alternative procedure involves feeding a liquid acid precursor of an anionic surfactant., an inorganic alkaline material (e.g., sodium carbonate) and optionally other detergent ingredients in the high speed mixer / densifier (residence time of 5 to 30 seconds) to form particles containing a partially anionic surfactant salt or completely neutralized and the starting detergent ingredients. Optionally, the content in the high-speed mixer / densifier results in the finished high-density detergent composition. See E.U.A. 5,164,108. Optionally, high density detergent compositions can be produced by mixing conventional spray-dried detergent granules with detergent agglomerates in various proportions (e.g., 60:40 weight ratio of granules to agglomerates) produced by one or a combination thereof. procedures described in the present invention. Auxiliary ingredients such as enzymes, perfumes, brighteners and the like may be sprinkled or mixed with the agglomerates, granules or mixtures thereof produced by the methods described herein. For example, see, E.U.A. 5,569,645.

EXAMPLES 4-6 Various detergent compositions made in accordance with the invention and specifically for top loading washing machines are illustrated below. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed in a suspension and passed through a spray-drying tower having a countercurrent flow of hot air (200 -300 ° C) which results in the formation of porous granules. The blended agglomerates are formed from two feed streams of detergent ingredients that are fed continuously, at a rate of 1400 kg / hr, into a LODIG CB-30 mixer / densifier, one of which comprises a surfactant paste which contains surfactant and water and the other stream contains dry starting detergent material containing sodium carbonate and insoluble inorganic builder such as hybrid aluminosilicate or combination thereof with zeolite. The rotation speed of the arrow of the mixer / densifier Lódige CB-30 is approximately 1400. The contents of the Mixer / densifier Lódige CB-30 is continuously fed to a Lodige KM600 mixer / densifier for agglomeration by subsequent accumulation. The resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler prior to mixing with the spray dried granules. The remaining auxiliary detergent ingredients are sprinkled or added to the mixture of agglomerates and granules. Alternatively, the magnesium silicate can be added dry, in whole or in part, to the composition. 4 5 6 Aluminosilicate base granule 18.0 0 17.0 Sodium sulphate 10.0 8.0 19.0 Sodium Polyacrylate Polymer 3.0 3.0 2.0 Polyethylene glycol (MW = 4000) 2.0 2.0 1.0 Linear Alkylbenzenesulfonate of C12-13 of 6.0 6.0 7.0 Na Alkylsulfate secondary of C1-4-16 of Na 3.0 3.0 3.0 Ethoxylated CI-HS Alkylsulfate of Na 3.0 3.0 2.0 Sodium silicate 1.0 1.0 2.0 Rinse aid 246 0.3 0.3 0.3 Sodium carbonate 7.0 7.0 25.7 DTPA1 0.5 0.5 - Mixed agglomerates Alkylsulfate of C.-MS of 5.0 5.0 - Alkylbenzenesulfonate of C12-13 2.0 2.0 - linear, Na.

Sodium carbonate 4.0 11.0 - Polyethylene glycol (PM-4000) 1.0 1.01- Hybrid aluminosilicate mixture - 20.0 5.0 Alkylated C12-15 ethoxylate (EO = 7) 2.0 2.0 0.5 Perfume 0.3 0.3 1.0 Polyvinylpyrrilidone 0.5 0.5 - Polyvinylpyridine N-oxide 0.5 0.5 - Polyvinylpyrrolidone-polyvinylimidazole 0.5 0.5 - Distearylamine and cumenesulfonic acid 2.0 2.0 - Dirt-freeing polymer2 2.0 2.0 - Lipolase Lipolase (100,000 LU / I) 4 0.5 0.5 - Termamyl amylase (60 KNU / g) 5 0.3 0.3 - CAREZYME® (100 CEVU / g) 4 0.3 0.3 - Protease (40 mg / g) 5 0.5 0.5 0.5 NOBS3 5.0 5.0 - Sodium percarbonate 12.0 12.0 - Polydimethylsiloxane 0.3 0.3 - Various components (water, etc.) the rest the rest the rest Total 100 100 100 Diethylenetriaminepentaacetic acid Made in accordance with the patent of E.U.A. 5,415,807, issued May 16, 1995. 3 Nonanoyloxybenzenesulfonate 4 Purchased from Novo Nordisk A / S 5 Purchased from Genencor purchased from Ciba-Geigy Aluminosilicate = 1-10 A Zeolite A

Claims (1)

1. NOVELTY OF THE INVENTION CLAIMS 1, - A detergent composition comprising: (a) 0.1% a 99% of a builder system comprising, in part, a particulate inorganic ion exchange builder material, said builder material comprising (i) a crystalline zeolitic aluminosilicate hybrid builder and (ii) by at least one occluded co-builder, preferably selected from the group consisting of an occluded silicate co-builder, an occluded non-silicate co-builder and mixtures thereof, preferably a co-builder of occluded silicate detergent, (iii) optionally, at least one co-builder or auxiliary other than said occluded co-builder adsorbed on or externally chemically bonded to said hybrid; wherein said hybrid preferably has a ratio of Si? 2 / Al2? 3 below 3 and is formed by a process comprising the step of adding an aluminum source to a concentrated silicate solution having a pH above 12. , said silicate solution having been at least partially depolymerized by heating before the addition of said aluminum source and (b) from about 0.1% to about 99% of at least one detergent auxiliary selected from auxiliaries other than any auxiliary of said builder system, most preferably from the group consisting of: (i) detersive surfactants, preferably from 0.1% to 30% by weight of said detergent composition, preferably selected from the group consisting of: cationic surfactants, surfactants anionic, surfactants having at least one biodegradable branched hydrophobe and mixtures thereof, wherein The surfactant having at least one biodegradable branched hydrophobe is preferably selected from CQ-C Q alkyl sulphates branched with C 1 -C 4 at the half chain, alkyl alcohols of ethoxylated, propoxylated or butoxylated branched CS-CJ S with C- 1-C4 in the middle of the chain, CS-CJ S alkyl ethoxylates branched with C 1 -C 4 in the middle of the chain, C alqu-C- | 6 alkylbenzenesulfonates branched with C -] - 4 4 in the middle of the chain and mixtures thereof; (ii) organic polymeric materials selected from the group consisting of oligomeric esters blocked at the ends; hydrophobically modified polyacrylates, terpolymers compenising maleate or acrylate, polymeric dye transfer inhibitors, polyimine derivatives and mixtures thereof; (iii) oxygen bleach promoter materials selected from the group consisting of organic bleach activators, transition metal bleach catalysts, photobleaching agents, bleach promoting enzymes and mixtures thereof; (iv) fabric care promoting agents other than softeners or said organic polymeric materials; and (v) optionally, a double chelator system having at least one aminofunctional chelator that is not phosphonate and at least one functional phosphonate chelator; and (vi) optionally, a polycarboxylate polymer, preferably a Murphy-type polycarboxylate polymer system; wherein said polycarboxylate polymer, when present, is in said detergent composition at a level of less than 2% by weight of the composition; and (vii) mixtures of (i) - (vi). 2 - The detergent composition according to claim 1, further characterized in that said crystalline zeolitic aluminosilicate hybrid comprises 0.01 to 1.0 weight fraction of said builder system and said crystalline zeolitic aluminosilicate hybrid is characterized by an ability to sequester calcium in excess of the amount of charge inducing aluminum in the zeolitic aluminosilicate and / or said crystalline zeolitic aluminosilicate hybrid is characterized by a calcium ion exchange capacity of at least 15% greater than the calcium ion exchange capacity of a reference material selected from zeolite A not hybridized. 3. The detergent composition according to any of the preceding claims, further characterized in that said occluded non-silicate co-builder is selected from (i) the group consisting of occluded phosphate, occluded carbonate, occluded borate, occluded nitrate, occluded nitrite, occluded sulfate, Na2? occluded, occluded NaOH and mixtures thereof; and (i) mixtures of said occluded co-builder which is not silicate and occluded silicate; provided that in any of said occluded co-builder mixtures that is not silicate and occluded silicate the weight fraction of occluded silicate is not greater than about 0.99, preferably not more than about 0.80. 4. The detergent composition according to any of the preceding claims, further characterized in that said co-builder adsorbed or chemically linked externally or auxiliary is an auxiliary that does not contain detergency builder and wherein said auxiliary that does not contain builder detergency reduces the negative surface charge of the hybrid relative to the untreated hybrid, whereby said component (a) has improved compatibility with cationically charged surfactants and / or enzymes. 5. The detergent composition according to any of the preceding claims, further characterized in that said occluded co-builder is selected from the group consisting of co-builder that does not contain occluded silicate and co-builder mixtures. which does not contain occluded silicate and occluded silicate co-builder, and wherein said occluded co-builder that does not contain silicate is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitrite , sulfate occluded, Na2? occluded and mixtures thereof. 6. The detergent composition according to any of the preceding claims, further characterized in that said hybrid preferably comprises at least about 0.01 weight fraction of said builder system and wherein said occluded co-builder is selected from the group which consists of occluded silicate builder, non-silicate occluded co-builder and blends of said silicate occluded co-builder and said occluded co-builder which is not silicate; and wherein said occluded non-silicate co-builder, when present, is at a weight ratio to the silicate occluded co-builder of from about 1: 1000 to about 1000: 1 and is selected from the group consisting of occluded nitrate, occluded phosphate, occluded carbonate, occluded borate, occluded nitrite, occluded sulfate, Na2? occluded and mixtures thereof. 7. The detergent composition according to any of the preceding claims, further characterized in that said hybrid comprises at least about 0.10 weight fraction of said builder system and wherein from about 0.10 to about 0.90 weight fraction of said builder system is selected from the group consisting of zeolite A, zeolite B, zeolite P, zeolite MAP, zeolite X, zeolite .AX, clays, layered silicates, chain silicates, soluble silicates, citrates, nitrilotriacetates, ethercarboxylates, carbonates, polyacetal carboxylates and mixtures thereof, wherein said ether carboxylates are preferably selected from the group consisting of carboxymethyloxysuccinate, tartrate-monosuccinate, tartrate-d-succinate, oxydisuccinate and mixtures thereof and wherein said carbonates are preferably selected from the group It consists of sodium carbonate, sodium bicarbonate and mixtures thereof. 8. The detergent composition according to any of the preceding claims, further characterized in that the builder system has measurable hydroxisodalite as evidenced by the powder pattern of XRD, preferably as evidenced by peaks 14.0, 24.3 and 25.1 degrees 2 teta in the XRD powder pattern of the detergency builder system taken as a whole; very preferably where the hybrid has measurable hydroxisodalite as evidenced by peaks at 14.0, 24.3 and 25.1 degrees 2 teta in the powder pattern of XRD of the hybrid examined as such. 9. The detergent composition according to any of the preceding claims, further characterized in that said hybrid builder material has a capacity to sequester calcium in excess of the amount of charge inducing aluminum in the crystals of the hybrid builder material. 10. The detergent composition according to any of the preceding claims, further characterized in that said builder material is characterized by a calcium ion exchange capacity of at least 25% greater than the capacity of calcium ion exchange. of a reference material selected from unhybridized zeolite A. 11. The detergent composition according to any of the preceding claims, further characterized in that the total SIO2 in said hybrid builder material can be 1.02 to 1.50 times the Si02 of the working frame as determined by diffraction comparison. X-ray, X-ray fluorescence and 9Si NMR analysis. 12. The detergent composition according to any of the preceding claims, further characterized in that the step of depolymerizing the sodium silicate solution preferably consists of heating at temperatures of 50 ° C to 85 ° C for a period of 10 minutes or more . 13. The detergent composition according to any of the preceding claims, further characterized in that the composition comprises soluble silicate as a non-occluded co-builder and wherein the total level of soluble silicate in said composition as a whole is limited, and is preferably not greater than the equivalent of about 3% by weight of the 2.0 g sodium silicate composition. 14. The detergent composition according to any of the preceding claims, further characterized in that said builder system comprises the particulate hybrid aluminosilicate material together with at least one traditional builder material, at a ratio of hybrid aluminosilicate to tradiiconal builder material from 5: 1 to approximately 1: 5. 15. The detergent composition according to any of the preceding claims, further characterized in that said hybrid has a ratio of SiO2 / AI2O3 below 3 and formed by a process comprising the step of adding an aluminum source to a solution of concentrated silicate having a pH above 12, said silicate solution having been at least partially depolymerized by heating before the addition of said aluminum source and in addition, optionally but preferably, at least one source of co-builder occludable that is not silicate that has been added in any step and / or in addition, optionally but preferably, at least one surface treatment agent that has been applied to the external surfaces of said hybrid after the formation thereof; subject to at least one of the following considerations with respect to the composition of said builder system: - the builder system has measurable hydroxisodalite as evidenced by peaks at 14.0, 24.3 and 25.1 degrees 2 teta in the dust pattern of XRD of the detergency builder system taken as a whole and / or; -the hybrid has measurable hydroxisodalite as evidenced by peaks at 14.0, 24.3 and 25.1 degrees 2 teta in the powder pattern of XRD of the builder system taken as such and / or; - the hybrid has occluded co-builder that is not silicate as directly and / or indirectly evidenced by any combination of elemental analysis, XRD powder pattern, 29Si NMR or other known techniques and / or; - the hybrid has measurably different surface wetness and / or caraga compared to an untreated hybrid on its surface. 16. The detergent composition according to any of the preceding claims, further characterized in that said hybrid comprises occluded silicate; wherein said hybrid is characterized by 9Sl NMR peaks in the range of -81 to -85 ppm. 17. The detergent composition according to any of the preceding claims, further characterized in that said detergent composition has the form of a bar for laundry, tablet, granule or low density powder, granule or powder of high density (for example, >600 g / liter), paste or gel or liquid having dispersed solids, wherein said hybrid has a measurable improvement in the sum of calcium binding and magnesium binding compared to zeolite A, delta-layered silicates and mixtures of the same. 18. The detergent composition according to any of the preceding claims, further characterized in that said detergent composition has a solid form and the process for preparing the detergent composition comprises at least one step of combining said hybrid material with a film-forming polymer. . 19. The detergent composition according to any of the preceding claims, further characterized in that the hybrid material has measurably different wetting and / or surface loading as compared to the untreated hybrid on its surface; and wherein said measurable difference is achieved by the step of treating the hybrid material with PEG or a film-forming polymer. 20. The detergent composition according to any of the preceding claims, further characterized in that said chelator, when present, is in said detergent composition at a level of less than 2% by weight of the composition, preferably from 0.1% to 1.5 % of the composition; wherein said chelator is preferably selected from the group consisting of: DTPA, EDTA, S, S'-EDDS and mixtures thereof.