MXPA01003079A - Detergent compositions - Google Patents

Abstract

The invention relates to detergent compositions comprising from 10 to 60% by weight of a surfactant system and having a maximum Residual Index of 25 and a maximum Secondary Residual Index of 15, the claimed detergents provide good washing performance with based on the amounts of detergent components in the composition

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD The present invention relates to detergent compositions, in particular, to laundry detergent compositions.

BACKGROUND OF THE INVENTION All detergents for laundry applications contain surfactants and builders. In general, most detergents comprise a base powder, obtained by spray drying or by granulation of builder components and surfactant components, for example, by agglomeration or extrusion. Frequently, the base powder is further treated with post-treatment steps such as dry-adding other particulate detergent components, spraying other liquid components such as surfactants, particularly non-ionic surfactants, and / or post-dusting steps using finely particulate solids to reduce cake formation and tackiness of the solid detergents produced. Environmental pressures have led to the need to produce detergents that are as efficient as possible. The tendency to using smaller quantities of more highly compact detergent compositions, for example, having a density greater than 600 g / l or 650 g / l, or greater than 700 g / l or even greater, has emphasized the need to ensure total yield of all components detergents in the wash. However, solid detergents tend to form lumps or gel after coming into contact with water. The lumps of gelled material can then fall into the sink of a washing machine, where they are not mechanically altered, or due to their method of use in a machine, the solid detergents do not dissolve, resulting in poor supply of the product from a supply compartment of a washing machine or from a supply device and / or once in the machine itself. Poor use of all detergent components is therefore achieved. The inventors have found that in order to counteract this problem a combination of properties is required. This can be achieved by controlling the detergent and the detergent making process so that combinations of different detergent components, when formed into particles to make finished detergent are modified to obtain the maximum yield benefit for each detergent component. This results in detergent compositions that have good solubility and minimal gelling and therefore, maximum supply of detergent components to washing, for example, by minimizing the interaction of certain detergent components and carrying to the maximum the interaction between other detergent components. These benefits lead to good washing performance and minimize any damage to fabrics due to high concentrations of localized bleach.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, a solid detergent composition comprising from 10 to 60% by weight of a surfactant system and having a maximum Residue Index of 25 and a maximum Secondary Residue Index of 15 is provided. Waste can be calculated as follows: 1 liter of deionized water is placed in a tergitometer (Erweka DT6-R hereinafter referred to as the "Sotax" apparatus) (USP 711 standard solution). The Sotax is adjusted with a perspex lid to avoid evaporation, it is calibrated at a temperature of 5 ° C with the agitator (paddle) set at 200rpm. The blade has two blades fixed on the central axis directly opposite each other so that in general the two blades provide the blade with a diameter of 75 mm. The pallet is placed in the center of the Sotax apparatus with a distance between the bottom of the pallet and the bottom of the 25 mm tergitometer. The overall height of the pallet sheets is 19 mm. A wire basket with side walls and a base made of 20 mesh stainless steel wire (850μ), a diameter of 25 mm and a height of 41 mm is provided. The wire basket is filled with a product detergent, the surface of the detergent product is leveled and a non-permeable cap is used to close the upper part of the wire basket. The wire basket is suspended in a stationary position in the middle part between the central axis of the Sotax and the side wall, at a height such that the base of the wire basket is 7 mm above the upper surface of the pallet. After twelve minutes the assembly of the wire basket is removed from the Sotax apparatus and the residue is removed to a previously heavy container. The transfer step must be quantitative; if necessary, a rinsing step with deionized water is acetab- lized. The residues are dried in an oven at 70-80 ° C until no additional weight loss is recorded. The weight of the dry residue is recorded. The percentage of basket residue is calculated as a proportion of the mass of the initial sample of the detergent composition that was placed in the Sotax. An average residue percentage remaining for two identical samples provides the Waste index number. The Residue Index for the detergent compositions of the invention should not be greater than 25, preferably not greater than 20, still very preferably not greater than 15. The Secondary Waste Index is calculated as follows: Using the same apparatus, 800 ml of deionized water are charged to the Sotax device and the temperature is allowed to equilibrate at 20 ° C with a stirring speed of 200 rpm. 2 grams of the product are added to the deionized water and stirred at a stirring speed of 200 rpm for 20 minutes. After 20 minutes, the deionized water containing the detergent sample is filtered through a circle of black cloth C70 (from Empirical Manufacturing Company) placed in a Buchner funnel with the smooth side of the fabric at the top. The black cloth is removed from the Buchner funnel and placed on a sheet of paper. The black cloth is allowed to dry at room temperature for 24 hours. Three replicates are obtained for each test and an average of the percentage of residue remaining on the black cloth circle is calculated as a proportion of the total detergent sample loaded in the Sotax. The average residuals for the three replicates provide the Secondary Residue Index number which should be a maximum of 15. Preferably, the maximum Secondary Waste Index is 10, still very preferably, the maximum Secondary Residue Index should be 5. or less.

Detergency Enhancement System The detergent compositions comprise a builder system which can be provided by a builder or mixtures of more than one builder. Water soluble and / or water insoluble builders can be used. The builder system generally comprises from 1 to 90% in weight of the detergent composition, preferably 20 to 80% by weight of the composition.

Water-soluble or partially water-soluble detergency modifiers The builder system in the compositions according to the invention preferably contains a water-soluble and / or partially water-soluble builder compound, typically present at a level of 1. % to 80% by weight, preferably in amounts up to 50% by weight, or up to 40% or even 35%. Preferably, water-soluble builders are present in amounts of at least 3% or 8%, but are preferably present in amounts of 6 to 25% by weight. The detergent compositions of the invention may comprise a phosphate-containing builder material, such as tetrasodium pyrophosphate, or more preferably anhydrous sodium tripolyphosphate. The phosphate builders can be present at a level of 0.5% to 60%, or 5% to 50%, or even 8% to 40% by weight. However, crystalline layered silicates are also suitable builders partially soluble in water. The preferred crystalline layered silicate herein has the general formula: NaMSi? 02X + 1.yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and e is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0164514, and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4 and is preferably 2. M is preferably H, K or Na or mixtures thereof, preferably Na. The most preferred is a-Na2S205, ß-Na2S205 or d-Na2Si205, or mixtures thereof, with preferably at least 75% Na2Si205, for example available from Clariant as NaSKS-6. The crystalline layered silicate material, in particular of the formula Na2S205, may optionally comprise other elements such as B, P, S, for example, obtained by processes as described in EP 578986-B. The partially water soluble builder is preferably present at a level of up to 40%, more preferably up to 35%. When present, it may be preferred that the composition of the invention comprises from 10% to 40%, more preferably from 12% to 35%, or even from 15% to 25% by weight of the composition, of the partially soluble builder. in water Water-soluble builders include organic carboxylic acids and salts thereof. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, acids homopolymeric or copolymeric polycarboxylics or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. In addition to these water-soluble builders, polymeric polycarboxylates, including homopolymers and copolymers of maleic acid and acrylic acid, and their salts may be present. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid, and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, malic acid and fumaric acid, as well as ether carboxylates and the sulfinylcarboxylates. Polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241, Lactoxysuccinates described in British Patent No. 1, 389,732, and aminosuccinates described in the Netherlands application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1, 387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane tetracarboxylates, 1, 1, 3,3-propane tetracarboxylates and 1, 2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1, 398,421 and 1, 398,422 and in the US patent. No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1, 439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. Acid progenitors of monomeric or oligomeric polycarboxylate chelating agents, or mixtures thereof with their salts, for example, citric acid or citrate / citric acid mixtures, are also contemplated as useful builders components. More preferred may be acetic acid, citric acid, malic acid and fumaric acid, or their salts or mixtures thereof. It may be preferred that mixtures of the salt and acid form are present. The water-soluble builder is preferably present at a level of up to 40%, more preferably up to 35%. When present, it may be preferred that the composition of the present invention comprises from 10% to 40%, more preferably from 12% to 35%, or even from 15% to 25% by weight of the composition, of the water-soluble builder. It may be preferred that the polymeric or oligomeric polycarboxylates be present at levels less than 5%, preferably less than 3%, or even less than 2% or even 0% by weight of the compositions. Borate builder builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or detergent wash conditions, are water soluble builders useful herein. Other suitable water-soluble builder materials are polycarboxylic acids or polymeric polycarboxylates, including homo- or co-polymeric water-soluble polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms. Polymers of the latter type are described in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight of 1000-50000, preferably 10000 or even 7000, and copolymers of (poly) acrylate and maleic acid or anhydride, said copolymers preferably having a molecular weight of from 2,000 to 100,000, especially from 40,000 to 80,000.

In a preferred embodiment of the invention, the water soluble or partially insoluble builder, and in particular, the crystalline layered silicate when present, is present at least partially, for example, at least 50% by weight, in an intimate mixture with a surfactant, preferably an anionic surfactant. It has also been found that when highly water soluble carboxylic acid or carboxylate containing compounds are present in an intimate mixture with one or more of the surfactants and optionally other ingredients, the dissolution rate of the intimate mixture and also of the the surfactants and other ingredients. In this way, a faster delivery of surfactants and other ingredients can generally be achieved. In this manner, a preferred particulate component in the detergent compositions of the invention herein may comprise an intimate blend of preferably from 25% to 75% by weight, more preferably from 35% to 68%, even more preferably from 45% to 62% by weight, of the crystalline layered silicate component or water soluble builder, and from 25% to 75% by weight, more preferably from 32% to 62% by weight, most preferably from 38% to 48% by weight weight of the component of an anionic surfactant. Said particulate component preferably comprises less than 10% by weight of free moisture, preferably less than 5%, or • even less than 3%, or even less than 2% by weight. The free moisture content, as used herein, can be determined by placing 5 grams of the particulate component in a Petri dish, and placing this Petri dish in a convection oven at 50 ° C for 2 hours, and measuring Subsequently, the weight loss due to evaporation of the water. The anionic surfactant preferably comprises 50% to 100% by weight, preferably 60% or even 75% to 100% of the anionic surfactant of a sulfonate surfactant, preferably an alkylbenzene sulfonate surfactant, as described later. Up to 50% by weight or more, based on the total amount of anionic surfactant in the detergent composition, is preferably incorporated into said particulate component. Preferably, said particulate component is present in the detergent composition in amounts of 0.5% to 60% by weight, preferably 3% to 50%, more preferably 5% to 45%, even more preferably at a level of at least 7% by weight of the composition. Preferably, the weight ratio of the crystalline layered silicate and / or one or more water-soluble builders: the anionic surfactant in the intimate mixture is from 4: 5 to 7: 3, more preferably from 1: 1 to 2: 1, most preferably from 5: 4 to 3: 2. Said component may also comprise additional ingredients, for example, in amounts of 0% to 25%, generally not greater than 20% or even 15% by weight of the particulate component. The The precise nature of these additional ingredients, and the levels of incorporation thereof, will depend on the application of the component or compositions, as well as the physical form of the components and compositions. It may be preferred that the particulate composition comprises less than 15% or even less than 10% or even 5% by weight of the granulated material of the ethoxylated nonionic alcohol surfactant, preferably less than 15%, or even less than 10% or even less than 5% of any nonionic surfactant. It may be preferred that the particulate composition comprises less than 10% by weight, preferably less than 5% by weight of an aluminosilicate material. If any aluminosilicate material is present, it may be preferred that the particulate composition be dusted with the aluminosilicate material. The particulate component may comprise polymeric binder material, although it is preferred to use as little as possible of it. It may be preferred that the intimate blend comprises less than 25%, preferably less than 10%, more preferably less than 5% by weight, most preferably 0% by weight of ethylene oxide polymers. The particulate component preferably has a weight average particle size of at least 50 microns, preferably 150 microns to 1500 microns, or more preferably 80% by weight of the particles have a particle size no greater than 300 microns. (80% by weight in 48 mesh Tyier sieve) and less than 10% by weight of the particles have a particle size greater than 1180 microns or even 710 microns (in mesh size 24 of Tyier). Preferably, the density of the particulate component is from 380 g / liter to 1500 g / liter, or more preferably from 500 g / liter to 1200 g / liter, more preferably from 550 g / liter to 900 g / liter. The particulate component may be present in the detergent compositions of the invention as a separate particle, or may be further mixed with other ingredients by further agglomeration, compaction, tabletting or extrusion. Said intimate mixture or the particulate component can be prepared by any well-known method to form said detergent particles, for example, by agglomeration, spray drying, roller compaction and / or extrusion, or combinations of these process steps. Said methods can optionally be followed by a drying step or a dusting step and / or a spray step. The granulated material produced is then preferably mixed with the other detergent ingredients. The highly water soluble and / or crystalline layered silicate builder may also be in intimate admixture with other materials, including one or more of the water soluble builders or polymeric compounds such as acrylic acid polymers and / or maleic acid, acids or inorganic salts, including carbonates and sulfates, or small levels of other silicate materials, including amorphous silicate, metasilicates and aluminosilicates, as described herein. It may be preferred that all water-soluble detergency improver or part thereof, in particular, monomeric or oligomeric (poly) carboxylic acid or salt thereof, be in the form of a separate particle, whereby it may be preferred that the The average particle of this builder material is then preferably less than 150 microns, or even less than 100 microns. It may be preferred that part of the water-soluble or partially water-soluble builder is used as a dusting agent, to reduce cake formation of the product, when necessary. In particular, when small amounts of the insoluble builder are present in the compositions, a polycarboxylate polymer such as polymer and copolymer of anhydride or maleic acid and (poly) acrylic acid and its salts, it can be incorporated at a level of 0.5% to 15%, preferably from 1% to 12%, or even from 2% to 8% by weight of the composition. In this way, it may be preferred that the water-insoluble builder and the polymer are not intimately mixed together. The inventors have also found that when a polymeric polycarboxylate is present, it may be preferred that the polymer be comprised in an intimate mixture with other detergent components, preferably in a spray-dried particle, which is prepared mixing first a carbonate salt and the polymer, and then adding and intimately mixing other ingredients.

Insoluble Detergency Meters The compositions of the invention may contain an insoluble builder compound. In general, these are present in amounts of not more than 30% by weight based on the detergent composition as a whole, preferably not greater than 25% by weight. Examples of detergents mainly water-insoluble builders include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(AIO2) z (S¡O2) y], xH2O, wherein z and y are at least 6; the molar ratio of z: y is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is in hydrated form, and is preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but preferably are derived synthetically. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS, and mixtures thereof. Zeolite A has the formula: Na12 [AIO2)? 2 (SiO2) 12] .xH20 where x is from 20 to 30, especially 27. The zeolite of X has the formula Na86 [(AIO2) 86 (SiO2) 106] .276 H20 Another aluminosilicate zeolite preferred is the zeolite MAP builder. Zeolite MAP is described in EP document 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon: aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33, and more preferably within the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicon: aluminum ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect, the zeolite MAP builder has a particle size, expressed as a d50 value of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably 2.5 to 5.0 microns. The d50 value indicates that 50% by weight of the particles have a smaller diameter than that figure. The particle size can be determined, in particular, by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by a laser granulometer. Other methods for establishing d5o values are described in EP 384070A. It has been found that water-insoluble builders, in particular aluminosilicates, contribute to the problems of use general deficiency of the components of the detergent compositions. Therefore, its incorporation into detergent compositions is at low levels, or requires specific processing to allow maximum efficiency of all detergent ingredients in a detergent composition. Thus, in one embodiment of the invention, the alminosilicate builder is preferably in amounts of less than 9% by weight, preferably 6% by weight or 4% by weight. It may even be preferred that substantially no water-insoluble builder is present. Preferably, a detergent composition will contain low levels of amorphous silicates, for example, less than 5% by weight of the amorphous sodium silicate composition, more preferably less than 2% by weight. In a preferred aspect, the detergent composition preferably comprises a builder system comprising less than 30% or even less than 20% or even less than 10% by weight of water-insoluble builder, whereby in the preferred embodiments , the rest of the builder system are water-soluble builders and / or builders partially soluble in water. When present, the aluminosilicate may be contained in a component containing other detergent ingredients, such as surfactants, for example, in a detergent agglomerate, extrudate or blown powder. You can even prefer that substantially no aluminosilicate is present as a separate particulate ingredient (added dry). Also, preferably less than 3% or even less than 1.5% or even less than 0.8% by weight of amorphous silicate is present. When present, the amorphous silicate is preferably contained in a component containing other detergent ingredients, such as surfactant, for example, in a detergent agglomerate, extrudate or blown powder. It may be preferred that substantially no amorphous silicate be present as a separate particulate ingredient. As described above, the detergent compositions of the invention preferably comprise at least one particulate component containing an intimate mixture of one or more of the water-soluble or partially water-soluble builders, and one or more surfactants . Preferably, at least two of said particulate components are present in the detergent composition. In a further embodiment of the invention, it is desired to incorporate a nonsoluble builder, particularly aluminosilicate in amounts of, for example, 5% by weight or more, wherein the compositions also comprise anionic surfactant, for example, in amounts of 5% or more, the detergent composition is preferably such that there are at least two detergent components (i) (n) in the composition, and the degree of mixing (M) of the anionic surfactant and aluminosilicate builder is 0 to OJ, where: and s is the fraction of the anionic surfactant of the composition comprised in component (i); ? is the fraction of the aluminosilicate of the composition comprised in component (i). To achieve a particularly good detergent supply, it is preferred that M be from 0 to 0.6, or even from 0 to 0.5. In said embodiment of the invention, the detergent composition herein comprises at least two multi-ingredient components (ie, no more than 95% by weight of a single ingredient in each component), which comprise an anionic surfactant or an aluminosilicate, or mixtures thereof, whereby if mixtures of aluminosilicate and the surfactant are present in one or more of the components, the degree of mixture M is less than OJ, as defined by the formula. In this way, each component comprises all the aluminosilicate or part thereof, all the anionic surfactant or part thereof, or mixtures thereof, provided that M is from 0 to 0J. The components together comprise the aluminosilicate builder at a level of at least 5% by weight of the composition, and the anionic surfactant at a level of at least 5% by weight of the composition. Preferably, the components comprise the aluminosilicate at a level of at least 7%, or more preferably at least less 10%, or even 15% by weight of the composition. Depending on the precise formulation of the composition and the conditions of use, the compositions of the invention may comprise higher levels of aluminosilicate, such as more than 20% or even more than 25%, as long as they provide an improved supply of the laundry detergent. Preferably, at least 7% or more preferably at least 10% or even at least 12% by weight of the anionic surfactant composition is present in the components. Depending on the precise formulation of the composition and the conditions of use, it may be preferred to have anionic surfactant levels of 18% by weight of the composition, or more. Said components are prepared as described above, by any granulation method such as agglomeration, co-compaction, spray drying or extrusion.

Effervescent System Any effervescent system known in the art can be used in the detergent compositions of the invention. A preferred effervescent system for incorporation into the practice of the invention comprises an acid source, capable of reacting with an alkaline source in the presence of water to produce a gas. Preferably, when the effervescent system comprises two or more reagents, these will be provided in an intimate mixture as a effervescent component. More preferably, the effervescent component comprises an intimate mixture of substantially anhydrous stabilizing agent with acidic and alkaline reagents. The acid source component can be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. Preferably, the acid source component comprises an organic acid. The acid source is preferably substantially anhydrous or non-hygroscopic, and the acid is preferably soluble in water. It may be preferred that the acid source be excessively dried. Suitable acid source components include citric, malic, maleic, fumaric, aspartic, glutaric, tartaric, succinic or adipic acid, monosodium phosphate, boric acid, or derivatives thereof. Citric, maleic or malic acids are especially preferred. More preferably, the acid source provides acidic compounds having an average particle size in the range of about 75 microns to 1180 microns, more preferably 150 microns to about 710 microns, calculated by sieving a sample of the source of acidity in a series of Tyier sieves. As described above, the effervescence system preferably comprises an alkaline source; however, for the purposes of the invention, it should be understood that the alkaline source may be part of the effervescent particle, or may be part of the composition of cleaning comprising the particle, or it may be present in the wash solution, to which the particle or cleaning composition is added. Any alkaline source that has the ability to react with the acid source to produce a gas may be present in the particle, which may be any gas known in the art, including nitrogen, oxygen and gaseous carbon dioxide. Preferred may be the perhydrate bleaches, including perborate and silicate material. The alkaline source is preferably substantially anhydrous or non-hygroscopic. It may be preferred that the alkaline source be excessively dried. Preferably, this gas is carbon dioxide, and therefore the alkaline source is preferably a carbonate source, which can be any carbonate source known in the art. In a preferred embodiment, the carbonate source is a carbonate salt. Examples of preferred carbonates are the alkali metal and alkaline earth metal carbonates, including sodium or potassium carbonate, bicarbonate and sesquicarbonate, and any mixture thereof with ultrafine calcium carbonate, as described in the German patent application. No. 2,321, 001, published November 15, 1973. Salts of alkali metal percarbonate are also suitable sources of carbonate species, which may be present in combination with one or more other carbonate sources. The carbonate and bicarbonate preferably have an amorphous structure. The carbonate and / or bicarbonate can be coated with materials from coating. It may be preferred that the carbonate and bicarbonate particles have an average particle size of 75 microns or preferably 150 μm or greater, more preferably 250 μm or greater, preferably 500 μm or greater. It may be preferred that the carbonate salt be such that less than 20% (by weight) of the particles have a particle size of less than 500 μm, which is calculated by sieving a carbonate or bicarbonate sample in a series of Tyier sieves. Alternatively or in addition to the above carbonate salt, it may be preferred that less than 60% or even 25% of the particles have a particle size smaller than 150 μm, while less than 5% have a larger particle size than 1.18 mm, more preferably less than 20% have a particle size greater than 212 μm, which is calculated by sieving a carbonate or bicarbonate sample in a series of Tyier sieves. The molecular ratio of the acid source: alkaline source present in the core of the particle is preferably from 50: 1 to 1: 50, more preferably from 20: 1 to 1: 20, most preferably from 10: 1 to 1: 10, more preferably from 5: 1 to 1: 3, more preferably from 3: 1 to 1: 2, most preferably from 2: 1 to 1: 2.

Stabilizing agent Preferred stabilizing agents are substantially anhydrous stabilizing agents. The stabilizing agent may comprise one or more components. It may be preferred that the agent of Stabilization comprises compounds that are, at least partially, soluble in water. Preferably, the stabilizing agent is solid under normal storage conditions, for example, the component preferably has a melting point greater than 30 ° C, more preferably greater than 45 ° C, or even more preferably greater than 50 ° C, and it may be preferred that the stabilizing agent be such that it rapidly forms a molten material at more than 80 ° C. Preferably, the stabilizing agent comprises one or more components selected from the group comprising alkoxylated alcohols, including polyethylene glycols and / or propylene glycols and / or alkoxylated alcoholamides, including ethanolamides, alkoxylated ethanolamides, alkoxylated fatty acid amides or ethanolamides, and non-surface active agents. Specific ionics, including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants and specific alkylpolysaccharide surfactants, and mixtures of these compounds, as described herein. Preferably, one or more of the components comprised in the stabilizing agent is a detergent active agent which may contribute to the cleaning performance of the particle or cleaning composition comprising the particle. Substantially anhydrous and highly preferred components in the particle stabilizing agent of the invention are one or more nonionic surfactants selected from the group of nonionic alkoxylated surfactants, including alkoxylated alcohol surfactants, polyhydroxy fatty acid amide surfactants, fatty acid amide surfactants, alkoxylated fatty acid amides, fatty acid alkyl esters and alkyl polysaccharide surfactants , and mixtures thereof, as described hereinafter. In a highly preferred aspect of the invention, the stabilizing agent comprises a mixture of polyhydroxy fatty acid amides and / or polyethylene glycols and / or alkoxylated fatty acid amides and / or condensation products of aliphatic alcohols with 1 to 15 or more. preferably 11, moles of alkylene oxide, as described in more detail below in the description of suitable surfactants. When present, the ratio of the polyhydroxy fatty acid amides: the condensation products of aliphatic alcohols, is preferably from 20: 1 to 1: 20, more preferably from 10: 1 to 1: 10, most preferably from 8: 1 to 1: 8, more preferably from 6: 1 to 1: 6, most preferably from 2: 1 to 1: 3. When present, the ratio of the polyhydroxy fatty acid amides: the polyethylene glycol is preferably from 20: 1 to 1: 8, more preferably from 15: 1 to 1: 3, most preferably from 12: 1 to 1: 1, more preferably from 10: 1 to 1: 1. When present, the ratio of the polyhydroxy fatty acid amides: the alkoxylated fatty acid amides is preferably from 20: 1 to 1: 20, more preferably from 15: 1 to 1:10, most preferably from 10: 1 to 1:10.

Suitable Surfactants for Use in the Detergent Composition The detergent compositions of the invention may contain one or more surfactants selected from anionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, or nonionic surfactants as described below, and mixtures thereof. A typical listing of these surfactants is given in U.S.P. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Other examples are given in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217, issued to Murphy on March 31, 1981. Some examples are given below.

Anionic Surfactant Any anionic surfactant can be incorporated into the compositions of the invention. The anionic surfactant herein preferably comprises at least one sulfate surfactant and / or a sulfonate surfactant, or mixtures thereof. It may be preferred that the anionic surfactant comprises only an alkyl sulfonate surfactant or optionally combined with salts of fatty acids or soap salts thereof. Alternatively, it may be preferred that the composition comprise only a surfactant of alkyl sulfate, but it is preferred herein that at least one branched alkyl surfactant in the middle region of its chain be present, or that at least two alkyl surfactants be present. Depending on the precise formulation of the composition and the use thereof, it may be preferred that the compositions herein comprise a particulate component, as described above, preferably in the form of a flake of an alkyl sulfate or sulphonate surfactant. , preferably an alkylbenzenesulfonate present at a concentration of 85% to 95% of the particle or flake, the remainder being a salt of sulfate and moisture, the particle or flake being mixed with the other components or detergent ingredients. Other possible anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C? 2-C? 8 monoesters). ), sulfosuccinate diesters (especially saturated and unsaturated Cß-Cu diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in, or derived from, tallow oil. Depending on the precise formulation of the composition and the use thereof, it may be preferred that the compositions herein comprising a component containing high levels of an alkyl sulfate or sulfonate surfactant, or mixtures thereof, preferably an alkylbenzene sulfonate, intimately mixed with a sulfate salt and moisture. For example, said component comprises from 85% to 95% of an anionic sulfate or sulfonate surfactant, and from 15% to 5% of sulfate salt, and moisture. Said component can be in the form of a flake, which can be mixed or added dry to the other components of the detergent composition herein.

Sulfonate Anionic Surfactant The sulfonic anionic surfactants according to the invention include the salts of linear or branched C5-C20 alkylbenzene sulphonates, alkyl ester sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, polycarboxylic acids sulfonates, and any mixture thereof. Highly preferred is a linear C12-C16 alkylbenzene sulfonate. The preferred salts are sodium and potassium salts. The alkyl ester sulphonate surfactants are also suitable for the invention, preferably those of the formula: R 1 -CH (S03M) - (A) x -C (O) -OR 2 wherein R 1 is a C 6 -C 22 hydrocarbyl, R2 is a Ci-Cß alkyl, A is a C6-C22 alkylene II, alkenylene, x is 0 or 1, and M is a cation. The counter ion M is preferably sodium, potassium or ammonium.

The alkyl ester sulphonate surfactant is preferably an alpha-sulfo alkyl ester of the above formula, wherein x is 0. Preferably, R 1 is an alkyl or alkenyl group of 10 to 22, preferably 16 carbon atoms, and x it is preferably 0. R2 is preferably ethyl, or more preferably methyl. It may be preferred that the R 1 of the ester is derived from unsaturated fatty acids, preferably with 1, 2 or 3 double bonds. It may also be preferred that R1 of the ester is derived from a naturally occurring fatty acid, preferably palmitic acid or stearic acid, or mixtures thereof.

Anionic Alkyl Sulfate Surfactant The present anionic sulfate surfactant includes linear and branched alkyl and secondary alkylsulfates and disulphates, alkyl ethoxy sulfates having an average ethoxylation number of 3 or less, fatty oleoyl glycerol sulfates, ether sulfate ethylene of alkylphenol, the acyl-N- (C1-C4 alkyl) and -N- (hydroxyalkyl of C? -C2) glucamine sulfates, and sulfates of alkylpolysaccharides. The primary alkyl sulfate surfactants are preferably selected from the linear and branched primary C 0 -C 18 alkyl sulfates, more preferably the straight or branched chain alkyl sulfates of C 11 -C 15, or more preferably the C straight chain alkyl sulphates. 2-C? 4.

Preferred secondary alkyl sulfate surfactants they are of the formula: R3-CH (S04M) -R4 wherein R3 is a C8-C2o hydrocarbyl, R4 is a hydrocarbyl, and M is a cation. The alkyl ethoxy sulfate surfactants are selected from preference of the group consisting of C-io-C-iß alkyl sulphates, which have been ethoxylated with 0.5 to 3 moles of ethylene oxide per molecule. More preferably, the alkyletoxisulfate surfactant is a Cu-Cia alkyl sulfate, more preferably Cn-C 5, which has been ethoxylated with 0.5 to 3, preferably 1 to 3, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention uses mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. The preferred salts are the sodium and potassium salts.

Branched anionic surfactants in the middle region of its chain The primary branched alkyl chain sulfate active agents in the middle region of its chain preferred for use herein are of the formula: R R1 R2 I I I CH3CH2 (CH2) CH (CH2) CH (CH2) CH (CH2) OS03M These surfactants have a linear primary alkyl sulfate chain base structure (ie, the longest linear carbon chain that includes the sulfated carbon atom), which preferably comprises from 12 to 19 carbon atoms, and their portions of branched primary alkyl preferably comprise a total of at least 14, and preferably not more than 20, carbon atoms. In the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl portions is preferably within the range of more than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one primary branched alkyl sulfate surfactant having a longer linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and The total number of carbon atoms, including the branch, must be at least 14 and, moreover, the total average number of carbon atoms for the branched primary alkyl portion is within the range of more than 14.5 to about 17.5. R, R1 and R2 are each independently selected from hydrogen and C3 alkyl group (preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided that R, R1 and R2 do not be all hydrogen. Also, when z is 1, at least R or R1 is not hydrogen.

M is hydrogen or a cation that forms salts, depending on the synthesis method; w is an integer from 0 to 13, x is an integer from 0 to 13, and is an integer from 0 to 13, z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14.

A branched primary alkyl sulfate surfactant in the middle region of its preferred chain is a primary alkylsulphate surfactant having 16 carbon atoms in total having 13 carbon atoms in the base structure, and having 1, 2 or 3 units of branching (ie, R, R1 and / or R2) of a total of 3 carbon atoms (whereby, in this manner, the total number of carbon atoms is at least 16). The preferred branching units can be a propyl branching unit or three methyl branching units. Other preferred surfactants are branched primary alkyl sulphates having the formula: R1 R2 I I CH3CH2 (CH2)? CH (CH2) and CH (CH2) zOS03M wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the total average number of carbon atoms in the branched primary alkyl portions having the formula above, is within the range of more than 14.5 to about 17.5; R1 and R2 are each independently hydrogen or C? -C3 alkyl; M is a cation soluble in water; x is from 0 to 11; and is from 0 to 11; z is at least 2; and x + y + z is from 9 to 13; provided that R1 and R2 are not both hydrogen.

Dianionic surfactants The dianionic surfactants are also anionic surfactants useful in the present invention, in particular those of the formula: wherein R is an optionally substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length of Ci to C28, preferably of C3 to C24, more preferably of C8 to C2o, or hydrogen; A and B are independently selected from the alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amidoalkylene groups of chain length from Ci to C28, preferably from Ci to C5, more preferably C1 or C2, or a covalent bond, and preferably A and B contain in total at least 2 atoms; A, B and R contain in total from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group comprising carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably; and M is a cationic portion, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ion.

The most preferred dianionic surfactant has the formula given above, wherein R is an alkyl group of chain length from C to C, A and B are independently Ci or C2, X and Y are sulfate groups, and M is a potassium ion. , ammonium or sodium.

Preferred dianionic surfactants include herein: (a) 3-disulfate compounds, preferably straight or branched chain or C3-C23 alkyl or alkenyldisulfates (ie, the total number of carbon atoms in the molecule), more preferably having the formula: wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C to about C2o; (b) 1,4-disulfate compounds, preferably straight or branched chain alkyl or alkenyldisulfates of 1.4 C8-C22, more preferably having the formula: wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C-? 8; Preferred R is selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, haxadecyl, octadecyl, and mixtures thereof; Y (c) 1,5-disulfate compounds, preferably straight or branched chain alkyl or alkenyldisulfates of 1.5 C9-C23, more preferably having the formula: oscyivr wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C18. It may be preferred that the dianionic surfactants of the invention are alkoxylated dianionic surfactants. The alkoxylated dianionic surfactants of the invention comprise a structural backbone of at least five carbon atoms, to which two anionic substituent groups separated by at least three atoms are attached. At least one of said anionic substituent groups is a sulfate or sulfonate group bonded to alkoxy. Said structural backbone may comprise, for example, any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide. Preferred alkoxy portions are ethoxy, propoxy, and combinations thereof.

The structural skeleton preferably comprises from 5 to 32, preferably from 7 to 28., more preferably from 12 to 24 atoms. Preferably, the structural skeleton comprises only carbon-containing groups, and more preferably comprise only hydrocarbyl groups. More preferably, the structural skeleton comprises only straight or branched chain alkyl groups. The structural skeleton is preferably branched. Preferably, at least 10% by weight of the structural backbone is branched, and the branches are preferably 1 to 5, more preferably 1 to 3, most preferably 1 to 2 atoms in length (not including the sulphate or sulfonate group attached to the branch). A preferred alkoxylated dianionic surfactant has the formula: wherein R is an optionally substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length of Ci to C28, preferably C3 to C24, more preferably C8 to C20) or hydrogen; A and B are independently selected from optionally substituted alkyl or alkenyl group of chain length from C1 to C28, preferably from C1 to C5, more preferably C1 or C2, or a covalent bond; EO / PO are selected alkoxy portions of ethoxy, propoxy and mixed ethoxy / propoxy groups, wherein n and m are independently within the scale of about 0 to about 10, with at least m or n being at least 1; A and B contain a total of 2 atoms, A, B, and R contain a total of 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group; and M is a cationic portion, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ion. The most preferred alkoxylated dianionic surfactant has the formula described above, wherein R is an alkyl group of chain length from Ci to C-is, A and B are independently Ci or C2, n and m are both 1, X and Y are groups sulfate, and M is a potassium, ammonium or sodium ion. Preferred alkoxylated dianionic surfactants herein include: ethoxylated and / or propoxylated disulfate compounds, preferably ethoxylated and / or straight or branched chain alkyl or alkenyl disulfates of C 10 -C 2, more preferably having the formulas: wherein R is a branched or chain-branched alkyl or alkenyl group of chain length from about C6 to about C-? 8; EO / PO are selected alkoxy portions of ethoxy, propoxy and mixed ethoxy / propoxy groups; and n and m they are independently within the range of from 0 to about 10 (preferably from about 0 to about 5), wherein at least m or n is 1.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ("alkylcarboxyls"), especially certain secondary soaps, as described herein. Suitable alkyl ethoxy carboxylates include those having the formula RO (CH2CH20) xCH2C00-M +, wherein R is an alkyl group of C6 to Cie, x ranges from 0 to 10, and the distribution of ethoxylate is such that, on a by weight, the amount of material where x is 0, is less than 20%, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO- (CHRrCHR2-0) -R3, wherein R is an alkyl group of C6 to C-? 8, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit attached to a secondary carbon. Soap surfactants Preferred by their use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-etl-1-decanoic acid, 2-propyl acid -1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2COOM, wherein R is a linear or branched alkyl or alkenyl group of C5-C? , R1 is an alkyl group of CrC, and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Non-ionic alkoxylated surfactants When nonionic surfactants are present, it may be preferred that the components of the compositions herein are free of nonionic alkoxylated alcohol surfactants or sprayed. It has been found that the supply of the composition to the wash water can be improved, and that the cake formation of the product can be reduced. It may be preferred that the composition comprises a non-ionic surfactant that is solid at temperatures below 30 ° C or even 40 ° C, preferably present in an intimate mixture with other ingredients. Essentially any alkoxylated nonionic surfactant may also be comprised in the detergent compositions of the invention. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the condensate classes of nonionic alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylated / propoxylated condensates with propylene glycol, and the nonionic ethoxylate condensation products. with propylene oxide / ethylenediamine adducts. Highly preferred are non-ionic alkoxylated alcohol surfactants, the condensation products of aliphatic alcohols being 1 to 75 moles of alkylene oxide, in particular about 50 or 1 to 15 moles, preferably up to 11 moles, particularly sodium oxide. ethylene and / or propylene oxide, are highly preferred nonionic surfactants in the anhydrous component of the particles of the invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing 8 to 20 carbon atoms, with 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.

Nonionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides are highly preferred nonionic surfactants for use in the invention, in particular those having the structural formula R2-CONR1Z wherein: R1 is H, hydrocarbyl Cpβ, preferably C 4, 2-hydroxyethyl; 2-hydroxypropyl; ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 6 alkyl, more preferably Ci or C 2 alkyl, most preferably Ci alkyl (ie, methyl); and R2 is a C5-C3-? hydrocarbyl, preferably straight-chain C5-C19 or C-C9 alkyl or alkenyl, more preferably straight-chain C9-C? 7 alkyl or alkenyl, most preferably alkyl or C11-C17 straight chain alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Preferably, Z will be derived from a reducing sugar in a reductive amination reaction; more preferably, Z is a glycityl. A highly preferred non-ionic polyhydroxy fatty acid amide surfactant for use herein, is an alkyl N-methyl glucamide of d2-C? 4, C? 5-C17 and / or C- | 6-C? . It may be particularly that mixtures of an alkyl N-methyl glucamide of C? 2-C? S and a condensation product of an alcohol have a alkyl group containing from 8 to 20 carbon atoms with 2 to 9 moles, and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol. The polyhydroxy fatty acid amide can be prepared by any suitable method. A particularly preferred process is described in detail in WO 9206984.

Nonionic surfactant of fatty acid amide The fatty acid amide surfactants or alkoxylated fatty acid amides include those having the formula R6CON (R7) (R8), wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms, or even from 11 to 13 carbon atoms, and R7 and R8 are each individually selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H O) xH, wherein x is on the scale of 1 to 11, preferably 1 to 7, more preferably 1 to 5, wherein one may prefer that R7 is different from R8, one having x that is 1 or 2, one having x that is from 3 to 11, or preferably 5.

Nonionic Surfactant of Aliphatic Fatty Acid Esters Alkyl esters of fatty acids include those having the formula: R9COO (R10), wherein R9 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms. carbon or even 11 to 13 atoms of carbon, and R10 is an alkyl of CrC4, hydroxyalkyl of C C4, or - (C2H4O) xH, wherein x is on a scale of 1 to 11, preferably 1 to 7, more preferably 1 to 5, wherein it may be preferred that R10 is a methyl or ethyl group.

Non-ionic surfactant of alkylpolysaccharide The alkyl polysaccharides can also be included in the anhydrous material of the particle of the invention, as described in the patent of E.U.A. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, for example a polyglucoside, hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula: R20 (CnH2nO) t (glucosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Cationic Surfactant Another preferred component of the compositions of the invention is a cationic surfactant, which is preferably present at a level from 0.1% to 60% by weight of the composition, more preferably from 0.4% to 20%, most preferably from 0.5% to 5% by weight of the composition. When present, the ratio of the anionic surfactant: the cationic surfactant is preferably from 25: 1 to 1: 3, more preferably from 15: 1 to 1: 1, most preferably from 10: 1 to 1: 1. The ratio of cationic surfactant: the stabilizing agent is preferably from 1: 30 to 20: 1, more preferably from 1: 20 to 10: 1. Preferably, the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, bis-alkoxylated amine surfactants, and mixtures thereof.

Cationic monoalkoxylated amine cationic surfactants The optional monoalkoxylated amine cationic surfactant for use herein has the general formula: wherein R1 is an alkyl or alkenyl portion containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, more preferably from about 6 to about 11 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R 4 is selected from hydrogen (preferred), methyl and ethyl, X "is an anion such as chloride, bromide, methylisulfate, sulfate, or the like, which provides electrical neutrality; A is selected from CrC 4 alkoxy, especially ethoxy (i.e. -CH2CH2O-), propoxy, butoxy, and mixtures thereof, and p is from 1 to about 30, preferably from 1 to about 15, more preferably from 1 to about 8. The highly preferred mono-alkoxylated amine cationic surfactants for use in the present, they are of the formula: wherein R 1 is C 1 -Cis hydrocarbyl, and mixtures thereof, preferably C 6 -C alkyl, especially C 6 -C n, preferably C 8 and C 1 0 alkyl, and X is any convenient anion that provides charge balance, preferably chloride or bromide. As described above, compounds of the above type include those in which the ethoxy (CH 2 CH 2 O) (EO) units are replaced by butoxy, isopropoxy units [CH (CH 3) CH 2 Oj and [CH 2 CH (CH 30] (i-Pr) or n units -propoxy (Pr), or mixtures of units EO and / or Pr and / or i-Pr.

Cationic bis-alkoxylated amine surfactant The bis-alkoxylated amine surfactant for use herein has the general formula: wherein R1 is an alkyl or alkenyl portion containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, more preferably from 6 to about 11, most preferably from about 8 to about 10. carbon atoms; R2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chloride, bromide, methylisulfate, sulfate or the like, sufficient to provide electrical neutrality.A and A 'can vary independently and each is selected from CC alkoxy, especially ethoxy, (ie -CH2CH2O-) , propoxy, butoxy and mixtures thereof, p is from 1 to about 30, preferably from 1 to about 4 and q is from 1 to about 30, preferably from 1 to about 4, and most preferred still both p and q are 1. The highly preferred cationic bis-alkoxylated amine surfactants for use in the present invention are of the formula wherein R 1 is C 6 -C 8 hydrocarbyl and mixtures thereof, preferably C 6 alkyl, Cs, Cι, C 2, C and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic structure of bis-alkoxylated amine indicated above, since in a preferred compound R1 is obtained from the alkyl fractions of C? 2-C fatty acids (coconut), R2 is methyl and ApR3 and A'qR4 they are each monoethoxy. Other cationic bis-alkoxylated amine based cationic surfactants useful in the present invention include compounds of the formula: wherein R1 is Cs-Cis hydrocarbyl, preferably C6-C4 alkyl, independently p is 1 to about 3 and q is from 1 to about 3, R2 is CrC3 alkyl, preferably methyl and X is an anion , especially chloride or bromide. Other compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced with units butoxy (Bu), sopropoxy [CH (CH3) CH20] and units (i-Pr) [CH2CH (CH30)] or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units .

Amphoteric Surfactant Amphoteric surfactants suitable for use in the present invention include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) ΔN (R5) 2f in which R4 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, which contains to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Preferred are the alkyl dimethylamine oxide of C? NC- | 8 and the acylamido-alkyldimethylamine oxide of C- | o- i 8- A suitable example of an alkylalfodicarboxylic acid is Miranol (TM) C2M Conc., Manufactured by Miranol, Inc. , Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the particle of the invention or compositions which they contain the particle of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO "in which R is a C6-C- | 8 hydrocarbyl group-each R1 is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group The preferred betaines are the betaines of dimethyl ammonium hexanoate of C12-C18 and acetylamidopropane (or ethane) dimethyl (or diethyl) betaines of C? oC- | 8- The complex beta-2 surfactants they are also suitable for use in the present invention.

Additional Detergent Ingredients The detergent composition of the invention may comprise any additional detersive active or ingredient known in the art. The exact nature of these additional components, and the levels of incorporation thereof will depend on the physical form of the composition, and the exact nature of the washing operation for which it is being used.

Other preferred ingredients comprise a perfume, brightener or colorant or mixtures thereof, which may be sprayed onto the particular component herein. The compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, builders, chelators, (additional) alkalinity sources, organic polymeric compounds, enzymes, brighteners, suds suppressors, soap dispersants, lime, agents for suspending and anti-redeposition of dirt and corrosion inhibitors.

Heavy metal sequestrant Heavy metal sequestrants are additional ingredients useful herein. By "heavy metal ion sequestrant" is meant herein a component that acts to sequester (chelate) heavy metal. These components may also have calcium and magnesium chelating ability, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level from 0.005% to 10%, preferably from 0.1% to 5%, more preferred from 0.25% to 7.5% and even more preferred from 0.3% to 2% by weight of the compositions Heavy metal ion sequestrants suitable for use in the present invention include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), ethylenediaminetri (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate, 1,1-hydroxyethane diphosphonic acid and 1,1-hydroxyethanedimethylenephosphonic acid. Another heavy metal ion sequestrant suitable for use in the present invention includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene diamine tetraacetic acid, ethylene diamine disuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamine diuccinic acid or any of the salts thereof. Other heavy metal ion sequestrants suitable for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryliminodiacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The binders of β-alanine-N, N'-diacetic acid, aspartic acid - N, N'-diacetic acid, aspartic acid - N-monoacetic acid and minodisuccinic acid described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino-based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528, 859 describes a suitable alkyliminodiacetic acid sequestrant. The dipicolinic acid and 2-phosphonobutane-1, 2,4-tricarboxylic acid are also suitable. In addition, glycinamide-N-disuccinic acid (GADS), ethylene diamine N, N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are suitable. Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N'-disuccinic acid (EDDS) and 1,1-hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. thereof.

Perhydrate bleaches Preferably the detergent compositions of the invention comprise oxygen bleach, preferably comprising a source of hydrogen peroxide and a bleach precursor or activator. Because the present invention improves the supply of product to the wash, it increases the efficiency and reduces the risk of damage to the fabrics by bleach present in the detergent. A preferred source of hydrogen peroxide is a perhydrate bleach, such as metal peborates, most preferably metal percarbonates, particularly sodium salts. He Perborate can be mono or tetrahydrated. Sodium percarbonate has the formula corresponding to 2Na2C? 3.3H2? 2, and is commercially available as a crystalline solid. In particular, the percarbonate salts are preferably coated. Suitable coating agents are known in the art, and include silicates, magnesium salts and carbonate salts. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions of the present invention.

Organic Peroxyacid Bleach System A preferred feature of the composition herein is an organic peroxyacid bleach system. In a preferred embodiment the bleaching system contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as perborate bleach of the claimed invention. In an alternative preferred embodiment a preformed organic peroxyacid is directly incorporated into the composition. Compositions containing mixtures of a source of hydrogen peroxide and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also contemplated.

Peroxyacid-based bleach precursor Peroxyacid-based bleach precursors are compounds that can react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Peroxyacid bleach precursors can generally be represented as: O II X-C- L wherein L is a leaving group and X is essentially any functionality, such that in perhydrolysis the structure of the peroxyacid produced is: O II X-C-OOH The peroxyacid bleach precursor compounds are preferably incorporated at a level of 0.5 to 20% by weight, most preferably from 1% to 15% by weight, still most preferably from 1.5% to 10% by weight of the detergent compositions. Suitable peroxy acid-based bleach precursor compounds typically contain one or more N-acyl or O-acyl groups, whose precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. The esters Suitable are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups The leaving group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (for example, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize to be used in a bleaching composition. The preferred L groups are selected from the group consisting of: R3 and I I - O- CH = C- CH = CH2 - O- CH = C- CH = CH2 R3 0 and II 1 - O- C 1 = CHR A4. and -N- S- CH- -R4 l II R3 0 and mixtures thereof, in which R1 is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain that contains 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a group solubilizer. Any of R1, R3 and R4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred solubilizing groups are -S? 3"M +, -C? 2" M +, - S? 4"M +, -N + (R3) 4X" and 0 < -N (R3) 3 and most preferably -S? 3"M + and -C? 2" M +, in which R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X is a halide, hydroxide, methylisulfate or acetate anion.

Precursors of bleach based on alkylpercarboxylic acid The precursors of bleach based on alkylpercarboxylic acid form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarboxylic acid bleach precursors of the imide type include the tetraacetylated N- .NN ^ I alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the algerylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particulate material of the present invention, but is preferably present in the detergent composition, which contains the particulate material.

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

Amide-substituted alkylperoxy acid precursors Amide-substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: R1- C-N-R2- C- L R1- N-C-R2- C- L II I c II II II OR R5 O or R5 0 O wherein R ^ is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Precursor of perbenzoic acid The perbenzoic acid precursor compounds provide perbenzoic acid in the perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Preformed Organic Peroxyacid The detergent composition may comprise, in addition to, or as an alternative to, a precursor bleach precursor compound based on organic peroxyacid, a preformed organic peroxyacid, typically at a level of 1% to 15% by weight, more preferably 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R1- C-N- R2-C-OOH II I = II O R5 O or R1- N-C-R2-C-OOH Ul II R5 O O wherein R1 is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl that contains from 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include diacyl and tetra-acylperoxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Also suitable in the present invention are monoperazelaic and diperazelaic acid, monoperbrasyl and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Enzyme Another preferred ingredient to be used herein is one or more additional enzymes. Additional preferred enzyme materials include lipases, cutinases, amylases, neutral or alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated in detergent compositions. Suitable enzymes are exemplified in the patents of E.U.A. Nos. 3,519,570 and 3,533,139.

Organic polymeric compound Organic polymeric compounds are preferred additional components of the compositions herein.

The term "organic polymeric compound" refers essentially to any organic polymeric compound commonly used as a dispersant, anti-redeposition agents and soil suspension in detergent compositions, including any of the high molecular weight organic polymer compounds described as clay flocculating agents in the present invention, including ethoxylated quaternized (poly) amine anti-redeposition / dirt removal agent. An organic polymeric compound is incorporated into the detergent compositions at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions. Examples of organic polymeric compounds include the organic homo- or co-polymeric polycarboxylic acids soluble in water or their salts wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are described in GB-A-1, 596,756. Examples of such salts are the polyacrylates of MW 1000-5000 and their copolymers with maleic anhydride, said copolymers having a molecular weight of 2,000 to 100,000, especially 40,000 to 80,000. Polyamino compounds are useful in the present invention including those aspartic acid derivatives such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Also suitable for incorporating into the compositions of the present invention are terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional and useful organic polymeric compounds are the polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and more preferably around 4000. The highly preferred polymeric components herein are cotton and cotton soil release polymers. no cotton according to the US patent 4,968,451, Scheibel et al., And patent of E.U.A. 5,415,807, Gosselink et al., And in particular in accordance with US application No. 60/051517. Another organic compound, which is a preferred clay dispersing agent / anti-redeposition agent, for use herein, may be ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (e.g. , ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b = 0), n is at least 16, with a typical scale of 20 to 35; for cationic diamines (b = 1), n is at least 12 with a typical scale of 12 to 42. Other dispersing agents / anti-redeposition agents to be used herein are described in EP-B-011965 and US 4,659,802 and EUA 4,664,848.

Foam suppressing system The detergent compositions of the invention, when formulated for use in machine wash compositions, may comprise a foam suppression system at a level of from 0.01% to 15%, preferably from 0.02% to 10%, still most preferably 0.05 to 3% by weight of the composition. The foam suppressor systems suitable for use in the present invention can comprise essentially any known antifoam compound, including, for example, silicone-based antifoam compounds and 2-alkyl alkanol antifoaming compounds. The term "antifoam compound" in the present invention refers to any compound or mixtures of compounds that act to reduce the foaming or sudsing produced by a solution of a detergent composition, particularly when stirring that solution. Particularly preferred defoaming compounds for use herein are silicone anti-foaming compounds defined herein as any defoaming compound including a silicone component. Said silicone anti-foaming compounds also typically contain a silica component. The term "silicone" as used herein, and in industry generally, comprises a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoaming compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable defoaming compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 atoms. of carbon. Suitable salts include the alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts. Other suitable defoaming compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of C? B-C or (eg, stearone) amino triazines N -alkylated such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamin-clortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms, propylene oxide, amide of bis stearic acid and di-alkali metal phosphates of monostearyl (eg, sodium, potassium, lithium) and phosphate esters. A preferred foam suppression system comprises: (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersant compound, most preferably comprising a silicone glycol bent copolymer having a content of polyoxyalkylene of 72-78% and a ratio of ethylene oxide to propylene oxide of about 1: 0.9 to 1: 1.1, at a level of 0.5% to 10%, preferably 1% to 10% by weight; A particularly preferred silicone glycol bent copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising a C16-C18 ethoxylated alcohol with an ethoxylation degree of from 5 to 50, preferably from 8 to 15, at a level of from 5 to 80%, preferably from 10% to 70%, by weight. A supremely preferred particulate foam suppression system is disclosed in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C. , wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 describes other preferred particle foam suppression systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof , with a melting point of around 45 ° C to 80 ° C. Other highly preferred foam suppression systems comprise polydimethylsiloxane or silicone blends, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of secular and acrylic acid.

Polymeric Dye Transfer Inhibitory Agents The compositions of the present invention may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be cross-linked polymers.

Optical brightener The compositions of the present invention also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as is known in the art.

Polymeric dirt-releasing agent Polymeric soil-releasing agents, hereinafter "SRA", may optionally be employed in the compositions herein. If they are used, the SRAs will generally include about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions. Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain adhered thereto through the conclusion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This allows spots that occur subsequent to treatment with the SRA to be more easily cleaned in subsequent washing procedures. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that involve at least one transesterification / oligomerization, often with a metal catalyst such as titanium (IV) alkoxide. Said esters can be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely intertwined general structure. Suitable SRAs include a sulphonated product of a substantially linear ester oligomer consisting of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and of sulfonated end portions obtained from allyl covalently attached to the base structure, for example as describes in the USA patent No. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Said oligomeric esters can be prepared: a) ethoxylating allyl alcohol; b) reacting the product of a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-step transesterification / oligomerization process; and c) reacting the product of b) with sodium metabisulfite in water. Other SRAs include polyesters of 1,2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,711, 730, of December 8, 1987 to Gosselink and others, for example those produced by the transesterification / oligomerization of the methyl ether of poly (ethylene glycol), DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRAs include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721, 580, from January 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and sodium 3,6-dioxa-8-hydroxyoctanesulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. No. 4,702,857, from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG blocked-methyl (Me), or a combination of DMT, EG and / or PG, PEG blocked-Me and Na-dimethyl-5-sulfoisophthalate; and the esters of terephthalate blocked at the anionic ends, especially sulfoaroyl of the patent E.U.A. No. 4,877,896 of October 31, 1989 to Maldonado Gosselink and others, the latter being typical SRAs for use in fabric conditioning and laundry products. An example of these is an ester composition made of monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally, but preferably also comprising PEG, e.g., PEG 3400. SRAs also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see U.S. Pat. No. 3,959,230 to Hays of May 25, 1976 and the patent E.U.A. No. 3,893,929 to Basadur, July 8, 1975; cellulose derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; C1-C4 alkylcelluloses and hydroxyalkylcelluloses of CA, see US Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al., And methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity from about 80 to about 120 centipoises measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRAs include: (I) non-ionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see E.U.A. 4,201, 824, Violland et al. and E.U.A. 4,240,918 Lagasse et al .; and (II) SRA with carboxylate end groups made by adding trimellitic anhydride to known SRAs to convert terminal hydroxyl groups into trimethylate esters. With the right selection of catalyst, the trimellitic anhydride forms bonds at the polymer terminals through a carboxylic acid ester isolated from trimellitic anhydride instead of opening the anhydride linkage. Anionic or nonionic SRAs can be used as starting materials with the proviso that they have hydroxyl end groups that can be esterified. See E.U.A 4,525,524 Tung et al. Other classes include: (lll) SRA based on anionic terephthalate of the variety bound to urethane, see E.U.A. 4,201, 824, Violland et al.

Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, specks, colors or dyes, filler salts, with sodium sulfate being a preferred filler salt. In addition, minor amounts (eg, less than about 20% by weight) of neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, may be present. antioxidants, bactericides and colorants, such as those described in the US patent 4,285,841 to Barrat et al., Issued August 25, 1981 (incorporated herein by reference). Highly preferred are the encapsulated perfumes, preferably comprising a starch encapsulate.

In the compositions of the invention, it is preferable that when the dyes and / or perfumes are sprayed on the other component, the component does not comprise sprinkled nonionic alkoxylated alcohol surfactant.

Form of the compositions The composition of the invention can be made through a variety of methods involving the mixing of ingredients, including dry blending, compaction such as agglomeration, extrusion, tableting, or spray drying of the various compounds contained therein. detergent component, or mixtures of these techniques, by means of which the components of the present invention can be made, for example by compaction, including extrusion and agglomeration, or spray drying. The compositions herein can take a variety of physical solid forms including forms such as tablets, chips, lozenges and bars, and preferably the composition is in the form of granules or a tablet. The compositions according to the present invention can be used in or in combination with bleaching additive compositions, for example comprising chlorine bleach.

The compositions preferably have a density of more than 350 gr / liter, most preferably more than 450 gr / liter or even more than 570 gr / liter. The following are examples of detergent compositions according to the invention.

Abbreviations used in the examples In the detergent compositions that are exemplified below, the abbreviated identifications of the components have the following meanings: LAS: Linear sodium alkylbenzene sulfonate of Cn.?3 LAS (I): Flake containing linear sodium alkylbenzenesulfonate of Cn-13 (90%) and sodium sulfate and moisture LAS (II): Linear potassium alkylbenzene sulfonate of Cn-13 MES: a-sulfo methyl ester of C? 8 fatty acid TAS: Sodium alkyl sulfate CxyAS: Sodium alkyl sulfate of C? xC- | and C46SAS: (2,3) Cu-Cie secondary sodium alkyl sulfate CxyEzS: C- | xC- | sodium alkyl sulphate and condensed with z moles of ethylene oxide. CxyEz: Primary alcohol of C- | x-C < | and predominantly linear condensed with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C? 2-C? 4 QAS 1: R2.N + (CH3) 2 (C2H4OH) with R2 = C8-Cn SADS: C? 4 sodium alkyldisulfate -C22 of the formula 2- (R). C4H7.-1, 4- (S04") 2 wherein R = C? 0-C? 8 SADE2S: C-C22 sodium alkyldisulfate of the formula 2- (R) .C H7.-1, 4- (S04") 2 in which R = C oC? 8, condensed with z moles of ethylene oxide APA: Amidopropyl dimethylamine of C8-? 0 Soap: Linear sodium alkylcarboxylate derived from a 80/20 mixture of coconut fatty acids and sebum STS: Sodium toluene sulphonate CFAA: (coco) alkyl (C- | 2-Ci4) -N-methyl glucamide TFAA: N-methyl glucamide of Ci ß- i8 alkyl TPKFA. Whole cut fatty acids of C12-C14 STPP: Tri-poly anhydrous sodium phosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na-12 (Al? 2Si? 2) i2- ^ H2? - which has a primary particle size in the range of 1 to 10 microns (weight expressed on an anhydrous basis) NaSKS-6 (I): Crystalline layered silicate of formula d-Na2Si2? 5 which has an average particle size of 18 microns and by at least 90% by weight with a particle size of less than 65.6 micras NaSKS-6 (II): Crystalline layered silicate of formula d-Na2Si2? 5 which has an average particle size of 18 micras and at least 90 % by weight with a particle size of less than 42.1 microns Citric acid: Anhydrous citric acid Borate: Sodium borate Carbonate: Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm Bicarbonate: Anhydrous sodium bicarbonate with a distribution of particle size between 400 μm and 1200 μm. Silicate: Amorphous sodium silicate (Si? 2: Na2? = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425 μm and 850 μm. MA / AA: Copolymer 1: 4 of maleic / acrylic acid, average molecular weight of about 70,000 MA / AA (1): Copolymer 4: 6 of maleic / acrylic acid, average molecular weight of about 10,000 AA: Sodium polyacrylate polymer of average molecular weight of 4,500 CMC: Sodium carboxymethyl cellulose Cellulose ether: Cellulose methyl ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme, having 3.3% in active enzyme weight, sold by NOVO Industries A / S under the trade name Savinase. Protease I: Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO95 / 10591, sold by Genencor Int. Inc. Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A / S Cellulase: Cellulolytic enzyme, which has 0.23% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Carezyme Amylase: Amylolytic enzyme, which has 1.6% by weight of active enzyme, sold by NOVO Industries AS under the trade name Termamyl 120T Amylase ll Amylolytic enzyme, as described in PCT / EUA9703635 Lipase: Lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries AS under the trade name Lipolase Lipase (I): Lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Ultra Endolasa: Enzyme endoglucanase, which has 1.5% by weight of active enzyme, sold by NOVO Industries A / S. PB4: Sodium perborate tetrahydrate of nominal formula NaB02.3H2O.H2? 2 PB1: Anhydrous sodium perborate with nominal formula NaB? 2.H2? 2 Percarbonate: Anhydrous sodium percarbonate of nominal formula 2Na2C? 3.3H2? 2 DOBS: Decanoiloxybenzenesulfonate in the form of sodium salt: DPDA: Diperoxidodecanoic acid. NOBS: Nonanoiloxybenzenesulfonate in the form of sodium salt.

NACA-OBS: (6-nonamidocaproyl) oxybenzenesulfonate LOBS Dodecanoyloxybenzenesulfonate in the form of sodium salt. DOBS Decanoiloxybenzenesulfonate in the form of sodium salt. DOBA decanoyloxybenzoic acid TAED: Tetraacetylethylenediamine DTPA: Diethylenetriaminpentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060 EDDS: Ethylenediamine-N, N'-disuccinic acid, isomer [S, S] in the form of its sodium salt Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in or transported by soluble polymer or sulfonated aluminophthalocyanine encapsulated or transported by a, soluble polymer Brightener 1: 4,4'-bis (2-sulfoestyryl) biphenyl disodium Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1, 3,5-triazin-2-l) disodium stilbene-2,2'-disulfonate HEDP: 1,1-hydroxydanediphosphonic acid PEGx: Polyethylene glycol with a molecular weight of x (typically 4,000) PEO: Polyethylene oxide, with an average molecular weight of 50,000. TEPAE: Tetraethylenepentamine-ethoxylate. PVI: Polyvinylimidazole, with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA: bis ((C2H5?) (C2H4?) N) (CH3) - N + -C6H12-N + - (CH3) bis ((C2H5?) - (C2H4? N)), where n = from 20 to 30 SRP 1: Anionically blocked polyesters at the ends SRP 2: Poly (short block polymer) 1, 2propylene) diethoxylated terephthalate PEI: Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Silicone Antifoam: Foam controller based on polydimethylsiloxane with siloxane-oxyalkylene copolymer as the dispersing agent with a ratio of said controller to said dispersing agent from 10: 1 to 100: 1 Opacifier: Mono-styrene-latex mixture with aqueous base, sold by BASF Aktiengesellschaft under the trade name Lytron 621 Wax: Paraffin wax EXAMPLE 1 A detergent composition comprising blowing powder, an agglomerate comprising crystalline layered silicate and anionic surfactant, an effervescent particle and dry bleach activator particle, sodium percarbonate, sodium citrate and suds suppressor was formed. The individual particulate materials were prepared and mixed dry together with gentle mixing, for example in a Nautamixer for a period of at least 4 minutes.

Preparation of the blown powder The composition of the final blown powder was as follows: Ingredient% blown powder Linear sodium alkyl sulfonate (LAS) 20 Acrylic / maleic acid copolymer 5 Sodium sulfate 16 Sodium carbonate 31 Sodium citrate 20 Water 8 The blown powder was prepared by a standard spray drying process. The above ingredients were mixed in a suspension with water. The aqueous suspension can be prepared by a batch or continuous procedure. In this case, we used a batch mixer, or "steam jacketed mixer" in which various detergent components were dissolved in, or were suspended with, water to provide a suspension containing 35% water. The water content can vary from about 20% to about 60% by weight of water, preferably from about 30% to about 40% by weight of water. In this example the order of addition of the ingredients to the water to form the aqueous suspension was listed above in the final composition of the blown powder. The aqueous suspension was pumped at high pressure through spray nozzles in a spray-drying tower where the excess water was directed, producing a flowable powder (blown powder). The fine materials were filtered through a mesh.

Preparation of crystalline layered silicate / anionic surfactant particle An agglomerate comprising 70% SKS6 and 30% LAS was prepared by a conventional agglomeration process.

Preparation of the effervescent particle The particles were prepared having the following composition: Ingredient Composition% Malic acid 44 Sodium bicarbonate 40 Sodium carbonate 16 The particle was made through a roller compaction process. The raw materials in the proportions indicated above were fed to a pressure force of 80kN on a Pharmapaktor L200 / 50 P roller, fitted with smooth concave rollers with an installed 0.3 mm axial corrugation. The flakes produced were compacted using a FC200 flake crusher with a selected mesh size to produce the required particle size. The product was filtered to remove fine materials. Those three components were mixed with the additional dry aggregate ingredients listed below, in the listed proportions, to form a detergent composition according to the invention.

Ingredient% in detergent composition Spray drying 42 Bleach activator 3 Sodium percarbonate 15 Sodium citrate 10 SKS6 / LAS granulate 10 Foam suppressor particle 4 (95% PEG, 5% silicone) Effervescent particle 16 EXAMPLE 2 Further examples of detergent compositions of the invention are given as formulations A-D in the following table which also indicates the method of preparation of the examples.

Claims (1)

NOVELTY OF THE INVENTION CLAIMS

1- A solid detergent composition comprising 10 a 60% by weight of a surfactant system and having a maximum Residue Index of 25 and a maximum Secondary Residue Index of 15. 2. The detergent composition according to claim 1, further characterized by having an index of Maximum residue of 20. 3. The detergent composition according to claim 2, further characterized in that it has a maximum Residue index of 15. 4. The detergent composition according to any of the preceding claims, further characterized by having a Secondary Waste Index of 10. The detergent composition according to any of the preceding claims, further characterized in that it comprises a builder system comprising from 60 to 100% by weight of water soluble builders or mixtures of the same. 6. The detergent composition according to any of the preceding claims, further characterized in that it comprises aluminosilicate builder in amounts of less than 9% by weight based on the detergent composition as a whole. 7. The detergent composition according to any of the preceding claims, further characterized in that it comprises amorphous sodium silicate in amounts of less than 5% by weight based on the detergent composition as a whole. 8. The detergent composition according to any of the preceding claims, further characterized in that at least part of the surfactant system is present in the detergent composition as a particulate component comprising an intimate mixture of surfactant with at least part of the detergency builder system. 9. The detergent composition according to any of the preceding claims, further characterized in that it comprises an aluminosilicate builder and anionic surfactant, the detergent composition comprises (n) components (i), n being at least 2, total level of aluminosilicate builder in the detergent composition being at least 5% by weight and the total level of anionic surfactant in the detergent composition being at least 5% by weight, and the degree of mixing (M ) of the anionic surfactant and the aluminosilicate builder is 0 to OJ, M where? ¡n = 1 V (s¡ •? ¡) where s is the fraction of the surfactant anionic composition in component (i) and? is the fraction of the aluminosilicate of the composition in component (i). 10. The detergent composition according to claim 9, further characterized in that M is from 0 to 0.5. 11. The detergent composition according to any of the preceding claims, further characterized in that it comprises a granulate, the granulate comprises from 35 to 68% by weight of crystalline layered silicate, from 32 to 55% by weight of an anionic surfactant and a maximum moisture free content of less than 10% by weight. 12. The detergent composition according to any of the preceding claims, further characterized in that it comprises nonionic surfactant that has been sprayed on preformed particulate materials comprising surfactant and solid carrier material. 13. The detergent composition according to any of the preceding claims, further characterized in that it comprises a cationic surfactant. 14. The detergent composition according to any of the preceding claims, further characterized in that it is substantially free of alkylsulfate surfactant. 15. The detergent composition according to any of the preceding claims, further characterized in that it comprises an effervescent component comprising an intimate mixture of substantially anhydrous stabilizing agent and an effervescent system. 16. The detergent composition according to any of the preceding claims, further characterized in that it comprises a source of percarbonate bleach. 17. The detergent composition according to any of the preceding claims, further characterized in that it is in the form of a detergent tablet. 18. The use of a detergent composition as claimed in any of the preceding claims, in a laundry procedure for laundry.